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Interpol's Forensic Science Review [1 ed.]
 1439826587, 9781439826584

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Interpol Forensic Science Symposium Reports 2007

Editors Niamh Nic Daéid, PhD Centre for Forensic Science University of Strathclyde Glasgow, Scotland Max M. Houck West Virginia University Morgantown, WV, USA

Interpol Forensic Science Symposium Reports 2007

Table of contents iii



Section 1 - Chemical Criminalistics Technical co-ordinator: Prof. Kimmo Himberg, National Institute of Forensic Science, Finland. 2 19 51 70 89



Drugs Toxicology

Chapter 8 Chapter 9

Forensic Audio and Visual Evidence Digital Evidence

Section 4 - Fire, Explosives, and Hazardous Materials Technical co-ordinator: Dr. Niamh Nic Daéid, Centre for Forensic Science, University of Strathclyde, Scotland, UK 415

Chapter 10

455 529

Chapter 11 Chapter 12


Chapter 13

Hazardous Materials: Chemical Biological Radiological and Nuclear Environmental forensic science Analysis and Detection of Explosives and Explosives Residues Fire Scene and Fire Debris Analysis

Section 5 - Individual Evidence Technical co-ordinator: Mr Kevin O’Sullivan, Forensic Science Service, UK 591 673 695


Chapter 6 Chapter 7

Section 3 - Electronic Evidence Technical co-ordinator: Dr. Peter Pfefferli, Kantonspolizei, Zurich, Switzerland 353 393


The Forensic Examination of Fibres Firearms The Forensic Examination of Marks Forensic Geology Paint and Glass

Section 2 - Drugs and Toxicology Technical co-ordinator: Mr. Thomas Janovsky, Drug Enforcement Agency, USA 153 281


Chapter 1 Chapter 2 Chapter 3 Chapter 4 Chapter 5

Chapter 14 Chapter 15 Chapter 16

Biological Evidence and Forensic DNA Profiling Questioned Documents Fingermarks, Bitemarks and Other Impressions (Barefoot, Ears, Lips)



Interpol Forensic Science Symposium Reports 2007

Preface The Interpol Forensic Science Symposium is held every three years and is a forum for forensic managers from all Interpol Member States. The IFSS facilitates information exchange about scientific contributions in criminal investigations and the administration of justice, provides a forum for discussion of current forensic issues and possible solutions, identifies trends and their potential effects on forensic science, creates bridges with the international forensic community supporting Interpol’s mission, and presents updates made in forensic sciences over the previous three years. It is to this last area that this volume is dedicated. The reports are presented at the IFSS orally and the reports are distributed at the Symposium but are also available on the Interpol website1 as PDFs. Nevertheless, we felt that there was significant benefit to having all the reports pulled together in one source for reference, research, and teaching. Both of us are journal editors2, so anything that makes research and referencing easier is a bonus. The publication of the US National Academies of Science report, Strengthening Forensic Science in the United States: A Path Forward in 2009 also places greater responsibility on the forensic community worldwide to support their science and methods through education, training, research, and publication. We intend to continue to offer these volumes every three years, with Interpol’s permission. Proceeds from the sale of this volume will help to defray the costs of the IFSS and makes it more accessible to nations who are seeking to improve the science that assists their justice systems. We would like to thank Interpol for their indulgence in allowing us to promote the fruits of their labor and make them available to a larger but no less eager audience. Becky Masterman of CRC Press and the people at Taylor & Francis also deserve our thanks: They did everything they could to make this project happen at a reasonable cost in a very short period of time. Because each chapter was prepared and written by different authors (and many had multiple authors) and we wanted to retain the original authors’ words (they are the experts, after all), stylistic variation was inevitable. We strove, therefore, to impose as little structure on the manuscript as necessary to make it readable and as consistent as possible. References were kept in their original citation and bibliographic styles. We hope you find this first volume useful, interesting, and practical. NND MMH

1 2 NND is Editor in chief of Science and Justice; MMH is Co-Editor of Forensic Science Policy and Management.


Interpol Forensic Science Symposium Reports 2007

Review authors Chemical criminalistics The Forensic Examination of Fibres Ray Palmer The Forensic Science Service Ltd, Hinchingbrooke Park, Huntingdon, Cambridgeshire PE296NU, UK Firearms Sébastien Charles, PhD Jan De Ceuster, PhD Patrick De Smet, PhD Desiré Laza, PhD Bart Nys, PhD INCC – NICC, Chaussée de Vilvorde 100, 1120 Brussels, Belgium The Forensic Examination of Marks Nadav Levin, MSc Head, Toolmarks and Materials Laboratory, Division of Identification and Forensic Science (DIFS), Israel National Police Headquarters, Jerusalem 91906, Israel Forensic Geology Sugita R, MSc Suzuki S, PhD Katsumata Y, PhD National Research Institute of Police Science, 6-3-1 Kashiwanoha, Kashiwashi, Chiba 277-0882, Japan Paint and Glass Maureen J. Bradley, PhD Andria L. Hobbs, MS Diana M. Wright, PhD Robert D. Koons, PhD Federal Bureau of Investigation Laboratory, Quantico, Virginia, USA 22135

Drugs and Toxicology Drugs Jeffrey Comparin U.S. Department of Justice, Drug Enforcement Administration, Office of Forensic Sciences, Alexandria, Virginia, USA Toxicology S.C.Leung W.M. Tam, PhD W.C. Cheng PhD Florence S.Y. Chan, MPhil C.W. Hung, MPhil T.T. Wong, PhD


Interpol Forensic Science Symposium Reports 2007

Billy K.O. Leung, PhD W.S. Hui, PhD W.S. Lee, PhD W.L. Mak, PhD Government Laboratory, 7/F, Homantin Government Offices, 88 Chung Hau Street, Ho Man Tin, Kowloon, Hong Kong, China

Electronic evidence Forensic Audio and Visual Evidence Jurrien Bijhold Arnout Ruifrok Zeno Geradts Sabine Ehrhardt Ivo Alberink Netherlands Forensic Institute (NFI) Michael Jessen Bundeskriminalamt Germany (BKA) Digital Evidence Paul Reedy Brian Diplock Michael Dunlop Australian Federal Police, Canberra, ACT, Australia

Fire, explosives and hazardous materials Hazardous Materials: Chemical Biological Radiological and Nuclear Peter Baines Detective Inspector , National Institute of Forensic Science, Australia Environmental Crime Jennifer A. Suggs EPA-NEIC Bldg. 25, Denver Federal Center Denver, Colorado USA 80225 Diana A. Love Director, National Enforcement Investigations Center, Denver, Colarado Analysis and Detection of Explosives and Explosives Residues Sean Doyle, B.Sc. Principal Scientist, The Forensic Explosives Laboratory, Dstl, Fort Halstead, Sevenoaks, Kent TN14 7BP, UK Greg Czarnopys, B.S. Chief, Forensic Science Laboratory – Washington, Bureau of Alcohol,Tobacco, Firearms and Explosives. Fire Scene and Fire Debris Analysis Grzegorz Zadora, PhD Rafal Borusiewicz, PhD Institute of Forensic Research, Westerplatte 9, Krakow, Poland


Interpol Forensic Science Symposium Reports 2007

Individual evidence Biological Evidence and Forensic DNA Profiling Ronald M. Fourney, PhD Allison N. DesRoches, MSc Joseph L. Buckle, MSc Forensic Science and Identification Services, National Police Services, Royal Canadian Mounted Police Questioned Documents Thibaud Fritz Institut de Recherche Criminelle de la Gendarmerie Nationale (IRCGN), Rosny Sous Bois, France Fingermarks, Bitemarks and Other Impressions (Barefoot, Ears, Lips) Andy Becue, PhD C. Champod, PhD Pierre A. Margot, PhD Ecole de Sciences Criminelles / Institut de Police Scientifique, Faculté de Droit et des Sciences Criminelles, Université de Lausanne, CH-1015 Lausanne-Dorigny, Switzerland


Section 1- Chemical Criminalistics Technical Coordinator: Prof. Kimmo Himberg, National Institute of Forensic Science, Finland


Chapter 1 The Forensic Examination of Fibres Ray Palmer1 Introduction This report catalogues the research and advances in scientific methodology relating to the forensic examination of fibres since the 14th INTERPOL Forensic Science Symposium held in October 2004. This report primarily consists of a literature review of published articles in forensic science journals and the proceedings of various working groups between May 2004 and August 2007. It also contains references from other sources such as periodicals, text books and the Internet. General The scientific working groups in Europe and North America continue to be active in training and collaborative research - not only in developing laboratory methodology but also in the production of data useful for more robust interpretation of this evidence type. The European Fibre Group (EFG) of the European Network of Forensic Science Institutes (ENFSI) [41] and the Fibre subgroup of the Scientific Working Group for Materials Analysis (SWGMAT) led by the FBI continue to be the main organisations promoting and developing this evidence type. Many of the citations in this document originate from the activities of these groups and/or their members. The EFG has remained committed to disseminating best practice and over the last 3 years has introduced a program of themed ‘development’ workshops, aimed at court reporting practitioners with less than 3 years experience. The workshop planned for this year is in Krakow, Poland and the theme is ‘intelligence’. In addition production of a document outlining the best use of fibre evidence in terrorist cases is underway. Once complete, the intention is to disseminate this to all law enforcement agencies in Europe (and abroad). The EFG continues to collaborate with colleagues in SWGMAT and Australia and this remains extremely productive. Likewise, the fibre subgroup of SWGMAT continues to be active. A review of the revisions to the Fibre Examination Guidelines document (originally published in 1998) is ongoing. Collaboration with colleagues in the EFG and SMANZFL continues, with work underway on a MSP project as well as the assessment of backpack fabric damage due to explosions. Representatives from SWGMAT continue to attend the annual meeting of the EFG and vice versa.


The Forensic Science Service Ltd, Hinchingbrooke Park, Huntingdon, Cambridgeshire PE296NU, UK


Fibre Recovery The recovery and preservation of fibres (whether at the crime scene or in the laboratory) is arguably the most crucial step in the examination process since in the majority of instances there will be little if any opportunity to re-perform this process. The ‘GIFT’ (‘get it first time’) principle remains the paramount objective. Over the last few years there has been increased interest in the process of fibre recovery involving the 1:1 taping method whereby a detailed distribution map of transferred fibres can be made which may assist in elucidating the nature of contact between victim and assailant - either for intelligence or corroborative purposes in an investigation. Whilst many law enforcement agencies have seen the potential value of this technique, uptake has been poor due to the immense resources required at the scene and laboratory to achieve the end result. Palmer [3] argued that whilst there is no doubt that true 1:1 taping at scenes can produce highly detailed maps of fibre distribution (such as reported by Nehse [40]), there is a question over whether this level of detail and the resources required are completely necessary. He reported on an alternative method which The Forensic Science Service has adopted, referred to as ‘Zonal’ taping. Although this method produces a map of fibre distribution which is less detailed than 1:1 taping, it has been demonstrated to be a more pragmatic ‘fit for purpose’ approach and much less resource intensive at the scene and in the laboratory. This technique essentially involves recovering fibres from predetermined zones on a body rather than using a single strip of tape to equate to an equal area of surface. This method is now beginning to find favour amongst police forces in the UK. The subsequent searching of fibre tape lifts (regardless of whether 1:1, zonal or the ‘standard’ method is employed) remains the most time consuming part of the examination process. Various instruments attempting to automate this process have become available over the last decade; however, none have been shown to reliably compete with human searching. The most recent evaluations of such instruments have shown that these still suffer from the problems identified in previous instruments. Monard-Sermier et al [26] compared automatic fibre searching (using the Maxcan fibre finder) with manual searching, in terms of efficiency. The effect of several parameters (including colour, thickness, and background) on the efficacy of the fibre search was investigated. In the laboratory, 18 experimental tapes containing different target fibres and different background populations were prepared. Operators from four European laboratories carried out fibre searches, either manually or automatically with the Maxcan instrument. The results obtained suggest that automated searching with this particular instrument was as efficient as manual searching, except (as with previous instruments) when very pale or very dark fibres are involved. However, it was noted that the laboratory-prepared tapes may not have been representative of tapes submitted in actual casework situations. The performance of a different instrument, the Q550fifi (Leica) was assessed by Campioli et al [2] who found that its performance was marred by a large number of false positives.



A consistently reliable automated fibre searching system therefore remains to be developed. Coyle [1] highlighted the usefulness of fluorescence stereomicroscopy for the searching of tape lifts for fibre evidence. This approach exploits the fluorescent properties of fibres in order to enhance the contrast between the target fibre and background fibres. This is particularly useful when the target fibre and the background fibres are similar in terms of shade and/or structure. The process of discriminating between colourless fibres can also be enhanced by fluorescence stereomicroscopy. This method therefore provides the potential to speed up the searching process without the use of automation. The subsequent recovery and preservation of fibre evidence from tape lifts onto the microscope slide in preparation for examination, requires the use of a suitable mountant, which needs to conform to specific criteria. Since established sources of such material can become unavailable (due to economic factors or health and safety concerns) the identification of suitable alternatives becomes extremely important. Wiggins and Drummond [32] investigated possible replacements for the XAM Neutral Medium Improved White mounting medium which has now become unavailable. The replacement media tested were Clarion, Entellan, Eukitt, Euparal, home-made Phytohistol, and Practamount. The performance of each mounting medium was assessed in terms of colour, refractive index, setting, fluorescence, ease of handling, bubbling, crystal formation, shrinkage, yellowing, cracking, microspectrophotometry (visible and UV/visible), Fourier Transform Infrared (FTIR) spectroscopy, and thinlayer chromatography (TLC). Of the mounting media tested, Entellan and Eukitt performed consistently well, resulting in the recommendation of Entellan for forensic fibre examinations. The robustness of fibre evidence not only depends on its correct recovery and preservation, but on the quality management systems in place within a laboratory to ensure subsequent contamination does not occur. Whilst anti-contamination issues relating to DNA evidence are often in place in a laboratory, it is disappointing that in some instances this is not applied to trace evidence. Akrap [3] conducted a survey of laboratory anti-contamination procedures at various laboratories throughout Europe. From the survey returns, it was concluded that in general terms, the standard of anti-contamination procedures employed by most forensic laboratories and police forces are very good. However, it became apparent that a number of scientists need to spend some time educating the police officers that they work with in order to improve the submissions to the laboratory. Disappointingly, there was also evidence that some laboratories need to considerably improve their working practices with regard to contamination. Analytical Methods As in previous years, publications report attempts to improve existing techniques in terms of efficiency, sensitivity or a combination of both. The current methodologies used in fibre examinations are by and large tried and tested in this respect and therefore improvements in time and/or increased discrimination afforded by new


instrumentation and/or methodologies have to be demonstrated before uptake is justified in terms of cost. Research into the application of RAMAN spectroscopy to the forensic examination of textile fibres has continued since the last review, with members of the European Fibre Group being the most active in this area [1, 2, 3]. Work by other researchers in this field [18] has complimented the efforts of the EFG. Despite this research, adoption of this technique into mainstream operational laboratories is still poor, primarily because it has yet to demonstrate any substantial improvement in discrimination afforded by the combination of existing analytical protocols against the cost of the instrumentation. Nevertheless, research in this area is active and it is possible that the problems associated with its application in this area may be resolved. The cross-sectional shape of fibres is an important comparative feature and a number of methods have been described for the preparation. Kolar [3] described the cork method, the metal plate method, microtome methods with various embedding media and polyethylene plastic tube method, etc., which could be used for cross section preparation. A new simple method for preparation of fibre cross sections has been tested in the ICP. Shirt buttons, power glue, a glass microscopic slide and abrasive paper have been used for the fibre cross sections preparation. The section fixed on a glass microscopic slide has been prepared by ablating and polishing the surface of the button to a very thin layer. This method is easy and fast. Infra Red spectroscopy still remains an important part of the standard protocol of fibre analysis and comparison and several workers have carried out projects to extend the scope of this technique. Causin et al [15] used infrared (IR) microspectroscopy to obtain absorbance peaks of nitrile, carbonyl and C-H groups for 48 colourless acrylic fibres. The carbonyl signal, related to the co-monomers most often used in acrylic fibres, was ratioed against the nitrile and C-H bands, pertaining to the polymer chain backbones. Ratios representing a relative measure of the co-monomer content of the fibre were used for sample differentiation. There was a decrease in the crystallinity of fibres with increasing co-monomer content. Analysis of different fibres from the same sample generated results which were reproducible to within 6%. The ability to discriminate between colourless acrylic fibres enhances their evidential value. Flynn et al [20] analysed bicomponent fibres using infrared chemical imaging. The fibres were examined either side-on or in cross-section. In six samples, infrared chemical imaging could spatially resolve two spectroscopically distinct regions when the samples were examined side-on. This technique yielded characteristic IR spectra for each component whilst providing images that clearly showed the side-by-side configuration of the components in the fibre. Preparing cross-sections of the fibres proved difficult for all but one of the samples. In five samples, the IR spectra could be used to identify the overall chemical composition of the fibres, in accordance with a published classification scheme, although the components of the fibres could not be spatially resolved. The analyses were also hampered by problems such as interference fringeing and sloping baselines, especially when acrylic-type fibres were examined. Whilst microspectrophotometry is still used routinely to compare fibre colour in an objective manner, there is still an inherent subjective component to this method – 5


particularly where very pale or opaque samples are involved and the resultant spectra are broad and featureless. The use of first derivative calculations is well documented in many areas of science but until recently there has been little (if any) literature relating to the potential of this technique to improve resolution and discrimination in forensic fibre examinations. Wiggins et al [31] measured a range of fibre samples across the visible and UV/visible wavelength ranges, respectively. The first derivative of the absorbance spectra was then calculated and studied. For many of the samples, calculating the first derivative did not add any extra value because of the high number of points of comparison in the absorbance spectra. When the absorbance spectra produced for some samples were broad and featureless, the first derivative spectra provided more points of comparison, which facilitated the interpretation of the results. However, for some samples which had a high level of variation in absorbance spectra, the associated first derivative spectra showed differences between fibres which could have suggested that they did not match. Because of this, considerable care needs to be taken when using first derivative calculations as a tool in forensic fibre analysis, in order to avoid false exclusions. One area of concern to the fibre examiner is the potential to falsely exclude a suspect fibre as having come from a particular source. It is known this potential can be increased if inadequate sampling of a garment is carried out where high intra-garment variability in colour exists. A collaborative study between the EFG and SWGMAT reported by Wiggins [2] found no evidence of MSP spectral variation across a garment. Methods of dye analysis (other than RAMAN) remain a fertile area of research. The use of reactive dyes to colour fibres has increased over the last 10-15 years and these are often seen in casework. Before the introduction of techniques that allowed reactivelydyed fibres to be compared using TLC, only comparison microscopy and microspectrophotometry were routinely carried out. Since many microspectrophotometer equipped laboratories possess only visible range instruments, it is therefore important to see which techniques could potentially provide additional information in terms of a direct examination of the dye itself. Wiggins et al [12] obtained samples of reactively dyed wool and cotton from a range of dye manufacturers, dye distributors and the Forensic Science Service (FSS) Fibre Data Collection. Red, blue and black fibres were selected as they are often encountered in casework. The results demonstrated that TLC and UV-MSP both provide important information over and above that obtained from comparison microscopy and visible range MSP. Whilst the use of Thin Layer Chromatography (TLC) is firmly established as a method for classification and comparison of dye stuff, relatively large amounts of dye are required for this technique to be effective. Work has continued to identify methods which may increase the sensitivity of dye analysis to allow the analysis of material presently precluded by the use of TLC. Petrick et al [19] assessed the usefulness of high-performance liquid chromatographyelectrospray ionisation mass spectrometry (LC-MS) in the analysis of fibre dyes in 6

forensic casework. A multi-stage chromatographic method using acidified water and acidified acetonitrile was developed to separate and identify a mixture consisting of 15 basic and 13 disperse dye standards. LC-MS was also applied to the detection and analysis of dyes extracted from individual 0.5 cm acrylic and polyester fibres which demonstrated its usefulness for this type of analysis. The advantage of LC-MS compared with other analytical methods of textile dye analysis was demonstrated by the differentiation of three black acrylic fibres that could not be fully differentiated on the basis of their UV-Vis spectra and/or chromatograms. Roux et al [30] assessed the usefulness of Ultra Performance Liquid Chromatography (UPLC) for the analysis of fibre dyes. The results obtained confirmed the potential of this technique for trace evidence analysis, although further research is needed. It appears that UPLC can successfully analyse dyes extracted from single, black, polyester fibres with sufficient sensitivity and selectivity. Huang et al [17] successfully used liquid chromatography-mass spectrometry (LC-MS) for the discrimination of textile dyes that could not easily be distinguished based on their UV/visible absorption profiles. LC-MS was used to identify seven pairs of commercially available dyes with almost identical UV/visible absorption profiles and absorption maxima within 5 nm. LC-MS was also capable of discriminating between two pairs of cotton fibres which were indistinguishable by microspectrophotometry. Dye elution from the column was monitored by a single-wavelength UV/visible detector. The uptake of these techniques as a standard means of dye analysis will require further work to demonstrate their efficiency with a broad spectrum of fibre type/dye combinations, against the cost of the instrumentation. Whilst colour remains the critical component of fibres in terms of their instrumental analysis, attempts have been made to increase the discrimination of non-coloured fibres which presently are generally perceived to have little or no evidential value. Causin et al [21] studied the application of pyrolysis gas chromatography mass spectrometry in the differentiation of colourless polyacrylonitrile-based fibres with similar structure. Fibres differ slightly in terms of the concentration and distribution of head-to-head arrangements of their monomers. Such structural variation can significantly affect the composition of the mixture of the pyrolysis products, allowing the fibres to be differentiated. It was found that hydrocyanic acid, acetonitrile, acetic acid, acrylonitrile, 1,3-dicyanopropene, 1,3-dicyanobutene, 2,4-dicyanobutene and 1,3,5tricyanohexane were the most suitable degradation products for discriminating between samples studied. Principal component analysis was used to evaluate the results. Interpretation Whilst many workers strive to improve the efficacy of the various methods of identification and comparison, the main emphasis on research over the last few years has been on the interpretation of fibre evidence. In many ways this is not surprising, since it is more often the case that fibre ‘matches’ are in themselves not contested, but that the significance of their presence is. For those employing the Bayesian approach to 7


interpretation, it is vital that empirical data is gathered and that this process is ongoing. Since many studies have consistently shown that the chances of finding two fibres matching by chance are extremely low, it is important to demonstrate that in an ever changing textile environment these findings continue to hold true. Was-Gubala [5] assessed the frequency of occurrence of different Czech Republic and Germany. To this end, fibres were collected transport in Krakow, Prague, and Stuttgart. The results of this similar to those obtained in previous studies carried out in Switzerland, and Austria and therefore the establishment of frequency databases may be feasible.

fibres in Poland, the from seats of public study were broadly the UK, Germany, pan-European fibre

A similar study by Leung [4] was carried out using clothing from casework to determine whether the probability of chance matches was increased in a small geographical area with a large population density (Hong-Kong). The results obtained were in accordance with previous studies performed in Europe. For many fibre examiners the discrimination of clothing comprising of ubiquitous fibres (such as indigo dyed denim jeans) has remained problematical – particularly in cases where these are the only garments potentially available for comparison. Biermann et al [22] investigated the use of microspectrophotometry for the discrimination of fibres dyed with indigo and seven derivative dyes. Normally, indigodyed fibres are excluded from fibre-transfer examinations because they are so widespread and, therefore, lack evidential value. However, indigo substitutes are used as dyes in the fashion industry and if the use of such dyes is widespread, it may be necessary to revise the assumption that all denim material is dyed with Vat Blue 1 dye. This work presented the results of a microspectrophotometric study of fibres from 160 samples of denim articles which showed that the use of derivatives is still comparatively rare and therefore if found in casework, are likely to be of high evidential value. Palmer [1, 2] reported casework examples where jeans dyed with indigo-blue were discriminated on the basis of fibre content and fluorescence. In many instances, there is an assumption that some fibre type/colour combinations are of low evidential value, usually because of the perception of their commonality at the generic level (e.g. ‘blue’ cotton, ‘blue’ polyester’, ‘blue’ wool). Since the combination of comparative tests available to the fibre examiner is highly discriminatory, this perception has been shown to be erroneous by a number of current studies. Target fibre studies, population studies and research into 'blocks of colour' by Biermann et al [2] have confirmed the polymorphism of textile fibres-especially man-made fibresand have demonstrated that when a questioned fibre is believed to have a specific putative source, the chance that it came from another source by coincidence is very small. A more recent study by Biermann et al [8] goes further, using blue polyester fibres to show that even within a narrow segment of the entire general fibre population, many examples of a specific colour/type of man-made fibre obtained from random sources can be compared and the chance of any two being identical is remote. 8

Another similar study by Biermann [3] showed that the very high discriminating power obtained using a combination of light microscopy, fluorescence microscopy and uv/vis microspectrophotometry means that even blue and red cotton fibres can provide excellent evidence when involved in fibre transfer cases. The discriminating power of microscopy alone was highlighted by Oein [1] who in a casework situation demonstrated that none of the 49 textiles containing black wool could be associated to the black wool fibre recovered from the evidence. Of these, comparison microscopy alone was able to distinguish 46 of the textiles, while microspectrophotometry was necessary to discriminate the final three samples. Based on these results, it seems that the evidential value of black cotton and black wool is higher than originally expected. Similar data was obtained by Wiggins and Drummond [9] who searched 58 garments for extraneous mid- to dark-blue wool fibres. The 2,740 blue wool fibres identified were subjected to microspectrophotometric analysis. Three hundred independent blue wool populations were identified on 56 of the 58 garments searched. Although blue wool is considered to be a common fibre type, 300 unique spectral shapes were identified by the use of microspectrophotometry alone. This demonstrated that the dyes used in the colouring of blue wool are highly variable. Fibre population studies seek to assess the frequency of fibre type/colour combinations at the generic level. Since these frequency figures are produced in the absence of instrumental analysis, the data is extremely conservative but nevertheless useful, particularly when the Bayesian approach is employed. Since the frequency of certain fibre types and/ or fibre type/ colour combinations may change due to fashion, season and geography, it is important that such data is kept current and any changes monitored. Marname et al [24] studied the total foreign fibre population on a small number of items of clothing. The number of coloured foreign fibres present on six white T-shirts after each garment had been worn for one day was determined, revealing that the Tshirts contained between 9,108 and 13,925 coloured foreign fibres. Microscopic examination of the coloured fibres was carried out in order to determine their colour, width and length, and classification (cotton, wool, synthetic, silk, or miscellaneous). Pair-wise comparisons of similar fibres were subsequently carried out in order to determine the number and size of the groups of foreign fibres present on the garments. These findings supplemented the information currently available on background foreign fibre populations on clothing and other items. Watt et al [7] investigated the coloured fibre population in domestic washing machines during spring in Sydney, Australia. This work involved the washing of white cotton Tshirts, individually and mixed with a normal load of washing, and the subsequent taping of the washed T-shirts for extraneous fibres transferred during the wash cycle. In total, 12,178 fibres recovered were classified according to length, colour and generic class. The most frequently encountered fibres were cotton (69.4%) and man-made fibres (24.2%). The most frequently encountered colour/generic class combinations were black/grey cotton (27%), blue cotton (20%), and red cotton (15.6%). Other combinations 9


accounted for less than 2% of the total fibres recovered. Most (65.9%) of the recovered fibres were less than 2 mm long. An important aspect in the interpretation of fibre evidence is the consideration of dye batch variation. Very few papers have been published on studies of this effect, the most recent being Wiggins and Holness [13]. They studied four sets of acrylic fibre samples which were obtained from a company that dyes fabrics for the fashion industry. Between seven and ten different batches of fibres constituted each set. Comparison microscopy, visible and UV range microspectrophotometry and Thin Layer Chromatography (TLC) were used to compare the dyes on each batch of fibres within the sets. Only one of the four sets exhibited variation when both microscopical and analytical techniques were used. In addition, two further sets of samples had been obtained from a company that produces carpets for the car industry. The first set consisted of 26 batches of acid-dyed orange nylon fibres. The second consisted of 21 batches of acid-dyed, mustard-coloured nylon and direct-dyed brown viscose fibres blended together. When the first set was viewed under UV light, one batch had more pale orange fibres present, which fluoresced more brightly than the other fibres. When tested using visible and UV range microspectrophotometry and TLC, further dye batch variation was not detected. The second set was examined after separating the nylon and viscose fibres from each other. The nylon fibres were indistinguishable when a range of microscopical and analytical techniques were employed; however, the viscose fibres showed dye batch variation when TLC was used. In the commission of crimes where the perpetrator conceals his identity using a mask/balaclava (e.g. robbery, terrorism etc) fibres may be transferred from the item in question to their hair. The value of the recovery of fibres from head hair was the subject of a paper by Palmer [4]. The persistence dynamics of these fibres have been the subject of a number of studies and can be used as a ‘time frame for wear’ (up to 7 days). However, when a suspect is apprehended outside this ‘window of persistence’ any value in attempting to recover fibres from their hair is usually lost. In these situations, anecdotal information suggests that consideration of potential secondary transfers may provide a useful alternative. This was the subject of a study by Palmer and Banks [10] who considered the effects of fibre type, hair style, time, and fibre persistence on the secondary transfer of mask fibres to pillowcases, via head hair. Volunteers with a range of hair styles and masks consisting of different fibre compositions were used in the study. Fibres from the masks were found to transfer from donor subjects to the pillowcases up to 14 nights after the mask had been worn. On average, the number of secondarily transferred fibres found decreased with time; however, this decrease appeared to be more 'linear' in nature rather than an exponential decay. The greatest degree of secondary transfer occurred with cotton, followed by acrylic, then wool. In a primary transfer/persistence experiment with a 50% acrylic/50% wool mask, wool was found to persist in the hair more readily than acrylic. The results also showed that the greatest degree of secondary transfer occurred via short, straight and long, straight hair, with no clear pattern emerging between medium-length hair (both straight and curly) and with long, curly hair. In a similar study involving the persistence of transferred fibres to bare hands and gloves, Marshall [2] reported a half life of persistence of around 5 minutes.


Textile/ Fibre Damage A number of studies into the effects of environmental challenges to textile fibres have been carried out since the last review. Was-Gubala and Krauss [23] investigated the damage to textiles and single textile fibres caused by direct contact with a heating plate as well as exposure to an open flame. Tests were carried out using textiles of different colours, fibre composition and textile construction. Optical and scanning electron microscopy (SEM) were used to examine the specific types of changes occurring in thermally degraded textiles and fibres. Hirschler et al [25] analysed 16 commercially available items of clothing in terms of their fabric composition which were then subjected to fire testing. The three fire exposures used were: (1) a simile of 16CFR1610, (2) a small vertical candle on a small swatch of fabric, and (3) a candle applied to a complete garment on a mannequin. Examination of the test results revealed a general correlation between increased fabric areal density (weight/unit fabric area) and improved fire performance. Where outliers to this generalisation were found, the improved fire retardation performance was because of the inherently superior performance of specific types of fabric such as silk. In general, the quantitative behaviour regarding the rate of flame spread after the ignition of cellulosic, thermoplastic and blended fabrics depended more on fabric areal density than on chemical composition. Very lightweight fabrics were found to pose a potential risk, with the regulatory value of 2.6 ounces per yard squared representing an arbitrary cut-off in this regard. Rosengarten [2] reported on the analysis of damage that occurred in nylon straps used at a military airport which was originally thought to have been caused by wolves. Visual inspection, low power microscopy and SEM were used and revealed a pattern similar to that of a hacksaw, thus the straps were found to be damaged as a result of sabotage and not by wolves. A similar case involving such methodology was also reported by Vasconcellos [1] in determining whether a parachutist’s straps had been deliberately cut. Calzetta et al [2] presented a case study of an assault which involved the use of a corrosive liquid against the victim. These authors attempted to determine the causes of the faded stains on items of clothing. Based on macroscopic and microscopic observations, and chemical tests involving questioned liquids, it was concluded that the damage to the clothing was caused by contact with hydrochloric acid. Causin et al [14] described a novel method, based on the integration of infrared (IR) absorption bands, for the differentiation of single poly(ethylene terephthalate) (PET) fibres. This technique used IR microscopy in transmission mode, differential scanning colorimetry and optical microscopy. Particular attention was paid to fibres which had been immersed in water and exposed to solar irradiation for a three-month period. It was found that this exposure to the elements had no effect on the morphology of the PET fibres; therefore the significance of fibre comparison results appeared unaffected by weathering.



Wąs-Gubała [3] investigated the kinetics of colour change in textiles and fibres treated with detergent solutions using a 14-day experiment involving blue, red and grey/black cotton, wool, acrylic and polyester textiles. The kinetics of the changes in the colour of the textiles were tracked in UV as well as visible lights, using fluorescence microscopy and MSP. Textile Technology The textile industry worldwide is in a permanent state of flux and it is essential that forensic fibre examiners keep up to date with technological developments, fashion trends, the emergence of new fibre types and dyes, optical brighteners and finishing agents. Grover et al [16] described the increasing interest in the use of eco-friendly natural dyes for the colouring of fibres and investigated the extraction of dyes from different parts of plants and the optimisation of dyeing variables of the natural dyes for the dyeing of silk. The use of metallic mordants to give a wide range of dye colours was also discussed. Greaves and Bainsford [11] looked at fibre samples between 1970 and 2005 in order to determine why there has been a steady increase in the production of Peru's coarser alpaca fibre at the expense of its finer, more commercial properties. Microscopical analyses and comparisons with older data (where available) were also carried out using llama, vicuna and guanaco fibres. Wiggins and Cornelius [29] performed a study to determine which processes used during fibre production have a significant effect on the spectral and chromatographic results seen in casework. Theoretically, any information obtained from spectra in the visible region is likely to be due to colouration whereas that in the UV region could be due to the dye or from other compounds used throughout the manufacturing process. This paper demonstrated that many of the processes used prior to dyeing have little or no effect on the finished item when examined using spectral or chromatographic techniques. The only exception was a colourless viscose sample which gave spectral information in the UV region, inferring that this may be due to optical brighteners and/or UV absorbers being used in production. Koch [28] produced statistics which showed that the production of cellulosic fibres is increasing. Such fibres are usually specialty-type fibres often found in underwear and active wear, with examples being Soy silk, Bamboo, Viloft, and Sea Cell. The article outlines some of the important characteristics of these fibres for the benefit of forensic microscopists who may encounter them during casework. Likewise Lunt [6] reported on Dow Cargill's Ingeo, which represents the first of a new class of manufactured fibres produced from annually renewable resources. This new fibre, which is a polylactic acid (PLA) polymer derived from the fermentation of natural plant sugars, possesses the full range of textile properties but has very little environmental impact. Other useful resources in this category include a number of recently published books [33 to 39]. 12

A number of internet web sites cited in the previous report [42 to 56] also remain useful sources of information. Miscellaneous Oien [1] reported that during the analysis of evidence recovered from an improvised explosive device, a question arose as to whether the superglue process for latent fingerprint immobilization should be conducted in the field in order to preserve potential latent fingerprints. Since the items subjected to this process could potentially be examined for other types of evidence, this study was undertaken to determine if there were any detrimental effects from latent fingerprint processes on fibre examinations. The effect of the superglue treatment was found to have no adverse effect on the fibre examinations. This was an important finding as it dispelled any concern about the pre-treatment of evidence using superglue prior to fibre examinations being conducted. Roux [3] reported a study in which natural and man-made fibres were exposed to increasing doses of radiation intended to simulate some degree of exposure to a typical category two industrial radiography source (e.g. Cobalt-60, Cesium-137, Iridium -192). At each juncture, the fibres were evaluated using a range of forensic techniques to ascertain if any radiation damage had been manifested. Changes were noted in the colour and resultant MSP spectra at high radiation doses. Bull et al [27] carried out a study into the transfer and persistence of trace particulates such as pollen using different clothing fabrics. The results of this were in accordance with previous studies involving fibres. The Future With the increased threat of terrorism, law enforcement agencies are continually looking to forensic science for the provision of intelligence in these (often) complex investigations-not only to identify the perpetrators of a specific attack, but also in preventing future incidents. Biermann [1] presented an overview of fibre and textile examinations carried out by laboratories dealing with general terrorist attacks, especially in relation to firearms, bomb and arson attacks (including letters), hidden depots, hiding places, kidnapping, letters claiming responsibility and letter bombs. Image comparison, size determinations of clothing found in hiding places, label evaluation (intelligence work by determination of manufacturers), country of production, time of sale, country of sale, region of sale, number of sold textiles, determination of garment age, fibre analysis, research & development, construction analysis, industrial enquiries and development of case databases were all cited as probative methods and lines of investigation. Oien [2, 3] reported on the role of the Terrorist Explosive Device Analytical Centre (TEDAC) and gave an update on fibre examinations relating to improvised explosive devices (IEDs) collected from Iraq and Afghanistan, which continue to be a major initiative for the FBI Laboratory. He reported that over 3000 devices had been examined in the Trace Evidence Unit, with an additional 2000 devices awaiting examinations. Numerous associations between different devices have been made based on the fibre 13


examinations alone, with additional associations being made with latent fingerprints, mitochondrial DNA examinations, and examinations of the IEDs themselves. The large number of fibres being identified on these devices have necessitated the development of a database of fibres, and future research projects are being contemplated on developing a useful, searchable database of fibre properties, including microspectrophotometry data, to facilitate the examinations in these cases. Collaboration between the EFG and SWGMAT in the research on the effects of explosions on textiles and also in a survey of fibres used in the manufacture of backpacks is on going and progress was reported by Was-Gubala [3]. Over the last few years fibre examinations have demonstrated their value as a powerful intelligence tool in large complex enquiries, providing invaluable investigative steers. As already mentioned, forensic science is being increasingly asked to provide answers in these enquiries and trace evidence examinations are becoming increasingly important – particularly as many criminals are ‘DNA’ aware. De Wael [1] described the use of fibres as an intelligence tool in a case where no donor source was found. Palmer [2, 40] reported on the use of fibres as a powerful intelligence tool with reference to major complex enquiries. Advances in label technology, in particular the use of transponder technology in this area, have been highlighted by Dillinger [2]. The potential value of these items particularly in intelligence led enquiries is potentially enormous due to the amount and nature of the information they contain. There is a general consensus that a ‘fibre database’ would be an invaluable tool not only in general casework, but also in terms of delivering intelligence in major enquiries. Drotz [3] outlined the ways in which such a database can assist in casework by allowing more robust interpretations and conclusions to be made. Whilst virtually all practitioners see the benefits of such a system, to date no significant progress has been made in this area. Summary The work of the ENFSI European Fibre Group and the fibre sub group of SWGMAT has continued to be pivotal in steering research and identifying ways in which fibre examiners can rise to the increasing challenges presented to them by law enforcement agencies. The considerable research carried out in this field over the last three years, particularly in the area of interpretation, reflects a willingness by practitioners to address the cogent issues facing them. The challenges facing forensic science and the ever changing nature of technology and the textile industry will ensure that this impetus will continue.


References 1.

Proceedings of the 12th European Fibres Group meeting, Prague, Czech Republic, 2004


Proceedings of the 13th European Fibres Group meeting, Bled, Slovenia, 2005


Proceedings of the 14th European Fibres Group meeting, Rome, Italy, 2006


Proceedings of the 17th International Association of Forensic Sciences, Hong Kong, China, 2005


Was-Gubala J. Comparative Population Studies of Fibres Secured in Poland, Czech Republic and Germany, Zagadnien-Nauk-Sadowych, 2004, 60, 58-77


Lunt J.Ingeo PLA Fibres: Chemistry, manufacture and application, TEXTILES, 2004, 31 (3), 15-16.


Watt R, Roux C, Robertson J. The population of textile fibres in domestic washing machines, Science & Justice 2005, 45(2); 75-83


Grieve M, Biermann T, Schaub K. The individuality of fibres used to provide forensic evidence – not all blue polyesters are the same, Science & Justice 2005, 45(1), 13-28


Wiggins K, Drummond P. The analysis and comparison of blue wool fibre populations found at random on clothing, Science & Justice, 2005, 45(3), 157162


Palmer R, Banks M. The secondary transfer of fibres from head hair, Science & Justice, 2005, 45(3), 123-128


Greaves P, Bainsford F. Camelid fibres compared and contrasted, Textiles, 2005, 32(3/4), 46-48


Wiggins K, Holness J-A, March B. The importance of thin layer chromatography and UV microspectrophotometry in the analysis of reactive dyes released from cotton and wool fibres, Journal of Forensic Sciences, 2005, 50(2), 364-368


Holness J-A, Wiggins K. A further study of dye batch variation in textile and carpet fibres, Science & Justice, 2005, 45(2), 93-96


Causin V, Marega C, Guzzini G, Marigo A. The effect of exposure to the elements on the forensic characterisation by infra-red spectroscopy of PET fibres, Journal of Forensic Sciences, 2005, 50 (4) 887-893




Causin V, Marega C, Schiavone S, Marigo A. A quantative differentiation method for acrylic fibres by infra-red spectroscopy, Forensic Science International, 2005, 151(2/3), 125-131


Grover E, Sharma A, Rawat B, Paul S, Jahan S. Dyeing of silk with natural dyes, International Dyer, 2005,190(10), 9-16


Huang M, Russo R, Fookes G, Sigma E. Analysis of fibre dyes by liquid chromatography mass spectrometry (LC-MS) with electrospray ionisation: discriminating between dyes with indistinguishable UV-Visible absorption spectra, Journal of Forensic Science, 2005, 50 (3), 526-534.


Thomas J, Buzzini P, Massonnet G, Reedy B, Roux-C. Evaluation of Raman spectroscopy for the analysis of coloured fibres: A collaborative study, Forensic Science International, 2005, 152 (2-3), September, 189-197.


Petrick L, Wilson T, Fawcet W. HPLC UV-Visible spectroscopy-electrospray ionisation mass spectrometry method for acrylic and polyester fibre dye analysis, Journal of Forensic Sciences, 2006, 51(4), 771-779


Flynn K, O’Leary R, Roux C, Reedy B. The Forensic analysis of bicomponent fibres using infra-red chemical imaging, Journal of Forensic Sciences, 2006, 51(3), 586-596


Causin V, Marega C, Schiavone S, Della- Guardia V, Marigo A. The forensic analysis of acrylic fibres by pyrolysis gas chromatography/mass spectrometry, Analytical Applications of Pyrolysis, 2006, 75, 43-48


Grieve M, Biermann T, Schaub K. The use of indigo derivatives to dye denim material, Science & Justice, 2006, 46(1), 15-24


Was-Gubala Y, Krauss W. Damage caused by the action of two types of heat, Forensic Science International, 2006, 159(2/3), 119-126


Marname R, Elliot D, Coulson S. A pilot study to determine the background population of foreign fibre groups on a cotton/polyester T-shirt, Science & Justice, 2006, 46(4), 215-220


Hirschler M, Umino P, Zicherman J. Forensic evaluations of fabric flammability, Proceedings of the 17th Annual Conference on Flame Retardancy, 2006, 335-357


Monard – Sermier F, Massonnet G, Buzzini P, Fortini A, Gason F, De-Wael K, Rovas P. A comparison of efficiency of manual and automatic fibres each with the Maxcan fibre finder, Forensic Science International, 2006, 160 (2-2), 102-108



Bull P, Morgan M, Sagovsky A, Hughes G. The transfer and persistence of trace particulates: experimental studies using clothing fabrics, Science & Justice, 2006, 46(3), 185-195


Koch S. Beyond cotton, nylon and polyester. The emergence of new fibres and yarns, Global Forensic Science Today, 2007, 1


Wiggins K, Cornelius J-A. A study in relation to the effect of processes used in the dyeing industry on the finished article, Global Forensic Science Today, 2007, 1


Roux C, Austin C, Bennett S, Beavis A, Dawson M, Doble P, Lennard C, Robertson J. Ultra performance liquid chromatography – an emerging technique for the forensic analysis of trace evidence, Global Forensic Science Today, 2007, 1


Wiggins K, Palmer R, Hutchinson W, Drummond P. An investigation into the use of calculating the first derivative of absorbance spectra as a tool for forensic fibre analysis, Science & Justice, 2007, 47, 9-18


Wiggins K, Drummond P. Identifying a suitable mounting medium for use in forensic fibre examination, Science and Justice, 2007, 47, 2-8


Fibres & Textiles in Eastern Europe, Instytut Biopolimerów i Włókien Chemicznych (Institute of Biopolymers and Chemical Fibres), Poland, 2007, Volume 15, 2(61)


Kadolph S, Langford A. Textiles, Prentice Hall, 10th Edition, 2006, ISBN: 9780131187696


Xin J. Total Colour Management in Textiles, CRC Press, 2006, ISBN: 9780849392078


Shishoo R. Textiles in Sport, CRC Press, 2005, ISBN: 9780849334863


Scott R. Textiles for Protection, CRC Press, 2005, ISBN: 9780849334887


Hu J. Structure and Mechanisms of Woven Fabrics, CRC Press, 2004, ISBN: 9780849328268


Shindler W, Haur P. The Chemical Finishing of Textiles, CRC Press, 2004, ISBN: 0849328256


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41. 42. 43. 17


44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56.

Thanks go to Martin McIvoy for the assistance in carrying out the literature search.


Chapter 2 Firearms2 Sébastien Charles, PhD3 Jan De Ceuster, PhD2 Patrick De Smet, PhD2 Desiré Laza, PhD2 Bart Nys, PhD2 Introduction This review paper covers advances in scientific methods applied to firearms (mainly ballistics and chemistry) reported since the 14th Interpol Forensic Science Symposium in October 2004. A literature review was conducted covering articles published in the principal forensic journals since 2004. Major forensic laboratories around the world were also asked to provide information. Firearms – Ballistics Firearms and toolmarks identification Criteria for identification Establishing criteria for identification is an ongoing matter of discussion, as it should be. Miller already published two articles on this subject in 1998 and 2000 (1,2). More recently in a third paper with similar title and subject, he addresses the consistency of determining what constitutes a matching line (3). Furthermore, the scientific reliability of using the Consecutive Matching Striae (CMS) theory as a criterion for identification of striated toolmarks is examined. The trainees that performed the test were first introduced to the history of firearms and toolmarks identification. They were told what constitutes identification and how known match/known non-match comparisons are necessary for the development of the CMS concept. Then the trainees had to perform comparisons between striated toolmarks produced in 35 mm photographic film emulsion using 60 grit sand paper. They were asked to count the lines and perform identifications using CMS, determine the highest total of matching lines as well as the highest percent of matching lines. The author found that counting the highest total matching lines and the highest percent of matching lines leads to false inclusions and false exclusions. By consequence, it should not be used as an identification criterion. Although variations in counting striae and consecutive groups of striae were noted, this had no effect on the conclusions reached by the examiner using the CMS criterion. A few missed identifications occurred only when the pattern area was limited. Miller used the data obtained by the trainees to perform a statistical study of the uniqueness of toolmark patterns. Nichols is also very active in this domain. In his literature overview, he discusses the criteria for identification through a study of ten consecutively manufactured extractors (4). It was observed that subclass characteristics were present and persisted on two surfaces of the extractor hooks. However, as no carry-over was 2 3

Approved by Jan De Kinder, PhD, Director INCC – NICC, Chaussée de Vilvorde 100, 1120 Brussels, Belgium 19


observed on the cartridge cases, the study demonstrated that it was of great importance to assess how the tool and the surface interact with each other. Apparently the corners adjacent to the two surfaces that bear the subclass characteristics have ridges that protrude away from the surfaces. These ridges have a significant impact on the toolmarks produced by the extractor so much that the issue of subclass characteristics is negated. Having discussed this, Nichols enters into detail about the AFTE Theory of Identification and the necessity of understanding the tool manufacturing processes. A great deal of attention goes also to the persistence of the individual characteristics and the issue of subclass characteristics. Nichols cites and discusses the relevant literature. In the framework of the AFTE Theory of Identification and the definition and measurement of the Best Known Non Match, he explains the concept of Consecutive Matching Striae for the description of pattern matching. He concludes that the underlying premises of the AFTE Theory of Identification and the conservative numerical criteria of CMS are scientifically valid and reliable. Besides establishing criteria for identification of striated tool marks, some first attempts were also made for impressed tool marks. In 2003, Stone published a theoretical statistical study on the uniqueness of impressed toolmarks from hypothetical hammer faces (5). Although this article is about toolmarks, the results can, to some extent, be translated to firearms identification since the firing pin impression and breechface signature are also impressed toolmarks. Stone considers five variables in the analysis of toolmarks: Origin, Resolution, Configuration, Orientation and Position. Furthermore he describes standardised individual characteristics: Point, Line, Curve, Enclosure and Three-dimensional Characteristics. He considers a hypothetical hammer face and determines the number of positions where a toolmark could be positioned, taking into account the conventional resolution and magnification factor of a comparison microscope. He then calculates the probability of finding a certain characteristic in a specific orientation and position. When the number of characteristics is increased, extremely low probabilities of obtaining these toolmarks by chance alone are very rapidly obtained. In other words, the probability of finding more and more individual toolmarks in a specific position, specific orientation and specific shape approaches zero. This theoretical model was subjected to an empirical study performed by Collins in 2005 (6). The author was able to detect the standardised individual characteristics as proposed by Stone on the faces of 20 worn hammers. With slight modifications to the original theory of Stone and using relatively conservative criteria, Collins was able to demonstrate that the probability of random occurrence of these features can indeed become extremely low as more and more characteristics are combined in the analysis. Collins furthermore applies his model to the firing pin of a firearm and demonstrates that the theory is also applicable in these situations. There are a few different approaches that a firearm examiner can follow when he evaluates a pattern of matching markings. Either he uses basic pattern matching looking at the amount of matching striae or the percentage of matching striae, or he can apply the conservative numerical criteria of the consecutive matching striae (CMS) method. In any case, he evaluates the pattern while comparing it with the 20

best known non-match that he has seen through his experience or that is published in literature, and he compares the match with what he would expect to see from a known matching pattern before reaching his conclusion. This weighing is, in fact, a Bayesian way of analysis. In the late nineties and the beginning of the years 2000, some papers were published that assessed the possibility of applying a true Bayesian likelihood calculation for a pattern match (see e.g. (7). Buckleton et al. published a paper in which they set up an exploratory Bayesian model for the interpretation of Bayesian toolmarks (8). The model is based on the CMS approach, although Bunch criticised this in 2000 (9). The data that were used to test the model was obtained through two previous CMS studies of the consecutively manufactured bullets and ten consecutively manufactured extractors. The probability of obtaining different runs of CMS was calculated. Whenever there was no data available for a certain CMS run, the authors simulated these values using conservative Deinet factors (i.e. taking a defined percentage of a neighbouring value). The likelihood ratios were then calculated by comparing the probabilities for known matches to the probabilities of known non matches. To express the results, the authors used a Bayesian reporting scale in which the likelihood ratio is translated to verbal scale. Buckleton et al. found that CMS and the Bayesian approach are not inherently incompatible but do stress that the model should be developed further using more data. The overall conclusion is that the higher the CMS count the larger the likelihood ratio. It is up to the examiner to determine his threshold for an identification based on the likelihood ratio reporting scale. A paper by Deinet et al. comments on the application of Bayes’ rule in the field of firearms and toolmarks comparison (10). First it is explained how the formula of Bayes’ rule is created. The formulation in which it is mostly used in forensic science is: posterior odds = likelihood ratio x prior odds where the likelihood ratio is defined as the ratio of p(E|H) and p(E|-H). However, the authors feel that the likelihood ratio is not what the court wants you to tell them. Further, the authors discuss the CMS model and the Renewal Theory Model, the latter being mostly used by these authors. Besides, they comment on the subjectivity of the determination of striae in patterns: Which striae are random? Which lines match, which don’t? Background statistics are required to be able to distinguish between the actual pattern and noise. The background statistics for p(E|H) are estimated from several comparison patterns of the questioned mark generator by testing the reproducibility of the pattern production. For p(E|-H) the background statistics are derived for accidental matches of striae. For this purpose, the authors have developed computer programs. The authors conclude that all theoretical probability models have pros and cons, so that they could perhaps complement one another. They propose the parallel use of different models in critical cases. After all the work that has been done to define criteria for identification, the discipline of firearms and toolmark examiners received a lot of criticism, especially in the amicus brief by Schwartz in 2005 (11). She criticises the reliability and admissibility of firearms and toolmark identification and states that because of systemic scientific problems, this field of expertise should be inadmissible across21


the-board. Schwartz comments on the absence of a sound statistical basis that helps to decide if a toolmark was made by a particular tool. According to the author, the courts have not yet understood the scientific issues concerning firearms and toolmark identification. Schwartz goes on and explains the pitfalls in firearms and toolmark identification: 1) the individual characteristics of toolmarks are comprised of non-unique marks, 2) subclass characteristics shared by more than one tool may be confused with individual characteristics unique to one and only one tool, and 3) the individual characteristics of the marks made by a particular tool change over time. No statistics have been developed on the rate at which subclass characteristics are produced by various types of tools. Schwartz often refers to fingerprint and DNA comparisons. Fingerprint and DNA consist of features that do not change over time whereas the opposite is very much true for firearms and tools. The similarities between toolmarks made by different tools and the differences between toolmarks made by the same tool imply that a statistical question must be answered to determine whether a particular tool was the source of a toolmark on an object recovered from a crime scene. Schwartz discusses the more objective CMS approach and highlights its drawbacks: it deals with striated toolmarks only and not with impressed toolmarks. Additionally, the danger of misidentifying on subclass characteristics when not recognised by the examiner still exists. To date firearms and toolmark examiners have not established databases of tools able to support their conclusions with a certain statistical significance. The error rate of the firearm and toolmark examiners could be derived from proficiency tests but the examiners are extra observant when the test is declared rather than blind. Computerised firearms identification does not always solve the issue of misidentifications and missed identifications. At present, the current systems are not yet ready to be used in large databases and certainly not for reference ballistic imaging databases. Using threedimensional images rather than two-dimensional images could yield more accurate results (see below). After the Daubert case, firearm and toolmark examiners were gravely concerned that increased judicial scrutiny might result in the exclusion of their testimony. However, both before and after Daubert, firearms and toolmark identification has largely been admitted as a matter of course. No court has recognised the systemic scientific problems with the field. Schwartz concludes by saying that all firearms and toolmark identifications should be excluded until the development of firm statistical empirical foundations for identifications and a rigorous regime of blind proficiency testing has been completed. In response to the critique from Schwartz, Nichols offered two publications to defend the scientific foundations of firearms and toolmark identification (12,13). First of all, he comments that while Schwartz was apparently aware of the large number of articles available that can be used to address many of the issues, there was no mention of them made in her argument. Nichols states that firearms and toolmark identification is rooted in scientific methods. He refers to the AFTE Theory 22

of Identification and to the many studies on known non-matches from consecutively manufactured tools to support the criterion for identification. He furthermore says that Schwartz has misinterpreted the information that she quotes or that she does not cite all of the available literature on the subject. In regard to subclass characteristics, Nichols says that knowledge and study of manufacturing processes of tools, in combination with the many studies addressing the issue of subclass characteristics, assist a trained and qualified examiner in easily discerning their potential for interference in comparative casework. He then discusses the studies on this issue and explains the rules that exist to distinguish between subclass and individual characteristics. Nichols admits that the surface of a tool will change over time. But, in contrast to Schwartz, he says that this does not make identification unreliable. Again he refers to a vast amount of literature, which proves that use of a firearm does not necessarily render identification impossible. In contrast to DNA identification, which is entirely based on subclass characteristics, firearms and tool mark identification is based on individual characteristics. Furthermore, by saying that the likelihood that another tool could have made the mark is so remote that it can be considered a practical impossibility, the AFTE Theory of Identification does not support claims of absolute individualisation. Nichols says that the implied need for representative statistical databases for each and every tool one might encounter is unfounded because the science of firearm and tool mark identification is based on manufacturing methods and on the ability to assess and distinguish among the class, subclass, and individual characteristics produced by the tool manufacturing process. Nichols comments on the application of statistics in firearm and toolmark examination. In regard to a Bayesian approach he says that the likelihood ratio does not answer the question as discretely as the judicial system may like. It is true that numbers representing the likelihood ratio are generated but the explanation for what those numbers mean in a real sense leaves the judicial system no closer to a real answer that has much more meaning than what is being offered now. Nichols waves away the comments of Schwartz on the proficiency tests by stating that they offer an assessment of laboratory practice, quality assurance, and quality control procedures. As it comes to the critique on computerised systems such as IBISTM, Nichols negates the opinion of Schwartz. The systems are developed to serve as a computerised database of data and images from bullets and cartridge cases for rapid searching of these images in an attempt to link cases that might have otherwise not been linked. As such it is an investigative aid only. Nichols concludes by reviewing the court decisions offered by Schwartz for which it appears that the courts do have adequate and sufficient knowledge regarding the intricacies of firearms and toolmark identification. A good attempt to statistically support the significance of consecutive matching striae is done by Howitt et al.(14). The conservative numerical CMS criterion is defined as a cut-off value above which a matching line pattern constitutes a match and below a non-match. Howitt understands that the idea of an absolute cut-off is unrealistic, but the statistical likelihood that a particular correspondence of the lines will occur by chance has never been properly assessed. Howitt et al. made a derivation of the probability of finding line correspondence and matching sets of consecutive striae on the surface of a bullet. They developed a statistical model for the calculation of the probability of occurrence of line sequences. They took into account the available, discernable line positions, sequence of lines and number of 23


lines present. The probability of finding three or more consecutive lines rapidly drops. The theory further demonstrates that if the criterion of consecutiveness is not taken into consideration, the probability of finding multiple lines matching is a lot higher. Thus, the concept of consecutiveness adds to the probability. The ENFSI Expert Working Group Firearms organised their first proficiency test for firearms identification in 2005 (FAID 2005). The test consisted of 15 sub-sets of castings of bullets and cartridge cases. This set-up ensured that all sixty participants were looking at the exact same markings. Each sub-set consisted of 2 known references (controls) and one unknown that had to be compared with the controls. The question for each sub-set was: “Is the unknown item from the same firearm as the two controls?” Results (15) show that not all participants of the FAID 2005 interpret the found similarities or differences equally. This test should therefore first be regarded as a collaborative study, to find ways to reduce differences in interpretation and have more (all) examiners use the same identification methodology. Parameters that influence identification There are a number of parameters that can affect the identification of recovered bullets and cartridge cases from a crime scene to the firearm that fired them. This part aims to cover a few of these parameter studies that were found in the literature. As gunshot victims are not always discovered immediately after the shooting took place, the bullets can become subject to the putrefaction of the bodies. Chow et al. performed a time dependent study of the damage to four types of bullets (16). They test fired into pig carcasses or simply put bullets obtained by test firing in a water tank into pig’s carcass at an acceptable depth. They express the time that elapsed in Accumulated Degree Days (ADD), a term also used in forensic entomology. After 200 ADD, the two copper bullets and one of the two brass bullets from the test either were not suitable for identification or the results were inconclusive. The other brass bullet and the aluminium bullet could still be identified after more than 400 ADD. Fired bullets and cartridge cases are not always immediately discovered as they can be regarded as fairly small objects with respect to furniture, grass, debris. Environmental exposure, depending on the medium and the length of deposition, can complicate or preclude microscopic laboratory comparisons of fired bullets and cartridge cases. Larrison evaluated the effect of the environment and time in situ (17). Bullets and cartridge cases were deposited in soil, water, open air, and a dog carcass. Larrison concluded that if the cartridge cases and bullets are kept in open air or soil, they can still be restored and identified after two years. Very likely the same is true in great excess of this time period. However, items left in an aqueous or decomposing tissue environment fare much worse and may not remain identifiable past two years, if not earlier. But small areas of identification can still survive beneath the oxidative scale. Copper jackets and nickel primers are vulnerable to the soft, fatty tissue of the abdominal cavity and the copper jackets degrade almost as rapidly in an aqueous environment. Nickel primers hold up quite well in an aqueous environment, keeping their individual characteristics intact over time.


Certain brands of ammunition, such as Sellier & Bellot and Geco have a primer sealant that is applied across the entire surface of the primer. When a cartridge is discharged, pressure not only drives the bullet out of the barrel but an equivalent pressure is working on the bottom of the cartridge case. The head of the cartridge is pushed with great force against the breechface of the firearm. During this action, toolmarks from the breechface are impressed on the head of the cartridge. Hayes et al. have investigated the absorbing effect that the primer sealant can have on the transfer of toolmarks (18). Cartridges with and without primer sealant were fired and consequently compared with each other. To objectify their observations, the IBISTM system was used to scan the imprint of the breechface in the primer. The authors observed a significant reduction of the quality of the striations, certainly the medium and light intensity markings. Hayes concludes that the lacquer acts as a shock-absorbing layer. The lacquer itself does seem to pick up breechface markings. While it might be standard operating procedure to remove the lacquer, it is recommended to investigate and photograph the cartridge case before this. Also, damage done to the firearm can affect a successful identification. Firearms that have to be searched for fingerprints are usually subjected to vaporous superglue. This means that the cyaonoacrylate glue will also set on the inside of the barrel and on the breechface of the slide. Bishop et al. have asked themselves whether or not this would hamper the identification of bullets and cartridge cases to the firearm (19). An experiment with a number of different firearms was performed. Bishop concluded that even though superglue did not hinder firearms identification, the practice of placing cotton in the barrel of a firearm when conduction latent print examination will protect the interior of the barrel and preserves any forensic evidence that might be of probative value prior to test firing the firearm. Fire damage can also be expected to cause a lot of trouble. The idea for a thorough study came to Gerber et al. after having done a case where the suspect had put fire to the crime scene where, afterwards, valuable firearms evidence was found. The authors want to assess the effects of fire and fire damage to the reliability of firearms identification (20). They have selected two different firearms: one with a ferrous and one with a non-ferrous frame. The guns were test-fired and then placed in a “homemade crime scene” that was consequently put to fire under controlled conditions. The firearms were recovered, cleaned, repaired and parts were exchanged with other firearms from the reference collection whenever necessary. After this, the guns were test-fired again and comparisons were made with the pre-fire test fires. The authors conclude that it is possible to identify bullets that have been fired from a gun prior to being burned in a fire to test fires taken after the firearms have been recovered. This proves also that it is feasible to clean and reassemble the damaged firearms into working order. The barrels show obvious signs of pitting and burning on the lands and grooves after the fire, which affected the amount and placement of the original individual markings. Consequently, some original individual markings disappeared while new ones appeared. Hess and Moran discuss a method for removal of superficial rust and corrosion from the working surfaces of firearms (21). After first having given an overview of the literature, the authors tested the chemical Whink® Rust Stain Remover. They propose a protocol for the treatment of firearms that are received in a bad condition 25


with the intent to restore any potentially surviving identifiable signature. The procedure has proven to be successful in addressing superficial to minor rusting of the working surfaces of firearms and is not intended as a method for “restoring” permanent damage to the working surfaces caused by rust/corrosion. A few authors also came up with some ideas to help improve identification or to critically evaluate the efforts that have been done in this direction. As it was proven by two empirical studies that the idea of a Ballistic Fingerprinting Database is not working with the currently available technology, the idea of nanotagging firearms gained interest. A NanoTagTM mark consists of a numerical code and possibly a bar code that is imprinted on top of or along the side of the firing pin. Krivosta has considered this idea and looked into its feasibility (22). He wanted to assess if the markings are readily decipherable, if they resist wear, and if they are susceptible to intentional defacement. Whereas the idea of a NanoTagTM seems simple and straightforward, many test fires demonstrate that a lot of change took place. It has been observed, by aid of the NanoTagTM mark, that a firing pin mark with four to five overlapping impacts as a result of one single firing does occur. The research has shown that implementing this technology will be much more complicated than burning a serial number on a few parts and dropping them into firearms being manufactured. It is widely accepted that a firearms open case file or a ballistic fingerprint file for that matter will become less and less efficient if the amount of data that is in it grows. It is likely that in certain countries a vast amount of firearms of the same make and model is used by criminals. These have, of course, similar class characteristics. For circular firing pin impressions, such as from the Kalashnikov assault rifle, Bati demonstrates that one can go one step further in using the width of the firing pin as a class characteristic to use as an exclusion parameter (23). A high reproducibility for the measurement of the width was obtained. This width can help to discriminate between different manufacturers of Kalashnikov rifles. Bati proposes a modified firing pin acquisition protocol for the IBISTM system that results in a much better performance of the correlation. As it is known to be quite a task to identify bullets that were fired through the polygonal barrels produced by Glock, the company has started to develop a barrel with more identifiable markings. The improvements were examined by the MiamiDade Police Department Crime Laboratory Bureau (24). The gross markings allow for quick indexing and the fine striations for improved identifications. These individual characteristics persisted after 3000 rounds and the bullets remained readily identifiable. One cannot, however, rely on the gross markings alone as they can be subclass carry-over. The new rifled barrel design is marketed by Glock as Enhanced Bullet Identification System (EBIS). Equipment This part aims to discuss the recent developments in equipment as the firearms and tool mark examiner strongly depends on it. Dutton had the opportunity to test the new generation of the LEICA comparison macroscope and made a critical comparison with the widely spread LEICA DM-C 26

(25). He firstly assesses the optics and objectives. The new FSC makes use of a turret which allows for six different objectives. On the macroscope he tested, there were only four installed. While the DM-C has the advantage of the zoom objective, Dutton feels that a comparison macroscope should never be used at different zooms as this is distorting the pattern and this means also changing reality. Furthermore, he looked at the available magnifications and the maximum is 60x. Dutton concludes that the available range could best be extended (e.g., with additional objectives) so that the range is from e.g. 2x to 90x. He also looked at the central control box that is available for the FSC. This control box commands the movement of the stages as the FSC is fully automated. Although the control box is straightforward to use, Dutton comments that it did take a little getting used to. The speed of the movement of the stages is variable for different magnifications. Overall, Dutton concludes that the new instrument certainly is an asset for any lab working in the field of firearms and toolmarks examination. His only reservation is the automation of the instrument, which makes it somewhat more difficult to operate. In a series of two papers Koch explains the technique of positive casts that was developed at the Bundeskriminalamt (26,27). With this technique one is able to make a complete replica of crime scene bullets and cartridge cases as well as any other object. The resolution of the casting is so high that even fine microscopic striation and impressed markings are duplicated. The castings can prove themselves useful in a number of situations, for example sending evidence to neighbouring countries without having to send the actual exhibit with the risk of loss or organising proficiency tests such that each participating institute will receive the exact same test items. Automation and 2D/3D imaging Recent research on automation and imaging techniques for forensic firearms applications has been continued by both commercial and government institutions. Additionally, several results have been reported by academia and other independent researchers. Some work reported on 2D imaging applications has been focused on the implementation of so-called “content based image retrieval” databases (28,29). CBIR databases allow objects to be searched for based on visual information such as shape, distance or relations between specific areas of interest (e.g., firearm screws), etc. New work on the analysis and automated comparison of projectile and cartridge case images (30,31,32) has also been reported on. Because it is very important to know how the performance of an automated system is affected, Nennstiel and Rahm discuss the parameters that have an important influence on the performance of the IBISTM correlator in (33,34). The first paper gives a general background whereas the second reflects the author’s experience with the open case file database. The success rate of the IBISTM correlator is defined as the probability of finding an existing match. This success rate depends on a number of variables: type of the mark taken into consideration (e.g. breech face, firing pin, …), number of evaluated mark types, mark quality, database size, number of test firings 27


and number of signatures from the same unrecovered firearm. Logically, the further one goes down the hit list ranking of the IBISTM correlator, the higher the chance for success. The authors demonstrate that the quality of the marks determines the success rate. Some brands of ammunition have better marks than others. It is important to select the same brand of ammunition for the test fires as was used to commit the crime. Besides, it is best to put multiple cartridge cases of the same gun in the system. However, the success rate will decrease with increasing size of the database. The data is best arranged in calibre/firearm subgroups. Based on the above parameters, the authors have tested their own system. They encourage inserting only the ammunition that is suitable for comparison as it is regarded essential for the use of any electronic pre-selection process. A success rate in the area of 75-95% for cartridge cases and 50-75% for bullets can be obtained under certain conditions. If these conditions are fulfilled, only the first 5 or 10 positions in the hit list should be checked, preferably regarding a combination of different marks. Insert more than one test fire and if available do the same for the specimens from the crime scene. It is furthermore advised to remove from the system any ammunition that passes a certain expiration period. Regarding the choice of ammunition, a study was performed by Bernard (35). The goals of this study were to determine if the IBISTM correlation scores are dependent on the brand of ammunition used, and which brand produces better scores. Bernard has test-fired Federal, Remington and Winchester jacketed ammunition through three different calibre guns: .38 revolver, .32 semi-automatic pistol and .45 semiautomatic pistol. The author not only compared the IBISTM scores of the cartridge cases: breechface, firing pin impression and ejector mark but also the Max LEA (land-engraved-area), Peak Phase and Max phase of the bullets. The results indicate that the calibre, ammunition brand or the two factors combined do not significantly affect the IBISTM ejector mark scores but they do affect significantly the Max Phase Scores, Breech Face Scores and Firing Pin Scores. However, the results did not reveal one best brand of ammunition. The author did not observe a statistically significant difference on the markings as a function of firearms use. De Kinder et al. assess the performance of a Reference Ballistic Imaging Database (RBID) (36). 600 9 mm Sig pistols were fired and inserted into the database. Two Remington cartridges and five additional brands were fired per firearm. One of the Remingtons of all 600 firearms was put in the database. Hereafter 32 firearms were randomly selected. For those firearms, the second Remington cartridge case as well as the five additional brands were compared to the RBID. Of the 32 Remington cases, only 72% ranked in the top 10 positions. Likewise, of the five different brands, only 21% ranked in the top 10 positions. It is very likely that a realistic reference ballistic imaging database may contain more than 600 firearms of the same brand and type. The results of the study illustrate that an RBID cannot adequately and efficiently compare specimens. Such a database is unsuitable for law enforcement work. Three-dimensional imaging methods have been studied in order to determine if 3D imaging methods can help to improve more traditional investigative work by providing 3D virtual microscopes and surface comparison tools (37,38,39). 28

Additionally, some results concerning the performance of (2D versus) 3D methods have been published (40,41,42). Using a comparison macroscope for the examination of pattern matching on bullets and cartridge cases will, to a certain degree, always imply some subjectivity of the examiner. And this is even before the examiner gets to the interpretation of the patterns. The illumination conditions to start with are very important; e.g., a grazing incident light allows the examiner to visualise 3-D features in the 2-D imaging plane. Any change in illumination may reveal a somewhat different pattern where striations may look broader or smaller. If the lighting for the two parts of the microscope is set differently, or equivalently, the questioned bullet or cartridge case is oriented in a different way, the examiner may potentially miss to see the matching pattern. Forensic Technology has developed and marketed over the past few years a new state of the art system that will analyse and compare the 3-D topography of the bullet or cartridge case rather than comparing 2-D images (43). This is an asset for ballistic comparisons as the third dimension contains valuable information. Using the improved MatchPoint+TM software it is furthermore possible to analyse the images using a combined 3D-2D visualisation, which should increase the success rate of the system. Forensic Technology challenged its newest 3D technology BulletTRAX-3DTM with a test involving 21 pairs of bullets, among which 20 are fired from consecutively manufactured and button rifled barrels (44). After scanning the bullets, the system performs an automated comparison of the land engraved areas (LEA) and returns a MaxPhase value. This value gives an indication of which LEA matches best with another LEA and adds up for the whole bullet. After a pre-training period of the system the authors found that the highest MaxPhase score for a known non match was 570. Therefore the authors defined a MaxPhase of 650 as a decision criterion. All bullets that were in a matching position exceeded this threshold value without any problem. Vorburger et al. (42) examine the feasibility and utility of a national ballistics database of casing and bullet images. Such a database would be set-up by conducting test firings for every weapon sold over the counter, with the intent of identifying any such weapon and its owner if the weapon would be used in a crime. This extensive and in-depth report (42) discusses issues such as distinguishability, gun and ammunition factors, region differences (breech face, firing pin, ejector marks), and topography and current optical technology. More specifically, the authors discuss results obtained using both a 2D-IBIS and their own 3D-measuring system, for two collections of test material (NBIDE, De Kinder). Among many other interesting (statistical) results, they conclude that the 3D measuring system demonstrated more accurate behaviour, but that the required performance for building a national database still remains an open problem. Similar studies are likely to appear in the future as 2D/3D issues may have an important impact on various aspects of currently used or developing investigative methods. In particular such studies may also extend existing and new work that discusses some performance issues of existing 2D identification database systems (32,36,42). 29


Shooting Incident Reconstruction General considerations Shooting Incident Reconstruction encompasses all techniques and knowledge that can be applied when examining a crime scene. Haag has recently combined his knowledge and expertise in a book (45) that provides the reader with a vast overview of criminalistic techniques that can be applied directly in field work. The book discusses how to recognise bullet impacts and how to prove them using chemical reagents, how to determine distance and orientation of the shot, how to reconstruct the bullet trajectory, what are the penetrating/perforating capabilities of bullets through different materials, how to recognise ricochet markings, what can be learned from trace evidence found on bullets, and many more items. Case examples and self performed shooting tests make the book easy to read and a must-have for every firearms examiner that goes out to process crime scenes. Although his book covers a great deal of information on shots through glass, Lucien Haag adds a few useful ideas in an AFTE Journal paper (46) Haag makes notice of the velocity drop of bullets perforating tempered glass under different angles. He further makes a suggestion for the determination of direction of fire as this can be more difficult than for bullet holes produced in single strength plate glass. Tempered glass is very fragile and it is likely to fall out of the window frame after impact. One should collect as many fragments as possible, especially ones with cone fractures. Notes of the interior and exterior side have to be made on samples of pieces of glass that are still stuck inside the frame. By use of ultraviolet light one side of the glass will strongly fluoresce. Not covered in his book is the issue of determining the calibre of bullets in surviving gunshot victims. It is not uncommon in cases of surviving gunshot victims that the projectile is not surgically removed. Sometimes an operation would do more damage or carry more risk than if one would just leave the bullet in place. It can be, however, important for the shooting reconstruction to know by which calibre/type of bullet the victim was struck. X-ray films can provide the means to determine this as bullets are radio opaque. The bullet length to diameter aspect ratio is independent of the scale of the photograph and can always be determined if the x-ray photograph is taken in a side-view. Haag et al. provide a table with the aspect ratios of some common encountered bullet types (47). As damaged or expanded projectiles do not have the same outlook as the pristine bullets, the authors suggest putting a reference projectile plate in the picture for easy comparison. In this reference plate one can put bullets that were fired in the water tank. This way, one can more easily distinguish the characteristics of e.g. the Federal Hydra-Shok or the Winchester Black Talon. Also Moran has written a chapter on shooting incident reconstruction in a book edited by Chisum (48. This chapter discusses general concepts in the investigation of shooting incidents with an emphasis on the reconstruction of events that occur at such scenes using a comprehensive approach that includes pre- and post-shooting incident considerations. Considerations for the forensic scientist are numerous in shooting incident reconstruction, but are not widely discussed in the literature. To this end, the author has attempted to organise the discussion into a chronological progression of considerations that include: 30

1) a philosophy of the critical thinking; 2) an introduction to various specific shooting incident/firearms related phenomenon that offer reconstructive information integrated with other forms of physical evidence; 3) practical approaches to reconstructive techniques that can be applied during the direct investigation of shooting scenes and/or resolving reconstructive issues that inevitably arise after the fact; and 4) practical considerations gleaned from a review of sources from both investigative and/or physical evidence prepared by various professionals in law enforcement and forensic science. However, within the confines of a single chapter, detailed descriptions of specific methods and procedures associated with shooting incident reconstruction are not practical. Therefore, emphasis in this chapter is placed on introducing the reader to an overall approach to shooting incident investigation and reconstruction. The ideas set forth in this chapter will better equip the reader to approach these investigations and thereby recognise pieces of the puzzle that might otherwise remain mute and to provide the best representation of such observations with regard to the application of the scientific method. This in turn will contribute towards a more successful shooting incident reconstruction. Klees presents a case report where the recovered fatal hollow point bullet showed no indication of expansion and only very slight deformation (49). He performed research into what could hamper the expansion or mushrooming of hollow point bullets. Hollow point bullets rely on simple hydraulic action to initiate radial expansion. As fluid enters the bullet’s nose cavity, the fluid gets compacted and will push the cavity walls aside under relatively high pressure. If a hollow point bullet impacts dry, intermediate targets first, the cavity might fill up with non-fluid material. This can prevent the cavity from expanding if the bullet consequently hits a fluid-like target. The worst non-fluid like material is probably wallboard that consists of gypsum. In a paper by Rowe, the author gives an exact calculation of the shotgun pellet pattern distribution of pellets impacting a flat surface (50). The pattern is usually visible as an elliptical mark. From the measurement of the shortest (W) and longest (L) axis of the ellipse, one can estimate the angle of impact. This can be done using a simplified formula sin = W/L. The author demonstrates that this simplified formula works well for most angles of impact. The error becomes larger for more grazing incident pellets. Sims and Barksdale have performed experiments to gain information about the ejection pattern of cartridge cases (51). The ejection is dependent on a number of variables: type of firearm, stance, hand and weapon position (grip) and movement. Five firearms with different calibre were test-fired from different stances (Weaver and Isosceles) and different grip: either two hands or one hand ‘gangster’ style. Among the five different weapons there were observable differences. The use of the original firearm and ammunition is, when possible, always the best choice. The different stances did not seem to have an important influence. The variable that 31


made the most difference was the grip. When fired with a normal grip, the casings end up to the right and slightly to the back of the shooter. When fired using a ‘gangster’ grip, the casings were located to the left and slightly behind the shooter. The type of surface the cartridge casings land on is bound to have an important influence as well. The authors learned the value of research when faced with the challenge of reconstructing the events of a crime scene. Wound ballistic simulations As the firearms examiner is frequently asked to assess the lethality or wounding capacity of projectiles, it is important to know which human body simulants could be used for the purpose of these types of tests. In a series of papers, Jussila thoroughly examines the existing techniques that are used nowadays for wound ballistic simulations. In a first paper (52), Jussila compares the different methods of gelatine fabrication that are reported. His research looks into the variables of preparing ballistic gelatine and their effects on penetration resistance. Jussila changed water pH, water temperature at different steps in the preparation and cooling time. Besides this, he looked at different gelatine batches. Reproducibility tests resulted in an empirical derived linear formula for the penetration depth versus impact velocity of a 4,5 mm steel BB. This formula and graph should be used for verification of the gelatine. Jussila makes the following recommendations: use purified water, calibrate every gelatine batch, do not use extreme water temperatures, store gelatine in a dark, dry and formaldehyde free environment and verify penetration with two shots at different velocities. Furthermore, Jussila describes a standard method for the preparation of 10% gelatine blocks. In a second paper, Jussila assesses the various methods that exist for the calculation of kinetic energy dissipation by a bullet into ballistic gelatine (53). The wound profile method (WPM), originally proposed by Fackler in 1985, gave the best correlation with the velocity drop as opposed to fissure surface area (FSA) and the total crack length method (TCLM). In the WPM, the lengths of the two largest cracks are added together to produce an estimate of the temporary cavity diameter. Correlation results of about 89% are obtained. Jussila suggests using an elastic shroud to hold the gelatine in place or, as an alternative, increase the size of the gelatine block. Besides testing the ballistic gelatine as a tissue simulant, Jussila compared various alternatives for the simulation of skin (54). It is generally accepted that the skin becomes an important factor once the bullets have very low velocities and/or impact under a grazing angle. The skin simulant should have values close to the average human skin, i.e.: threshold velocity of 94±4m/s, tensile strength 18±2N/mm² and elongation at break of 65±5%. Jussila first gives an overview of the literature where after 13 synthetic and natural alternatives are tested. A semifinished chrome tanned upholstery “crust” cowhide of 0,9 - 1,1 mm thickness gave the best results for the natural simulants. For the synthetic materials, the 1 mm thick rubber is a reasonable good alternative although its threshold velocity is somewhat lower than required. It can be used for worst case scenario ballistic reconstructions. Jussila is confident that a synthetic material with the desired properties can be developed for wound ballistic research.


Daubert hearings An important aspect of litigation may revolve around the scientific reliability and admissibility of investigative techniques and (resulting) evidence or testimony. This is particularly true in the U.S.A. where, at the trial of Daubert v. Merrell Dow Pharmaceuticals, Inc., the court outlined criteria which it believed could be important to establish the reliability of expert testimony. These criteria include the following:  Has the technique or theory been scientifically tested?  Does the technique or theory have a known or potential error rate?  Has the technique or theory been subjected to peer review and publication?  Is the technique or theory subject to standards governing its application?  Is the technique or theory generally accepted by the relevant scientific community? Although these criteria were not meant as a checklist, they are being applied in this way. If one of these criteria is not met, then any evidence or testimony may be found to be inadmissible. The SWGGUN website (55) provides an overview of information on Daubert as well as reports on Daubert hearings. The following Daubert hearings may be of interest to firearms examiners: 1. U.S. v. Edgar Diaz et al. Criminal #CR 05-00167 WHA, February 12, 2007 U.S. District Court of Northern District of California (Judge William Alsup)

2. U.S. v. Jamaal A. LEWIS. Criminal # U.S. Army 217-08-8512, October 3, 2006 Office of the Chief Circuit Judge, Fort Lewis, Washington (Judge Debra L. Boudreau) 3. Comm. of MA v. Jason MEEKS and Michael WARNER. Criminal Action #2002-10961 and #2003-10575, Sept. 27, 2006 Superior Court (Judge Raymond J. Brassard) 4. U.S. v. Darryl GREEN et al. Criminal #02-10301-NG, December 20, 2005 U.S. District Court of Massachusetts (Judge Nancy Gertner) 5. U.S. v. Amando MONTEIRO et al. Criminal #03-10329-PBS, November 28, 2005 U.S. District Court of Massachusetts (Judge Patti B. Saris) 6. U.S. v. Michael J. O'Driscoll. Criminal No. 4:CR-01-277, February 2003 7. U.S. v. Aaron DeMarco Foster. Criminal No. CCB-02-0410, February 2004 In summary, for each of these hearings, the court ruled that the firearms evidence and/or the expert’s testimony were sufficiently reliable. Nevertheless, some limitations or reservations were also formulated with respect to the scope, methodology or protocols used in some particular cases. Firearms – Chemistry During discharge from a firearm, primer and gunpowder residues as well as metal particles from the projectile and the cartridge case are escaping from the muzzle and other openings of the firearm. These residues are referred as primer residue, firearm discharge residue or Gun Shot Residues (GSR).



Inorganic GSR General considerations Scanning Electron Microscopy coupled to Energy Dispersive X-ray microanalysis (SEM/EDX) still is the method of choice for the identification of inorganic GSR on samples. In 2005 a group of internationally recognised GSR experts convened at an FBIorganised symposium to discuss the relevant topics related to inorganic GSR examinations using SEM/EDX (56): GSR definition, composition, sampling, contamination, case-acceptance criteria and report writing were discussed. A general consensus was reached that a spheroid, condensed or rounded particle morphology in conjunction with the three-component lead-barium-antimony should be considered as characteristic of GSR particles. On the topic of samples collected from suicide victims, it was concluded that the presence of GSR cannot determine with a high degree of certainty whether the victim’s death was the result of a homicide or suicide. Some recommendations were also stated with respect to testing of clothing. Finally most participants agreed that in order to compare GSR found on the suspect, it may well be interesting to analyse the victim’s clothing and/or the expelled cartridge case of the crime scene as reference material. It is, however, noted that residue produced in a test firing of the firearm may well contain contributions from other discharges, and that therefore interpretation of comparisons should be handled with caution. Fundamentals of GSR formation De Forest et al. determined the velocity of gunshot particles using high speed stroboscopic photography (57). While most particles have enough energy not to be influenced by normal wind velocity and to embed themselves on certain nearby targets, they decelerate rapidly, explaining why only few particles are found beyond a certain distance (e.g. 1 m range). Concerning the effect of revolver cylinder gap on GSR production, as expected the greater the space, the more the production of GSR to the side. This was illustrated with an example (58). With the increasing interest of the scientific community in nanomaterials and nanostructures, an application to GSR in this domain was proposed by Yang et al. (59), who analysed the formation of nanometer-sized lead particles from the condensation of the lead vapour emitted from the barrel at the time of discharge. The authors noted a marked linear relationship between the size of the nanoparticles (50 to 200 nm diameter range) and the distance to the target (10 to 50 cm range). The nucleation process of the lead spheres was modelled using thermodynamic and diffusion principles and the resulting calculated lead particle diameter is in accordance with the general findings on samples acquired from firing a Winchester 9mm cartridge from a semiautomatic handgun.


Interpretation Most handgun ammunition manufacturers now offer lead-free ammunition because of health concern on airborne lead produced by firearms. With lead removed, this ammunition does not produce the characteristic lead-barium-antimony particles, preventing correct identification of GSR (false-negatives). Oommen and Pierce studied eight lead-free ammunitions, in order to characterise the composition of the particles produced by these ammunitions (60). All of the eight ammunitions contain some combination of Al, Si, Cu and Zn, sometimes associated with specific elements such as Sr, Sn, K and/or Ba. With the increasing use of such ammunitions, this study points out the necessity of a case by case approach in order to prevent falsenegatives. However, further studies are necessary to identify environmental sources of particles containing similar compositions. Deposition of GSR particles in the shooting environment is an important study subject in the context of crime scene interpretation. Fojtasek and Kmjec (61), have studied the deposition time of microscopic particles in the vicinity of the shooter. Experiments with two pistols and a revolver show that the deposition of GSR particles takes place over a period of several minutes after the shot is fired. Interpretation of crime scene analysis results clearly need to take this deposition time into account as it is possible that a person entering the scene moments after the shot is fired can very well be contaminated, and the shooter who leaves the scene quickly may, on the contrary, show a less positive result as was formerly expected. Based on an empirical study of police vehicles and facilities, Berk et al. have evaluated the potential contamination risk due to secondary transfer (62). Although the potential for secondary contamination seems to be low, some recommendations such as transporting the suspects in vehicles with vinyl seats or not reusing equipment without maintenance are stated. These considerations have been summarised in the New Scientist by Mejia (63), in stating that due to the differences in evaluating the contamination risks by different crime labs and police forces, the credibility of the science behind GSR analysis is put to the test. Criminalists should therefore be more consistent in evaluating the test results in light of possible contamination by police forces, particle deposition times and composition with regard to possible other sources like brake pad linings. In the context of the interpretation of the GSR analysis results, a few interesting publications illustrating the use of Bayesian principles have appeared. Although their article is concerned with the application of Bayes’ theorem in toolmarks problems (see previous section), Deinet and Katterwe (10) show a very clear derivation of the principles behind the Bayesian approach and emphasise the need of the courts for the experts to offer not only a likelihood ratio, but also discuss prior probabilities. This is argued as the experts are the only ones able to assess these factors from their experience and scientific know-how. One of the first applications of Bayesian principles to GSR is reported by Biedermann and Taroni (64); they take as an example the interpretation using Bayesian principles of combined results of ballistic bullet striation comparisons and shooting range evaluation obtained by chemographic methods. It is shown that in 35


the case of experiments for which by their nature likelihood ratios are difficult to calculate, the use of Bayesian networks is still possible. Moreover Cardinetti et al. (65) show that the application of simple statistical techniques can offer substantial insight into the interpretation of results of GSR analysis experiments. Applying a statistical framework of Poisson distributed means for the calculation of probabilities of finding a number of GSR particles on the hands of a group of shooters and non-shooters after a certain time since firing, they show that the calculated likelihood ratio reveals very reasonable results for the expected number of GSR particles. This technique can easily be applied to similar experiments. Instrumental methods An extended application of SEM/EDX, i.e. X-ray mapping, has been proposed by Cardinetti et al. in order to discern between true GSR particles and other nonfirearm related particles with similar compositions (66). Specifically in the areas of automobile, pyrotechnics and electrical engineering a number of sources of the latter type of particles have recently been identified. X-ray mapping was applied on particles originating from brake linings of different models of cars, hand samplings of subjects with particular occupations, as well as from cartridge types of different make and calibre. The results show that all of these sources can potentially produce X-ray spectra with the characteristic lead-barium-antimony composition, making a correct GSR classification based on the spectrum alone problematic. Due to differences in the physical conditions of their formation, however, the spatial distribution of the elements in the particles differs. This effect can be visualised by X-ray mapping. The authors therefore suggest that the use of X-ray mapping is becoming an indispensable tool in discerning true GSR particles from similar environmental aggregates. While SEM/EDX is nowadays routinely used in forensic laboratories, bulk methods such as Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) are still attractive for special applications. Roeterdink et al. (67) report the analysis by ICP-MS of GSR extracted from larvae. Significantly higher concentrations of lead, barium and antimony were detected within larvae feeding on a shot piece of beef. This method could be used in caseworks for which there are no identifying marks on decomposing corpse, in order to establish whether a firearm was or was not involved in the death. Proficiency tests for GSR analysis by SEM/EDX Niewoehner et al. (68) published the results of the latest proficiency test program GSR2003. The principle of this test had already been reviewed in the previous report paper (14th Interpol Forensic Science Symposium), but for the first time threeelement composition lead-barium-antimony particles were prepared and distributed in four size classes (2.4 µm, 1.2 µm, 0.8 µm, 0.5 µm). As expected, the smaller the size, the lower the detection capability.


Estimation of shooting distance General considerations Nichols reviewed gunshot proximity testing in order to provide firearms examiners with a single comprehensive resource (69). Variables such as gun and cartridge characteristics, target material and environmental conditions are discussed. These variables have to be as far as possible controlled to achieve good interpretations of the evidence. Visual and chemical examinations were also reviewed. An additional paper (70) by the same author deals specifically with shotguns and related issues such as shot dispersion since examination and interpretation of shotgun proximity testing is substantially different from other firearms. Haag illustrates with an example (12 gauge shot shell) the necessity to use the same type of ammunition that was fired during an incident in order to estimate shooting distances (71). Another article deals with special cases where specific low-density particles, coming from plastic buffer material present in some American shotgun ammunitions, are used to determine shooting distances (72). The distribution of shotgun pellets after ricochet was studied by Rowe, using a geometric approach (50). Colour tests A muzzle-to-target distance determination necessitates GSR patterns visualisation. If this can be done by direct observation on light-coloured garments, chemical tests are often performed after visual examination since some residues are not visible to a macroscopic examination. This is particularly true for dark, multi-colored or bloodstained fabrics. The Modified Griess Test (for nitrites) followed by the Sodium Rhodizonate Test (for lead and barium) is still the preferred method for examining GSR patterns. The latter has to be conducted in an acidic environment in order to reveal the metals. However the acidic medium and the order of spraying seem to be major factors on colour intensity and persistency. Rawls et al. tested tartaric acid, acetic acid and sodium bitartrate media (73). They concluded that spraying 2% sodium bitartrate followed by rhodizonate solution is the best procedure to reveal lead, while still discriminating barium from lead. Copper can be detected by using either 2-nitroso-1-naphtol or dithiooxamide. These chemical tests were recently summarised by Haag et al. (74). The importance of colour tests was pointed out by Adeyi et al (75) who report a case for which a false conclusion could have been proposed just by observing the entrance wound. In this example the analysis of GSR dispersion using the Sodium Rhodizonate Test led to a different conclusion, illustrating that possible detailed examinations and additional tests have to be performed in order to yield correct interpretations. The Modified Griess Test protocol for nitrites identification uses desensitised blackand-white photographic paper. However with the increasing scarcity of such papers, an alternative is the use of inkjet photographic papers (76). It saves time and money since the desensitisation step and the use of a dark room facility are avoided. The performances of several commercial inkjet papers were evaluated (77,78). Though some of the tested papers are not suitable, others give better results than traditional black-and-white photographic paper; moreover these papers do not interfere with 37


the Sodium Rhodizonate Test (77), often used in conjunction with the Modified Griess Test. Nevertheless, these chemical techniques usually necessitate the GSR to be transferred to a support and so are destructive to evidence. Bailey et al. (79,80) report the use of a sodium hypochlorite solution for direct visualisation on dark and multi-colored fabrics, by bleaching the dyes and eliminating the background colour. Although the use of sodium hypochlorite does not influence the GSR pattern size, some fabrics (2 of 12 tested) cannot be bleached. Targets Marshall conducted experiments in order to evaluate fabric media and target pigskin on visible gunpowder particles dispersion and sodium rhodizonate patterns (81). If cotton seems to be a good simulant to pigskin, high variations between the fabrics were observed, probably due for the most part to differences in interaction with GSR. This again states the importance to use the same test material when conducting range tests, since visual and chemical examinations can lead to variations depending on the type of material being used. The issue of hair effects has also been reported (82): when trying to identify visual GSR and interpreting distance estimations, the hair can act as a filter and bad conclusions can be drawn if no (or only a few) GSR are observed. For very close distance for which target materials are not suitable because of their fragility, craft foam seems to be suitable (83). Non-destructive techniques The development of non-destructive techniques for direct observation of GSR patterns has also been reported. For instance alternative light sources are widely used in forensic laboratories for questioned documents, fingerprints etc. The use of these sources was extended to GSR patterns with success (84,85,86). However further investigation and validation studies are necessary to prevent misinterpretation and artefacts (84,85). X-ray techniques (85) may also be valuable methods for direct observation of GSR patterns. Recently, Berendes et al. reported the use of millimetre-X-ray fluorescence analysis (m-XRF) equipped with a special sample holder as a valuable technique for the investigations of GSR patterns (87). It allows XRF mapping of large surfaces (20x20 cm²) within 4 hours, with access to qualitative and semi-quantitative GSR distributions. Organic GSR Screening of gun propellant powder components Smokeless powder is the primary propellant in civilian and military ammunition and is used in the fabrication of improvised explosive devices (IEDs). This powder is composed of nitrocellulose (propellant), nitroglycerin (energetic material) and additives such as diphenylamine (stabiliser), ethylcentralite or methylcentralite (stabilisers and/or gelatinisers), dinitrotoluene isomers (flash suppressor). Diphenylamine is known to decompose into N-nitrosodiphenylamine and into 38

various nitroderivatives. Determining the additive contents presents an important forensic interest in the investigation of criminal cases for which the use of firearms or IEDs is known or alleged. Mathis and McCord developed a gradient reversed-phase liquid chromatographicElectrospray Ionisation Mass Spectrometric (ESIMS) method for the comparison of smokeless powders (88). The efficiency of electrospray ionisation was first studied by infusing individual standards of powder components in a methanol/aqueous ammonium acetate solution. A separation method (i.e. LC for Liquid Chromatography) was then developed using the optimised ESIMS parameters. The resulting LC-ESIMS method was applied to determine the organic additives in several smokeless powders. The authors concluded that the developed method should prove useful in the analysis of compositional variation and smokeless powder degradation. Additionally, the same authors studied the mobile phase influence on a positive electrospray ionisation for the analysis of smokeless powders with the above-mentioned method (89). In this study, several parameters were investigated. The results of the analysis showed that the electrospray ionisation of smokeless additives is affected by the acetate ammonium concentration, as well as by the pH of the solution. West et al. investigated the use of ion mobility spectrometry (IMS) for the detection of ethylcentralite, diphenylamine and some of its nitroderivatives (90). Standards and gunpowder samples were analysed in both positive and negative ion modes. The authors report that gunpowder stabilisers can be detected using dual-detection modes: ethylcentralite, diphenylamine and N-nitrosodiphenylamine are detected in positive ion mode; while nitroderivatives of diphenylamine are screened in negative mode. This mode is usually selected to detect nitro compounds such as nitroglycerin, dinitrotoluene and trinitrotoluene. To assess the accuracy of quantitative measurements of additive contents of propellants/explosives by the use of various analytical methods, the US National Institute of Standards and Technology (NIST) has developed a smokeless powder reference material (91), which provides reference concentrations with relative uncertainties less than 5% for nitroglycerin, diphenylamine, Nnitrosodiphenylamine and ethylcentralite. As smokeless powders contain also inorganic ions, Hopper and McCord used capillary zone electrophoresis methods to determine the inorganic ion contents of burned and unburned smokeless powders (92). A variety of smokeless powders and samples from deflagrated or intact pipe bombs were analysed. Notably, the authors pointed out that the concentration of inorganic ions in burned and unburned smokeless powders could yield information in the characterisation of such a material. Instrumental methods for organic gunshot residue (OGSR) analysis Muller et al. suggest a novel method for the analysis of discharged smokeless powder residues left on a target material (93). This method, including Modified Griess Test and gas chromatographic analysis (gas chromatography/thermal analysis and gas chromatography/mass spectrometry) of nitroglycerin, 39


dinitrotoluene and stabilisers, is devoted to the estimation of intermediate-to-long firing distance ranges. Full metal jacketed bullets were used to perform firings with a 9 mm Luger FN semiautomatic pistol. The authors concluded that in the firing distance range of 0,75-3 m, the Modified Griess Test is not adequate to confirm the GSR nature of the few particles found on the target because of its lack of specificity. A complementary instrumental analysis (using gas chromatography) of the organic components of the particles may confirm the nature of the GSR. OGSR analysis is also recommended when the traditional SEM/EDX analysis of metallic particles fails to confirm the presence of GSR, particularly due to the use of lead-free ammunition or ammunition without heavy metals. Laza et al. developed a quantitative liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) method for the analysis of common propellant powder stabilisers in gunshot residues (94). Samples were collected from hands of a shooter immediately after firings with various types of firearms and ammunition. Samples were prepared using a solid phase extraction protocol and were subsequently analysed by LC-MS/MS. The authors confirm that this method constitutes an alternative technique for OGSR analyses. However it should be optimised for an efficient detection of OGSR expelled from calibres smaller than 9mm Para. Zeichner et al. have conducted a feasibility study of the use of Ion Mobility Spectrometry (IMS) for the analysis of gunpowder residues collected from clothing worne by shooting suspects (95). They assess the applicability of the portable sampler combined with the fibreglass and the Teflon filters, which are supplied with the commercial IMS instrument. Samples collected by vacuuming were treated by solvent extraction and were subsequently analysed by IMS, gas chromatography/thermal energy analyser (GC/TEA) and by gas chromatography/mass spectrometry (GC/MS). The authors concluded that the IMS portable vacuum sampler was feasibility to use for gunpowder residue collection from the clothing of suspects even if this clothing was previously sampled by the tape-lift method for inorganic GSR analysis with SEM/EDX. GC/TEA and IMS were found sensitive enough to detect and identify gunpowder residues in real cases. Combining GC/TEA, IMS and SEM/EDX, Zeichner and Eldar proposed a novel method for extraction and analysis of gunpowder residues on double-sided adhesive-coated stubs which are usually used for the collection of primer residues (1) prior to SEM/EDX. The efficiency of the extraction procedure was studied using different solvent compositions and various samples which were composed of a standard working solution of nitroglycerin and 2,4-dinitrotoluene mounted on an adhesive-coated stub. An optimised extraction procedure was applied to the analysis of gunpowder residues and was tested in shooting experiments. Concluding on the feasibility of the extraction and analysis of gunpowder residues collected with adhesive coated stubs, the authors reported that the extraction may be carried out after the traditional analysis of the stub by SEM/EDX. Bird et al. (97) discuss the first (to their knowledge) application of time-resolved fluorescence microscopy to GSR particles. In their study macroscopic partially burnt propellant GSR particles, produced from firing a Winchester .38 special cartridge at 40

a cotton fabric target, were collected and individually mounted on microscope slides. The particles were imaged by time-resolved confocal laser scanning microscopy and the time-resolved imaging was carried out by time-correlated single photon counting. Theoretically, the major constituents of powder (nitro compounds like nitrocellulose and nitroglycerine) do not exhibit specific fluorescent behaviour, but the additives (stabilisers, oxidisers, etc.) may very well do. The authors demonstrate that a spatial distribution of the lifetimes of the emitting species allows for the identification of the GSR particles. The results indicate that the examined GSR particles do contain undetermined emitting species with different fluorophore lifetimes and that the fluorescent effect, observed when using forensic light sources on targets, originates from a light scattering effect in combination with pure fluorescence. Mahoney et al. (98) used Time-of-Flight Secondary Ion Mass Spectrometry (TOFSIMS) to characterise the organic composition of unburnt propellant powders. Smokeless powders, black powders and black powder substitutes were analysed. Positive results were obtained in analysing all additives in smokeless and black powder, both organic (like ethyl centralite, dibutyl phtalate and nitrocellulose) and inorganic (like potassium nitrate, potassium perchlorate and sulfur) in nature. Using Principal Component Analysis (PCA), the samples could be clustered in the different groups they belong to, showing the applicability of the technique in this field. This is very interesting in cases where unknown samples need to be compared to reference materials. Because of the high-vacuum conditions inside the instrument, however, the technique is not very well suited for the analysis of the more volatile components such as nitroglycerine. Use of special analysis or sampling techniques Sampling Hanson and Springer (99) discuss the use and applicability of the Instant Shooter Identification (IsidTM) Sampling Kits produced by Law Enforcement Technologies Inc. This binary test uses a swab and indicator liquid to yield a colour reaction on the presence of nitrates, upon which the results can be confirmed with SEM/EDX analysis of the swab. Shooters were sampled immediately after shooting or after a delay (from five minutes to three hours). It is concluded by the authors that the Isid Kit is inferior to the classic stub sampling method for several reasons such as i) the effectiveness of nitrate detection and its visual identification by the expected colour and ii) the effectiveness and the time-consuming of particle identification on the swab by SEM/EDX analysis. Hall and Fairley propose a single approach to the recovery of DNA and GSR on garments (100): prior to analysis, GSR are collected using the conventional tape-lift method. After SEM/EDX analysis, the adhesive tapes are removed from the aluminum stubs and the DNA is extracted for identification. The usefulness of this method is illustrated with two caseworks.



Ferrotrace The method used to visualise firearm imprints on hands is the “Ferroprint” or “Ferrotrace” test, consisting in spraying an aqueous solution of PDT (3-(2-pyridyl)5,6-diphenyl-1,2,4-triazine) and ascorbic acid on the hands; this test reveals the presence of iron due to the formation of a magenta complex. In order to determine why some persons develop clear marks while others do not, Almog et al. conducted quantitative studies on several factors influencing stain intensity (101,102). The authors demonstrated the relationship between stain intensity and quantity of iron present on the hands; they also pointed out palmar moisture level and gripping period as major factors influencing stain intensity. Finally the transfer process of iron was found to be a chemical dissolution rather than a mechanical dislodgement; in this process, chloride ions (present in high levels in palmar sweat) seem to have a significant effect by enhancing the dissolution. The analysis and use of bullet lead composition As was already known, there is a substantial bullet lead deposition inside the barrel of a firearm. This “lead memory” effect renders the association of bullet composition to the firearm – and hence the shooter – in most cases difficult. Zeichner et al. (103), have shown, using Multiple-Collector Inductively Coupled Plasma/Mass Spectrometry (MC-ICP/MS) that this memory effect is impossible to remove using mechanical and chemical means. However, in certain particular cases, where several firearms were used employing types of ammunition with bullet lead isotope ratios differing significantly between ammunition types/firearms, it may be possible to point out which bullet/firearm caused a particular gunshot entry in the target. Also, although there is a significant variation of lead isotope ratios among bullets, cartridges and primers produced by the same manufacturer, it is generally possible to distinguish specific batches of ammunition from different manufacturers. On the subject of eliminating the lead contamination from a gun barrel, Haag and Niewoehner (104) show that even after the firing of a substantial number of lead-free cartridges through a lead fouled barrel, the “lead memory” effect of the barrel remains visible with SEM/EDX in the elemental X-ray mapping mode. The residual lead deposition seems to be concentrated predominantly in the groove/land interface area. It is well known that bullet lead composition varies within the production lines of all manufacturers, even to the extent that the bullets in one box may show differences when analysed with the sensitive and accurate instruments of forensic science. The use of such analytical data in casework comparisons of bullet and shot samples is therefore often scrutinised. In the field of evidential value of lead trace element analysis for use in bullet matching, an article published in 2002 (105) stated that bullets with indistinguishable compositions could have come from different sources. However in a recent study Koons and Buscaglia (106) have compared a sample set of 1837 bullets and shot pellets selected from case samples received by the FBI Laboratory in the period 1989 to 2002. Analytical Inductively Coupled Plasma Optical Emission Spectrometry I(CP-OES) and Nuclear Activation Analysis (NAA) data of seven trace elements (Sb, As, Bi, Cd, Cu, Ag and Sn) was used in determining the uniqueness of a bullet in this set. The results of the study show that 42

the probability of the occurrence of an exact match is of the order of 10-3 to 10-5. It is therefore very unlikely that a bullet recovered from a crime scene having the exact same trace element composition as another bullet found on a suspect would come from a different source. References 1.

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Howitt D, Tulleners F, Cebra K, Chen S. A calculation of the statistical significance of the consecutive matching line criteria used for the analysis of bullets. Submitted for publication to Journal of Forensic Sciences. And additionally: The statistical significance of a bullet match. Presentation at the AFTE2007 trainings seminar. San Francisco, CA; The statistical significance associated with matching lines on a bullet. Presentation at the The Eighteenth Annual International Scientific Meeting on Scanning Microscopies, Monterey, CA.


Pauw-Vugts P. FAID 2005 – Proficiency test or collaborative study of firearms identification, presented at the AFTE 2007 training seminar in San Francisco, CA. (


Chow SM, Striupaitis P, Haskell N, Gaensslen RE. Time-dependent effects of the putrefaction in bodies on individualizing striation mMarks on bullets – A pig model. AFTE Journal 2003; 35(4); 388-393


Larrison RM. Degradation of fired bullets and cartridge cases in different environmental mediums. AFTE Journal 2006; 38(3); 223-230


Hayes CS, Basoa M, Freese R. Reduction of characteristic breechface marks due to primer sealants. AFTE Journal 2004; 36(2); 139-146


Bishop B, Rosati C, Leas R, Ennis M, Lee J, Janeksela V. Does superglue hinder traditional firearms identification? AFTE Journal 2005; 37(1); 3-7


Gerber K, Marsanopoli J. Effects of fire damage on the ability to make identifications part 1: bullets. AFTE Journal 2005; 37(3); 206-212


Hess PA, Moran B. The removal of superficial rust/corrosion from the working surfaces of firearms for the purpose of revealing their potentially identifiable signature and an application of this technique in a firearms identification. AFTE Journal 2006; 38(2); 112-132


Krivosta GG. NanoTagTM markings from another perspective. AFTE Journal 2006; 38(1); 41-47


Bati C. The width of the firing pin imprint as a class characteristic in 7,62 x 39 mm Kalashnikov cartridge cases. AFTE Journal 2007; 39(1); 24-30


Fadul TG, Nuñez A. Glock’s new “EBIS” barrel: the finale to the Miami barrel saga. AFTE Journal 2006; 38(2); 96-100


Dutton G. LEICA FSC comparison macroscope. AFTE Journal 2004; 36(4); 256261 44


Koch A. Abformungen bei der Waffen- und Munitionsuntersuchnung. Der Auswerfer. Sonderausgabe Schusswaffensymposium München. 67-80


Koch A. Abformtechniken für komplexe 3-D Strukturen. Der Auswerfer 18; 5783


Murthy SS, Mazumdar C, Rao MS, Pal AK. Digital image matching of 9mm pistols. AFTE Journal 2004; 36(2); 155-165


Wen CY, Yao JY. Pistol image retrieval by shape representation. Forensic Science International 2005; 155; 35-50




Brein C. Segmentation of cartridge cases based on illumination and focus series. SPIE Conference Proceedings, Image and Video Communications and Processing 2005; 5685; 228-238


Leon FP. Automated comparison of firearm bullets. Forensic Science International 2006; 156; 40-50


Nennstiel R, Rahm J. A parameter study regarding the IBISTM correlator. Journal of Forensic Sciences 2006; 51(1); 18-23


Nennstiel R, Rahm J. An experience report regarding the performance of the IBISTM correlator. Journal of Forensic Sciences 2006; 51(1); 24-30


Bernard M. The effects of ammunition brand and firearm use on IBIS correlation scores. Canadian Society of Forensic Science Journal 2005; 38(2); 6983


De Kinder J, Tulleners F, Thiebaut H. Reference ballistic imaging database performance. Forensic Science International 2004; 10; 207-215


Senin N, Groppetti R, Garofano L, Fratini P, Pierni M. Three-dimensional surface topography acquisition and analysis for firearm identification. Journal of Forensic Sciences 2006; 51(2); 282-295


Banno A, Masuda T, Ikeuchi K. Three dimensional visualization and comparison of impressions on fired bullets. Forensic Science International 2004; 140; 233-240


Song J, Vorburger T. Topography measurements and applications. SPIE Conference Proceedings, Third International Symposium on Precision Mechanical Measurements 2006; 6280

. Li D. Ballistics projectile image analysis for firearm identification. IEEE Transactions on Image Processing 2006; 15(10); 2857-2865




Thompson E. Editorial: Two dimensional characteristics. AFTE Journal 2006; 38(1); 10-13


Roberge D, Beauchamp A. The use of BulletTrax-3D in a study of consecutively manufactured barrels. AFTE Journal 2006; 38(2); 166-172


Vorburger TV, Yen JH, Bachrach B, Renegar TB, Filliben JJ, Ma L, Rhee HG, Zheng A, Song JF, Riley M, Foreman CD, Ballou SM. Surface topography analysis for a feasibility assessment of a national ballistics imaging database. NISTIR 7362 (National Institute of Standards and Technology), Gaithersburg, MD, USA, 2007,


Forensic Technology Inc. The development of IBIS-TRAX 3DTM: BulletTRAX3DTM and BrassTRAX-3DTM.


Roberge D, Beachamp A. The use of BulletTRAX-3D in a study of consecutively manufactured barrels. AFTE Journal 2006; 38(2); 166-172


Haag LC. Shooting incident reconstruction. Academic Press (Elsevier) USA 2006; ISBN-13:978-0-12-088473-5; ISBN-10:0-12-088473-9.


Haag LC. Sequence of shots through tempered glass. AFTE Journal 2004; 36(1); 54-64


Haag LC; Garrett, ML. Bullet length to diameter ratios and caliber determination of bullets in surviving gunshot victims. AFTE Journal 2007; 39(1); 31-43


Moran B. Shooting incident reconstruction. Chapter 8 (215-312) in the book entitled Crime Reconstruction by Chisum and Turvey. Academic Press (Elsevier) USA 2006; ISBN-10:0-12-369375-6.


Klees GS. The un-expanded hollow point bullet-observations of terminal effects from a shooting scene examination. AFTE Journal 2005; 37(3); 184-186


Rowe WF. The distribution of shotgun pellets after ricochet from an intermediate target surface. Forensic Science International 2005; 155; 188-192


Sims E, Barksdale L. The importance of careful interpretation of shell casing ejection patterns. Journal of Forensic Identification 2005; 55(6); 726-740


Jussila J. Preparing ballistic gelatine–-review and proposal for a standard method. Forensic Science International 2004; 141; 91-98


Jussila J. Measurement of kinetic energy dissipation with gelatine fissure formation with special reference to gelatine validation. Forensic Science International 2005; 150; 53-62






Jussila J. Ballistic skin simulant. Forensic Science International 2005; 150; 63-71


The Scientific Working Group SWGGUN:


Wright DM, Trimpe MA. Summary of the FBI Laboratory's Gunshot Residue Symposium, May 31-June 3, 2005. Forensic Science Communications 2006; 8(3)


De Forest PR, Martir K, Pizzola PA. Gunshot residue particle velocity and deceleration. Journal of Forensic Sciences 2004; 49(6); 1237-1243


Haag LC, Tew J. The effect of revolver cylinder gap on GSR production and projectile velocity. AFTE Journal 2006; 38(3); 204-212


Yang J, Gunn A, Palmbach T, Wei D, Sinha S. Nanoparticles in gun-shotresidue. 2006 IEEE Conference on Emerging Technologies - Nanoelectronics 2006; 269-272


Oommen Z, Pierce S. Lead-free primer residues: a qualitative characterization of Winchester Winclean™, Remington/UMC LeadLess™, Federal BallistiClean™, and Speer Lawman CleanFire™ handgun ammunition. Journal of Forensic Sciences 2006; 51(3); 509-519


Fojtasek L, Kmjec T. Time periods of GSR particles deposition after dischargefinal results. Forensic Science International 2005; 153(2-3);132-135


Berk RE, Rochowicz SA, Wong M, Kopina MA. Gunshot residue in Chicago police vehicles and facilities: an empirical study. Journal of Forensic Sciences 2007; 52(4); 838-841


Mejia R. Why we cannot rely on firearm forensics. New Scientist 2005;188(2527); 6-7


Biedermann A, Taroni F. A probabilistic approach to the joint evaluation of firearm evidence and gunshot residues. Forensic Science International 2006; 163(1-2); 18-33


Cardinetti B, Ciampini C, Abate S, Marchetti C, Ferrari F, Di Tullio D, D’Onofrio C, Orlando G, Gravina L, Torresi L, Saporita G. A proposal for statistical evaluation of the detection of gunshot residues on a suspect. Scanning 2006; 28; 142-147


Cardinetti B, Ciampini C, D’Onofrio C, Orlando G, Gravina L, Ferrari F, Di Tullio D, Torresi L. X-ray mapping technique: a preliminary study in discriminating gunshot residue particles from aggregates of environmental occupational origin. Forensic Science International 2004, 143;1-19


Roeterdink EM, Dadour IR, Walting RJ. International Journal of Legal Medecine 2004; 118; 63-70




Niewoehner L, Andrasko J, Biegstraaten J, Gunaratnam L, Steffen S, Uhlig S. Maintenance of the ENFSI proficiency test program on identification of GSR by SEM/EDX (GSR2003). Journal of Forensic Sciences 2005; 50(4); 877-882


Nichols RG. Gunshot proximity testing: a comprehensive primer in the background, variables and examination of issues regarding muzzle-to-target distance determinations. AFTE Journal; 2004 36(3); 184-203


Nichols RG. Shotgun proximity testing: a review of the literature regarding muzzle-to-target distance determinations involving shotguns. AFTE Journal 2006; 38(3); 192-203


Haag M. Shotgun pellet patterning: Federal’s FLITCONTROLTM law enforcement shotshell. AFTE Journal 2006; 38(3); 231-238


Haag LC. Shotgun range of fire determinations from skin stippling by plastic buffer material. AFTE Journal 2007; 39(1); 50-61


Rawls DD, Ryan JP. Modified Feigl test for lead. AFTE Journal 2006; 38(3); 213222


Haag M, Haag L. Trace bullet metal testing for copper and lead at suspected projectile impacts. AFTE Journal 2006; 38(4); 301-309


Adeyi O, Duval JV, Dupre ME, Andrew TA. Role of chemical tests and scene investigation in determination of range of fire. American Journal of Forensic Medicine Pathology 2005; 26(2); 166-169


Malikowski SG. Alternative modified Griess test paper. AFTE Journal 2003; 35(2); 243


Hess PA, Poole LL. The validation of inkjet photographic paper for use with the Modified Griess Test. AFTE Journal 2005; 37(3); 213-223


Gamboa FA, Kusumi R. Evaluation of photographic paper alternatives for the Modified Griess Test. AFTE Journal 2006; 38(4); 339-347


Bailey JA. Enhancement of gunshot residue patterns on dark colored fabric using sodium hypochlorite. AFTE Journal 2005; 37(3); 169-171


Bailey JA, Casanova RS, Bufkin K. A method for enhancing gunshot residue patterns on dark and multicolored fabrics compared with the modified Griess Test. Journal of Forensic Sciences 2006; 51(4); 812-814


Marshall J. Visual and chemical variability in gunpowder residue deposition on different fabric media. Canadian Society Forensic Science Journal 2006; 39(3); 115-124



Jason A. Effect of hair on the deposition of gunshot residue. Forensic Science Communications 2004; 6(2)


Martini L. Craft foam: a target material for distance determination. AFTE Journal 2004; 36(3); 242


Chaklos DL, Davis AL. Visualization of gunpowder residue patterns using a digital infrared camera and optical filters. AFTE Journal 2005; 37(2); 117-122


Giroux BN. Non-destructive techniques for the visualization of gunshot residue. AFTE Journal 2006; 38(4); 327-338


Atwater C.S, Durina ME, Durina JP, Blackledge RD. Visualization of gunshot residue patterns on dark clothing. Journal of Forensic Sciences 2006; 51(5); 1091-1095


Berendes A, Neimke D, Schumacher R, Barth Martin. A Versatile Technique for the Investigation of Gunshot Residue Patterns on Fabrics and Other Surfaces: m-XRF. Journal of Forensic Sciences 2006; 51(5); 1085-1090


Mathis JA, McCord BR. Gradient reversed-phase liquid chromatographicelectrospray ionisation mass spectrometric method for the comparison of smokeless powders. Journal of Chromatography A 2003; 988; 107-116


Mathis JA, McCord BR. Mobile phase influence on electrospray ionisation for the analysis of smokeless powders by gradient reversed phase highperformance liquid chromatography-ESIMS. Forensic Science International 2005; 154; 159-166


West C, Baron B, Minet JJ. Detection of gunpowder stabilizers with ion mobility spectrometry. Forensic Science International 2007; 166; 91-101


McCrehan WA, Bedner M. Development of smokeless powder reference material for propellant and explosives analysis. Forensic Science International 2006; 163; 119-224


Hopper KG, McCord BR. A comparison of smokeless powders and mixtures by capillary zone electrophoresis. Journal of Forensic Sciences 2005; 50(2); 307-315


Muller D, Levy A, Vinokurov A, Ravreby M, Shelef R, Wolf E, Eldar B, Glattstein B. A novel method for the analysis of discharged smokeless powder residues. Journal of Forensic Sciences 2007; 52(1); 75-78


Laza D, Nys B, De Kinder J, Kirsch-De Mesmaeker A, Moucheron C. Development of a quantitative LC-MS/MS method for the analysis of common propellant powder stabilizers in gunshot residues. Journal of Forensic Sciences 2007; 52(4); 842-850




Zeichner A, Eldar B, Glattstein B, Koffman A, Tamiri T, Muller M. Vacuum collection of gunpowder residues from clothing worn by hooting suspects, and their analysis by GC/TEA, IMS, and GC/MS. Journal of Forensic Sciences 2003; 48(5); 961-972


Zeichner A, Eldar B. A novel method for extraction and analysis of gunpowder residues on double-side adhesive coated stubs. Journal of Forensic Sciences 2004; 49(6); 1194-1206


Bird DK, Agg KM, Barnett NW, Smith TA. Time-resolved fluorescence microscopy of gunshot residue: an application to forensic science. Journal of Microscopy 2007; 226(1); 18-25


Mahoney CM, Gillen G, Fahey AJ. Characterization of gunpowder samples using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Forensic Science International 2006; 158(1); 39-51


Hanson A, Springer F. An evaluation of Instant Shooter Identification (IsidTM) gunshot residue kits. AFTE Journal 2005; 27(3); 172-178

100. Hall D, Fairley M. A single approach to the recovery of DNA and firearm discharge residue evidence. Sience & Justice 2004; 44(1); 15-19 101. Avissar YY, Sagiv AE, Mandler D, Almog J. Identification of Firearms Holders by the [Fe(PDT)3]+2 complex. Quantitative determination of iron transfer to the hand and its dependence on palmar moisture levels. Journal of Forensic Sciences 2004; 49(6); 1215-1219 102. Avissar YY, Sagiv AE, Mandler D, Almog J. Identification of firearms handling by the [Fe(PDT)3]+2 complex: chemical and time-dependent factors. Talanta 2005; 67; 328-333 103. Zeichner A, Ehrlich S, Shoshani E, Halicz L. Application of lead isotope analysis in shooting incident investigations. Forensic Science International 2006; 158(1); 52-64 104. Haag LC, Niewoehner L. The source and persistence of lead in gun barrels. AFTE Journal 2007; 39(1); 8-23 105. Randich E, Duerfledt W, McLendon W, Tobin W. A metallurgical review of the interpretation of bullet lead compositional analysis. Forensic Science International 2002; 127; 174-191 106. Koons RD, Buscaglia J. Forensic significance of bullet lead compositions. Journal of Forensic Sciences 2005; 50(2); 341-351


Chapter 3 The Forensic Examination of Marks Nadav Levin, MSc4 Introduction Toolmarks, footwear impressions, and other contact marks form important types of evidence found in major or volume crimes. Their efficient classification and treatment play an important role in identification and crime analysis. Current developments in these fields are highlighted in the present review. The impact of Daubert-type challenges has forced practitioners to review their discipline and its basic foundations. Several organizations are active in these fields, such as the newly formed Scientific Working Group on Shoeprint and Tire Tread Evidence (SWGTREAD) (1), the European Network of Forensic Institutes (ENFSI) Expert Working Group (EWG) Marks, the Association of Firearms and Toolmark Examiners (AFTE) and the International Association for Identification (IAI). Footwear and Tire-tread Impressions SWGTREAD has recently published several guidelines covering many aspects of these disciplines (2-13). These manuals describe the duties of footwear and tire tread examiners (2), establish their minimum qualification and training (10), and set a standard terminology for use (13). They also delineate procedures for the detection and collection of impressions, both in the field and in the laboratory (3-6, 8, 9), as well as instructions for photographing (11) and examining (12)these marks (Also available at the SWGTREAD web page The systematic use of footwear (among other) evidence, collected at scenes of crime, was studied by Burrows and Tarling of the FSS (14). Although the value of this type of evidence is well established both at intelligence or court proceedings levels, this study showed apparent differences in the way police services exploit the collected marks. Some services were shown to use a pro-active approach, taking advantage of crime analysis before the arrest of potential offenders; others adopted a purely reactive approach, waiting for potential suspects to be brought to their attention. A similar trend, focusing mainly on shoeprint evidence, was also observed by Rix (15).

Detection and Recording Photography

Footwear impressions can be digitally photographed or scanned. Shor et al. examined the evidential value of shoeprint images received from the scene or taken deliberately at an angle out of proper perspective (16). This study demonstrated that shoeprint images taken at an angle less than 40° to the perpendicular still preserve the evidential value of the acquired characteristics. At larger angles the original image could not be adequately restored. These findings may be highly useful in digitally rectifying distorted images to their proper dimensions. 4

Head, Toolmarks and Materials Laboratory, Division of Identification and Forensic Science (DIFS), Israel National Police Headquarters, Jerusalem 91906, Israel


Examination of Marks

A complementary approach was proposed by Chung using a Tilt-and-Shift lens for photographing impressions on reflective surfaces or on partially shielded areas (17). Buck et al. demonstrated that the non-destructive method of 3D optical surface scanning (by using the GOM ATOS II system) delivers more detailed results of higher accuracy than the conventional casting techniques (18). According to their findings the software calculates, within seconds, the high-precision 3D coordinates of up to 1.3 million object points per measurement. The results of this mobile 3D optical surface scanner were very satisfactory in different meteorological and snow conditions. The method is also suitable for impressions in soil, sand or other materials.

Casting and 3D Test Impressions

hfDental stone obtained from dental suppliers has been used worldwide at crime scenes for more than thirty years (e.g., Castone or Glastone by Dentsply International). A common practice consists of weighing a portion of dental stone (e.g., 1kg portions) into sturdy Ziploc or heat-sealed bags, which are carried to the crime scenes to be used if needed by adding a known amount of water (500cc per 1kg, usually). Bodziak and Hammer (19) provided basic information about dental stone and its recommended usage and compared it with the new "ready-to-go" kits (such as Traxtone and Crimecast). Even if the novel products gave excellent detail and adequate hardness, the authors finally recommended the use of bulk dental stone for the following reasons: it offers more flexibility regarding the size and amount needed, it is readily available from many dental suppliers, it costs less, and it sets up quickly. To obtain three-dimensional test impressions of known shoes examiners tend to use commercially available Biofoam. Some cases require test impressions for photographic work only, without need for preservation. For these circumstances Massey developed an inexpensive formula of Play-Dough that allows rapid production of high quality three-dimensional impressions (20), which will last for a few days or weeks before becoming crumbly. Wilson proposed using expandable polyurethane foam for producing 3D test prints of the tires in question (21). The polyurethane foam tested gave detailed, durable, costeffective and lightweight tire casts, showing this method to be the most practical compared with other three-dimensional casting techniques. Naples and Miller proposed hands-on laboratory-based activities to introduce forensic sciences to students, by casting and comparing shoemarks (22). This article is clearly intended for teachers and the general audience. Three-dimensional shoeprints and tire tracks in snow are enhanced and preserved prior to casting using various brands of aerosol spray wax, paraffin, or sulphur, following traditional photography methods. Other approaches utilize dry powder layers to build a protective "base" prior to the application of plaster or dental stone. Aerosol waxes, such as "Snow Print Wax", are more commonly used to form a protective layer between the snow impression and subsequent dental stone backing. Adair et al. proposed a method for casting shoe or tire impressions in snow using


Quikrete fast-setting concrete powder in conjunction with dental stone casting material (23). If the snow is somewhat "dry" or icy, the authors have found that pre-application of cold water to the impression improves the Quikrete powder preparation. The Quikrete method gave good results with regard to retention of fine details and is thus presented as an alternative to aerosol waxes. One disadvantage is that small voids, appearing as small defects in the outsole, can be formed where the powder material has not fully set. In another article Adair and Tewes also proposed a solution to harden sulphur casts of snow impressions (24). These casts are highly fragile (even minor abrasive forces can damage or obliterate the fine detail), so the researchers used Plasti-dip, a multipurpose rubber coating material, to coat the sulphur casts. The Plasti-dip coating provided an extremely tough protective layer with minimal to negligible effect on details.

Detecting and Lifting 2D Impressions Gelatine lifters are commonly used to lift dusty shoeprints off porous surfaces. Shor et al. proposed a novel technique to clean gelatine lifters from interfering contaminations using adhesive lifters (25). The technique consists of applying the adhesive lifter directly to the surface of the gelatine lifter and removing it instantly. The upper layer of the attached material on the gelatine filter is removed through this procedure and the quality of the visualized imprint is consequently improved. The cleaning process can be applied repeatedly, and the optimum number varies with substrate. The proposed procedure is routinely used in casework; nevertheless, the authors suggested that repeating the procedure too many times could harm the quality of the print severely. A similar approach, with comparable results, was later taken also by Ford and Baldwin (26). The Electrostatic Dust Print Lifter (EDPL) and the Electrostatic Detection Apparatus (ESDA) were compared by Craig et al. The goal of the study was to determine the optimal combination and order of application of these processes for lifting footwear impressions of the same or similar quality in order to develop the highest quality footwear impression (27). They determined that the EDPL gave impressions of better comparative value than the ones developed with the ESDA. On average, 72.4% of the individual characteristics from the known impression were identified using the EDPL, with an average of only 38.9% for the ESDA. If only one technique is used EDPL is thus highly recommended. The authors also recommended using ESDA before EDPL, to avoid any reversal of the colour that could appear if EDPL is used first. In an earlier work Licht and Murano, while focusing on indented writings, also studied the factors influencing the quality of the recovered impressions when using the ESDA (28). Adair and Doberson demonstrated the feasibility of lifting dusty shoeprints from human skin using the electrostatic dust print lifter (ESDL) (29). Footwear impressions differing in quality were tested using two widely used ESDLs. The test results confirm that this approach may be useful for lifting dusty footwear impressions from human skin. The routinely used method for lifting dust prints using the EDSL is not suitable for conductive surfaces. In order to overcome this limitation, Adair proposed using a non-


Examination of Marks

conductive film barrier, placed underneath the metallic film (30). The author reported obtaining good results with this modification. Adair and Tewes also demonstrated excellent results with a novel method for recovering footwear impressions from cylindrical surfaces, by applying the impression-carrying object to the lifting film, instead of the conventional way (31). Adair also showed that 2D bloody impressions on various surfaces, including human skin, could be easily transferred on alginate casting material (32). Alginate was the only casting materials tested to yield very good results with all surfaces tested, both with leucocrystal violet (LCV) treated and untreated bloody footwear impressions. Similar results, yet unpublished, were also obtained by the Israeli Police DIFS. Michaud and Brun-Conti proposed another method for lifting and enhancing impressions made in blood by impregnation of nylon transfer membranes with LCV (33). The lifted and/or enhanced impressions exhibited excellent detail, especially when the impression was made with very small quantities of blood supported by a nonporous surface. A comprehensive review of the methods used for the recovery of latent marks from human skin, focused mainly on fingerprints, was presented by Sampson and Sampson (34). Apparently, some of these methods may be applicable to footprints as well. Wilgus reported a case of shoeprint recovery from human skin, using cyanoacrylate fuming followed by the application of black magnetic powder and Mikrosil lifting (35). The recovered shoeprint from the victim's right forearm was found to match, by class characteristics, a shoe found in the possession of a suspect.

Digital treatment of footwear marks Digital image enhancement tools have become more accessible to handle footwear marks, mainly due to the availability of computer power to handle large images. Smith enhanced images by manipulating colour channels (36). The technique is well suited when the impression is distracted by colour backgrounds or detected by colourbased detection techniques. Berger et al. used a similar approach (37). Wen and Chen describe the use of an image fusion method, based on multi-resolution analysis, for forensic examinations (38). These authors use simulated and actual images to illustrate how the multi-resolution image fusion technique works. Hamiel, and Yoshida reported a similar technique (39). Several authors have studied the automatic classification of footwear marks achieved using various image processing and matching techniques such as Fourier transform (40, 41) or MSER feature detectors (42). To the best of this author’s (NL) knowledge none of these developments is yet known to be in operational use. Su et al. proposed pre-processing algorithms to transform the initial grayscale image into a binary image, taking advantage of the pixel context (43). This group also studied


automatic detection of quality of the input image using first- and second-order statistics combined with gradient-based and ridgelet-based quality measures (44). Tests using a database of 'good' and 'poor' shoeprint images indicated that the proposed approaches give a reasonable estimate of shoeprint image quality.

Individualization Process The basis for the evidential value of shoeprints examination, as with other types of contact marks, derives from the selectivity of manufacturing or acquired features found in the shoe sole. Kainuma (45) published a study based on a die-cut footwear model (100 pairs of Zori-Zori beach sandals). The study shows enormous variability in results of the die-cut process, and no two slipper soles involved were found to be identical. Nevertheless, the orientation of the patterns should still be regarded as a class, or at least sub-class, characteristic. Wyatt et al. showed that two months of regular wear can affect the ability to individualise, but even after this period of use positive shoeprint identification is still sometimes possible (46). Adair et al. demonstrated that following 7 hours of hiking, sufficient acquired features had been left on the soles of Altitude II hiking boots from Hi-Tec Corporation to distinguish all of them (47). The results obtained support the use of these features for the identification of footwear impressions and confirm the random formation of such damage by the wearer's use of the footwear. Stone suggested a statistical model to predict probabilities of theoretical types of acquired features present in shoeprints (48). The author stated that when the marks or combinations of marks are relatively complex, the magnitudes of the resulting numbers are remarkable, despite being entirely abstract and based on conservative assumptions. It should be stressed that the basic assumptions of the model (independence and uniform distribution of defects in the shoe sole) need to be taken with caution.

Reporting the Results The conclusions of the ENFSI EWG Marks Conclusion Scale Committee (CSC) have been published (49, 50). The committee collected conclusion scales, used by various forensic science laboratories throughout the world, and proposed a six-level harmonized verbal (not numerical) scale for reporting the evidential value of the examination’s findings. The harmonized scale incorporates also the Bayesian approach, as well as likelihood ratio, for interpreting evidence. The proposed scale was also adopted by the SWGTREAD (13). The assumptions made by the CSC regarding equal priors at the origin of the proposed scale, has been discussed by Taroni and Biederman (51) as well as by Biederman et al. (52). In any case, the rich discussion with regards to the scale of conclusions should force all examiners to rethink their reporting procedures. Kerstholt et al. investigated the influence of expectations and complexity on shoe print examinations in order to determine whether results depend on the examiner’s experience (53). It was found that neither expectation nor experience affected results;


Examination of Marks

the quality of the print was shown to be the primary factor influencing the assessment. When there was a noisy background, the acquired features were given a lower evidential value than when there was a clear background. Apparently examiners compensated for the quality of the print and drew more cautious conclusions in cases where the print was less clear. Assessing the evidential value of a footwear impression, Black reported a case where the data obtained from the manufacturer regarding the distribution of a specific brand of shoe was used in strengthening the conclusion reached (54). In a later letter-to-theeditor, Black noted that multiple uppers from the same or different manufacturers might share a common outsole design (55). Another case report, by Brooks Jr., showed how manufacturer’s information (in that case from Reebok) was useful in establishing the precise size, model and date of production of shoes that had left marks at a crime scene (56). At this point it should be mentioned that the ENFSI EWG Marks maintains an internetbased forum for exchanging information regarding unknown footwear impressions (

Other The routine production of a shoemark cast taken in soil may provide information other than shoe size and gait. Indeed, material adhering to the surface of the cast is a potentially fruitful source of information for forensic reconstruction. Bull et al. addressed issues of experimental design and reproducibility for routine comparisons of source and transferred soil samples (57). These principles were later demonstrated in reference to a murder case, which took place in the English Midlands (58). In this case pollen analysis, together with analysis of fibre and of physical and chemical characteristics of the soil, allowed reconstruction of three phases of previous activity of the wearer of the boot prior to leaving the footprint in the field after the murder had taken place. Linking the suspect to a pair of shoes, on the other hand, may be achieved by DNA analysis, as demonstrated by Bright and Petricevic (59). These researches studied the variation in the amount of the wearer’s DNA recovered from shoe insoles. A procedure for sampling and subsequent DNA extraction was developed. The usefulness of this technique was illustrated by a casework example where DNA from shoe insoles had provided useful forensic evidence. In a similar study, Hillier et al. examined whether a wearer’s identity could be determined consistently on the basis of DNA analysis (60). The results obtained suggest that, in some cases, DNA profiles can be obtained, but frequently the DNA profile was mixed, having multiple contributors, indicating secondary transfer. Ozden et al. developed regression formulae for the estimation of individuals’ sex and stature based on foot and shoe dimensions (61). This study confirmed that foot and shoe sizes can be used to estimate an individual's stature, and that the relationship between foot and shoe length and width can be used to aid stature estimation. Shoe


lengths are more useful than widths in determination of sex of wearer, and shoe measurements are preferable to foot measurements. Another example of reconstruction of a criminal event involved the use of tire track analysis. Tracks found on the clothing and corpse of a victim led Park et al. (62) to refute the suspect driver’s version of events. Toolmarks The Identification Process Recently, toolmark (as well as firearms) examinations have come under the same scrutiny as other classic identification areas. One of the main challenges to toolmark examination is exemplified by papers by Schwartz (63, 64) in the aftermath of the United States v. Kain, Crim. No. 03-573-1 (E.D. Pa. 2004). According to Schwartz, adequate statistical empirical foundations and proficiency testing do not exist for firearms and toolmark identification; all firearms and toolmark identifications should be excluded until the development of firm statistical empirical foundations for identifications and a rigorous regime of blind proficiency testing. These arguments were not left without rebuttal, especially by Nichols (65-67). In his response to the challenges raised by Schwartz, Nichols systematically critiqued Schwartz’s articles, reviewing their bibliographic references one-by one. He concluded, in contrast, that in fact a substantial body of literature demonstrates that toolmark and firearm examination have been critically studied according to the precepts of the scientific method and empirically validated. Addressing the statistical issues regarding toolmarks and firearms examinations, Miller and Neel investigated the scientific reliability of using the concept of consecutive matching striae (CMS) as a toolmark criterion for striation marks, and discussed the application to the CMS for the assessment of toolmark patterns (68). It was concluded that an incorrect identification could not be made if the CMS criteria were strictly adhered to, although such strict adherence could also eliminate certain identifications where only one land impression could be compared. As part as a more general trend suggesting to adopt a framework based on a likelihood ratio to interpret evidence, Buckleton et al. published a Bayesian model for assessing firearms and toolmark evidence (69). The proposed model was based on a CMS summary of the visual image of a striated tool mark comparison, and according to its authors the preliminary results are promising. The trend towards the adoption of a probabilistic approach may seem unavoidable, but its operational deployment and reporting procedures are not straightforward, as discussed by Deinet and Katterwe (70).

Marks of Various Types of Tools A statistical study on the defects observed on the faces of twenty hammers subjected to various degrees of wear and abuse through normal use was performed by Collins (71). The results of this study have led to a re-evaluation of Stone's work (72, 73) and to modifications of the related formulae. The new formulae were used to calculate


Examination of Marks

practical, conservative probabilities associated with impressed toolmarks using the collected data. Miller and Beach examined several types of consecutively manufactured tools, including pliers, cutters, punches, and chisels, for the presence of subclass characteristics and any possible effect of the tool on the toolmarks (74). The AFTE Glossary defines Subclass Characteristics as “discernible surface features of an object, which are more restrictive than Class Characteristics in that they are produced incidental to manufacture, are significant in that they relate to a smaller group source (a subset of the class to which they belong) and can arise from a source which changes over time” (75). Identification based on subclass characteristics and not on individual characteristics is considered fallacious and the aim of this article was to observe whether subclass characteristics were noted for each studied tool. In this study some subclass characteristics were found to have no influence on the resulting toolmarks. Walsh & Newton presented a case of sabotaged wooden power poles cut by a chainsaw (76). The article focused on the possibility that corresponding toolmarks found on one of the wood poles and the chainsaw of a suspect were subclass characteristics rather than individualizing ones. In order to test this conclusion consecutively manufactured chainsaw links were obtained from the manufacturer and studied to assess the reproducibility of marks arising from their manufacture. Miller performed a comparative study between marks left 10 years ago by bolt cutters on lead, and the toolmarks left nowadays by the same cutters after several years of use (77). The toolmarks were examined for subclass characteristics, for the persistence of identifiable individual characteristics and changes that occurred on the tools from use. Apart from the well-established mark-producing tools, other types of “tools” were also studied. Van Beest et al. studied the marks left by professional heat-sealing machines on plastic bags, mainly used in drug packing (78). They established relevant class and subclass characteristics, and individual marks (caused by manufacturing defects or due to use). Akao et al. studied the spur mark evidence on inkjet-printed documents, in the domain of counterfeit banknotes, securities, and passports (79). Spur marks are toolmarks created by the spur gears in the paper conveyance system of many inkjet printers. The relationship between printouts and printers was investigated by comparing spur marks found on printed documents with reference spur marks samples from known printers. Spur marks were considered to be effective class characteristics to identify certain brands of inkjet printers since spur gears are used in many types of these machines. It is, however, necessary to build a database allowing isolating families or groups of suspect printers. Novoselsky et al. reported the findings of a case where a motor vehicle, suspected of being stolen, was found severed (80). One of the sections was found in the possession of a suspect, while the other parts were deserted elsewhere. Physical match of the sections was incomplete, due to the width of the abrasion disc used for cutting them apart, but instead the parts were matched on the basis of brush strokes (striations) of a


polymer sealant which had been applied when the vehicle was manufactured. These marks were found to continue on both sides of the cut. In an article dealing with counterfeit 10 New Israeli Shekel (NIS) Coins in Israel, Tsach et al. describe various processes used for producing counterfeit coins, including the manufacturing defects (individual marks) associated with several of these processes (81). Kuppuswamy studied the formation, temporal evolution and forensic applications of camera "Fingerprints” (82). Negative films were exposed in various makes and models of cameras and exposures were performed at regular time intervals over a two-year period. The processed film negatives were then examined using transmitted light to detect the presence of discriminating features on the frame edges. The edge-marks were found to originate mainly from imperfections received on the film mask from the camera’s manufacturing process, and that camera settings have a considerable influence on recording of frame-edge marks with film exposure. Gorn and Hamer examined cable ties of different make and sizes, and found that these items may bear manufacturing-processes marks that can be used for comparison (83). Many other works dealing with toolmarks produced by firearms-related processes, such as the manufacturing of ammunition, are outside the scope of this review. The Examination of Stabbing and Cutting Marks Identification of the weapon in a murder case by stabbing is one of the difficult problems faced by forensic pathologists. In Ramirez v. State of Florida, 810 So.2d 836 (2001), the court excluded toolmark comparison from marks left in cartilage after a Frye hearing. In a commentary to this court decision, Meyers argued that the words novel, science fiction, and junk science (as used by the Florida Supreme Court in this case) are inapplicable to toolmark identification in general or, more specifically, to the procedure involved in this case (84). The possibility to identify the knife as the source of marks left in cartilage after stabbing has been thoroughly re-investigated by Clow, showing the quality of cartilage as a medium to accept toolmark and the ability to distinguish consecutively manufactured knives (85). The results of this study support the validity of previous studies into the uniqueness of toolmarks in cartilage stabbed by knives. A case study reported by Sitiene et al evaluated wounds and lesions of clothing in the area of injury (86). Their study revealed that precise knowledge of the assault circumstances enabled identification of the instrument of assault. In another work general class characteristics of cuts on human bone were shown to correlate with specific sharp (single blade knife) or sharp-blunt (hatchet) instruments (87). Similarity of macroscopic findings led to the conclusion that microscopic analysis is more effective in distinguishing sharp from sharp-blunt injury to the bone. Emphasis has been placed on the value of the scanning electron microscope (SEM) as an anthropologist's tool in bone lesion injuries. A case report by Ostrowski (88) concluded that toolmark findings from the skull of a victim could prove the injury had been inflicted by a hatchet.


Examination of Marks

The examination of damage to a paper towel, an item of evidence in a murder case, was described by Causin et al. (89). Simulations carried out with various tools and comparison of the lacerations present on the towel showed that the towel had been used to clean a sharp, pointed instrument. The paper towel also exhibited marks deemed characteristic of scissors. These findings were effectively used to challenge the suspect's version of events. Another study focused on different characteristics expected to be seen in knife cuts to tires (90). Different styles of knives were shown to yield a variety of characteristic marks. Toolmark findings may also be utilized in puncture marks. Food products can be intentionally contaminated by injection through the polypropylene packaging of certain foodstuffs. A paper by Abe and Matsuda describes a method designed to make controlled holes by needles at different angles on polypropylene bags (91). Their study demonstrated that almost all of the control holes were accompanied by scratch marks and that there was some correlation between needle diameters and scratch widths. Finally, from an historical point of view, Smith and Brickley proposed an analysis of toolmarks found on bones of a Neolithic tomb, consistent with the use of flint tools (92). Observation Methods Toolmark test exemplars can be produced by applying a tool's working surface to a piece of soft metal such as lead, since the lead will replicate the microscopic grooves of the tool surface. An alternative material for preparation of test toolmarks was presented by Petraco et al., who used carving waxes (jewellery modelling) (93). The replicas obtained from wax were exact, highly detailed 1:1, negative impressions of the exemplar tool's working surface, had a long shelf-life, and were suitable for use in toolmark examination and comparison cases. The comparison microscope is the basic tool used by toolmarks and firearms examiners. In 2004, Leica Microsystems released a new comparison macroscope, named the FSC (Forensic Solution Comparison). Dutton presented a review of the instrument’s main features and showed its ability to compare bullet and cartridge cases (94). Schecter et al. proposed a simple method to enhance the visualization of toolmarks found in the firing pin impressions (95). The proposed technique consisted in placing drops of a liquid on the base of cartridge cases so that the liquid forms a lens that enhances illumination and resolution of marks. Various liquids were tested and all presented disadvantages of some sort. However, acetone was shown to be the best adapted. The usefulness of this improvisation for toolmarks examination seems, however, quite limited. Firearms and cartridge cases are often treated for latent fingerprints prior to the firearms identification examination. Bishop et al. studied the influence of cyanoacrylate (superglue) fuming on the identification of unique, microscopic marks within the barrel of a firearm (96). Their findings were that in most cases superglue masks the microscopic marks to a minimal extent but does not interfere with conventional 60

methods of firearms identification. These findings are likely to be applicable to other types of toolmark examinations as well. Demoli et al. proposed an original method for identifying toolmarks based on SEM observations of the striation patterns, combined with an optoelectronic correlator device (97). The method includes acquiring striation patterns as digital image files by using an environmental scanning electron microscope (ESEM), followed by selection and extraction of features from the striation patterns and identifying tools by calculating the correlation measures. This approach relies on transforming the 2D striation patterns to 1D “bar-code” information, by which the starting information is well preserved and the obtained information is robust to deformations and noise. Physical Match Physical match, or fracture match, namely linking two or more objects by the morphology of fractured or torn surfaces, is usually viewed as one of the strongest ways for establishing common origin. De Forest recently stated, for instance, that “If the fracture surface is large enough, the detail present may be sufficient to allow a unique association to be demonstrated between the two portions” (98, p. 8). The evidential value of such physical matches, and their admissibility in court, seem to be taken for granted, considering the limited number of articles published in this discipline. Even so, several recent articles were aiming toward the foreseen Dauberttype challenges in this field. Bradley et al. used duct tape as the fractured medium, to study the validity and error rate associated with conducting end match (fracture match) examinations on this material (99). Five test designs, which varied either the source roll of tape or manner of separation (torn or cut) from the roll, were administered to four analysts with instructions to examine the assigned test sets for end matches. Results indicated that while tape grade did not hinder end match identification, the manner of separation could affect results. Tsach et al. took a more controlled approach, by using a tensile machine with set force and speed for rupturing homogeneous samples (100). The torn samples were then submitted for examination by several experts. The results obtained showed that, even when rupture is carried out under repetitive conditions, each ruptured sample has a different contour, demonstrating the individuality of the process. Katterwe (101) and Orench (102) also took a similar approach. In a study by Stone, consideration was given to the formation of two- and threedimensional fractures formed in brittle metals, and mathematical probability models were derived for the interpretation of fracture evidence (73). This study presents a model that, when validated, may assist examiners to quantify such fractures in casework. Miller and Kong reviewed the types of fracture patterns described in the literature, and considered the fracture process in metal objects (103). Actual samples were also examined in order to observe the pattern of the external break and the pattern of the internal fracture.


Examination of Marks

In addition to these research papers, several case reports were also published in this field. Streine describes the use of physical match in a murder case where the victim was dragged alongside a car for some distance (104). Pieces of material from which the wheel well was composed of, broke off and were recovered at the scene. These pieces were submitted to the author’s laboratory together with part of a wheel well from the suspect's vehicle. A physical fracture match between the items was confirmed. Karim reported an atypical pattern-fit identification of two parts of a severed exhaust pipe (105). One of the sections was severed from a vehicle that departed the scene of a murder and was found at the scene. The other section remained attached to the vehicle. After the vehicle was recovered one year later, a pattern-fit identification between the two parts was made. Restoration of Obliterated Marks Several articles have been published, regarding methods for the restoration of obliterated marks. Katterwe published a review on methods for serial numbers restoration in vehicles (106). Katterwe suggested a method to restore erased numbers from polymers surfaces using clove powder. Burke et al. explored this technique, presenting that clove powder, and especially the active component Eugenol, can be used to restore obliterated numbers from a wide range of polymers (107). Kuppuswamy and Senthilkumar proposed a procedure for the examination of vehicles involved in forgeries (i.e., vehicles whose engine numbers, chassis numbers or other identifying marks have been obliterated) (108). Several cases, where these procedures were utilized, are presented at this article. The Fry’s reagent (a solution of cupric chloride, concentrated hydrochloric acid, and water), was found to be the favourable solution for steel surface, as already reported by others. In a later article, Azlan Mohd. Zaili et al. studied reagents for the restoration of erased numbers on steel surfaces (109). Good results have been obtained by a reagent made of 5 g copper sulphate, 60 ml water, 30 ml concentrated ammonium hydroxide and 60 ml concentrated hydrochloric acid. This reagent restored marks erased to a depth of 0.04 mm below the engraving depth. Hogan and Smith compared MAPP gas (a stable, high energy fuel made of a mixture of methyl-acetylene-propadien and liquefied petroleum gas) with oxyacetylene in terms of its ability to restore obliterated vehicle identification numbers (110). The results obtained indicate that MAPP has significant benefits in terms of equipment weight and cost. Malikowski describes a case where digital photography and Adobe Photoshop software were used to enhance and restore a partially obliterated laser-etched barcode on a Smith & Wesson Sigma pistol, enabling the barcode to be scanned and recovered using a barcode reader (111). Utrata and Johnson studied the conditions that increase the likelihood of successfully applying the magnetic particle method to forensic casework (112). It was found that success depends on the magnitude and the orientation of the magnetic field, the correct


nature of the magnetizing current, and an appropriate choice of magnetic particle suspension. Crowe and Morgan-Smith reported that the metallurgical reagent aqua regia was proved to be effective in recovering an erased jeweller's mark on the inner band of a stolen 18-carat gold-and-diamond ring (113). Barratt and Smith report a case in which the printed serial number on a tax disc had been partially removed (114). In this case, the obliterated bar code could be restored and manually decoded, allowing the complete recovery of the serial number of the tax disc and the retrieval of the original entries. References (1) Wiersma, S. SWGTREAD. Journal of Forensic Identification, 2005, 55 (1), 47-48. (2) SWGTREAD. Scope of work relating to forensic footwear and/or tire treads examiners. Journal of Forensic Identification, 2005, 55 (6), 764-765. (3) SWGTREAD. Guide for the detection of footwear and tire impressions in the field. Journal of Forensic Identification, 2005, 55 (6), 766-769. (4) SWGTREAD. Guide for the collection of footwear and tire impressions in the field. Journal of Forensic Identification, 2005, 55 (6), 770-773. (5) SWGTREAD. Guide for the detection of footwear and tire impressions in the laboratory. Journal of Forensic Identification, 2005, 55 (6), 774-777. (6) SWGTREAD. Guide for the collection of footwear and tire impressions in the laboratory. Journal of Forensic Identification, 55 2005, (6), 778-780. (7) SWGTREAD. Guide for the preparation of test impressions for footwear and tires. Journal of Forensic Identification, 2005, 55 (6), 781-786. (8) SWGTREAD. Guide for lifting footwear and tire impression evidence. Journal of Forensic Identification, 2006, 56 (4), 630-634. (9) SWGTREAD. Guide for casting footwear and tire impression evidence. Journal of Forensic Identification, 2006, 56 (4), 635-641. (10) SWGTREAD. Guide for minimum qualifications and training for a forensic footwear and/or tire tread examiner. Journal of Forensic Identification, 2006. 56 (5), 788-793. (11) SWGTREAD. Guide for the forensic documentation and photography of footwear and tire impressions at the crime scene. Journal of Forensic Identification, 2006, 56 (5), 794-799. (12) SWGTREAD. Guide for the examination of footwear and tire impression evidence. Journal of Forensic Identification, 2006, 56 (5), 800-805. (13) SWGTREAD. Standard terminology for expressing conclusions of forensic footwear and tire impression examinations. Journal of Forensic Identification, 2006, 56 (5), 806-808. (14) Burrows, J. and Tarling, R. Measuring the impact of forensic science in detecting burglary and autocrime offences. Science and Justice, 2004, 44, 217-222. (15) Rix, B. (2004) The contribution of shoemark data to police intelligence, crime detection and prosecution. Findings, Home Office, Research, Development and Statistics Directorate (No. 236). (16) Shor, Y., Chaikovsky, A. and Tsach, T. The evidential value of distorted and rectified digital images in footwear imprint examination. Forensic Science International, 2006, 160 (1), 59-65. 63

Examination of Marks

(17) Chung, J. W. Use of Tilt and Shift Lens in Forensic Photography. Journal of Forensic Identification, 2006, 56 (1), 6-17. (18) Buck, U., Albertini, N., Naether, S. and Thali, M. J. (2007) 3D documentation of footwear impressions and tyre tracks in snow with high resolution optical surface scanning. Forensic Science International, 2007, In Press. (19) Bodziak, W. J. and Hammer, L. An evaluation of dental stone, traxtone, and crime-cast. Journal of Forensic Identification, 2006, 56 (5), 769-787. (20) Massey, S. L. Fingertips: Three-dimensional test impressions of footwear using home made play dough. Identification Canada, 2007, 30 (1), 19-22. (21) Wilson, J. D. Casting Tyres with Expandable Polyurethane Foam and Other Materials. Journal of Forensic Identification, 2004, 54 (2), 158-169. (22) Naples, V. L. and Miller, J. S. Making tracks: The forensic analysis of footprints and footwear impressions. The anatomical record (Part B: New Anat.), 2004, 279B, 915. (23) Adair, T. W., Hisey, S. and Tewes, R. Casting snow prints with "Quikrete" Fast setting concrete: An alternative to aerosol wax products. The Information Bulletin for Shoeprint/Toolmark Examiners, 2005, 11 (1), 34-40. (24) Adair, T. W. and Tewes, R. Strengthening sulfur casts with plasti-dip. The Information Bulletin for Shoeprint/Toolmark Examiners, 2006, 12 (2), 16-21. (25) Shor, Y., Tsach, T., Wiesner, S. and Meir, G. Removing interfering contaminations from gelatin lifters. Journal of Forensic Sciences, 2005, 50 (6), 1386-1393. (26) Ford, A. and Baldwin, D. Cleaning the Surface of Gelatine Lifts. FSS Report, 2006; No. TN896, 1-8. (27) Craig, C. L., Hornsby, B. M. and Riles, M. Evaluation and comparison of the electrostatic dust print lifter and the electrostatic detection apparatus on the development of footwear impressions on paper. Journal of Forensic Sciences, 2006, 51 (4), 819-826. (28) Licht, G. and Murano, E. ESDA Effects in Light of Current Discussions. Journal of the American Society for Questioned Documents, 2004, 7 (1), 7-48. (29) Adair, T. W. and Dobersen, M. Lifting Dusty Shoe Impressions from Human Skin: A Review of Experimental Research from Colorado. Journal of Forensic Identification, 2005, 56 (3), 333-338. (30) Adair, T. W. Electrostatic dust lifting on metallic surfaces using automotive window tinting film as a nonconductive barrier. Journal of Forensic Identification, 2005, 55 (5), 605-610. (31) Adair, T. W. and Tewes, R. Lifting Shoe Impressions from Cylindrical Objects: A Simple Method. The Information Bulletin for Shoeprint/Toolmark Examiners, 2006, 12 (1), 7-13. (32) Adair, T. W. Casting two-dimensional bloody shoe prints from concrete, fabric and human skin: A review of several methods with recommendations. International Association of Bloodstain Pattern Analyst (I.A.B.P.A.) News, 2005, March, 4-8. (33) Michaud, A. L. and Brun-Conti L. A method for impregnating Nylon transfer membranes with leucocrystal violet for enhancing and lifting bloody impressions. Journal of Forensic Sciences, 2004, 49 (3), 511-516. (34) Sampson, W. C. and Sampson, K. L. Recovery of latent prints from human skin. Journal of Forensic Identification, 2005, 55 (3), 362-385. (35) Wilgus, G. Latent shoeprint recovery on human skin. Journal of Forensic Identification, 2004, 54 (4), 428-432. 64

(36) Smith, J. Image enhancement and Adobe Photoshop: Using calculations to extract image detail. Journal of Forensic Identification, 2007, 57 (4), 493-505. (37) Berger, C. E. H., de Koeijer, J. A., Glas, W. and Madhuizen, H. T. Color separation in forensic image processing. Journal of Forensic Sciences, 2006, 51 (1), 100-102. (38) Wen, C. Y. and Chen, J. K. Multi-resolution fusion technique and its application to forensic science. Forensic Science International, 2004, 140 (2-3), 217-232. (39) Hamiel, J. S. and Yoshida, J. S. Evaluation and application of polynomial texture mapping in the area of shoe and impression evidence. Journal of Forensic Identification, 2007, 57 (3), 414-434. (40) de Chazal, P., Flynn, J. and Reilly, R. B. (2005) Automated processing of shoeprint image based on the Fourier transform for use in forensic science. IEEE Transactions on Pattern Analysis and Machine Intelligence (PAMI), 2005, 27 (3), 341350. (41) Hannigan, T. J., Fleury, L. M., Reilly, R. B., O'Mullane, B. A. & de Chazal, P. Survey of 1276 shoeprint impressions and development of an automatic shoeprint pattern matching facility. Science and Justice, 2006, 46 (2), 78-89. (42) Pavlou, M. and Allinson, N. M. (2006) Automatic extraction and classification of footwear patterns. Proc. Intelligent Data Engineering and Automated Learning (IDEAL06), 2006, Lecture Notes in Computer Science 4224 721-728. (43) Su, H., Crookes, D. and Bouridane, A. Thresholding of noisy shoeprint images based on pixel context. Pattern Recognition Letters, 2007, 28 (2), 301-307. (44) Su, H., Bouridane, A. and Crookes, D. Image quality measures for hierarchical decomposition of a shoeprint image. Forensic Science International, 2006, 163 (1-2), 125-131. (45) Kainuma, A. Manufacturing variations in a die-cut footwear model. Journal of Forensic Identification, 2005, 55 (4), 503-517. (46) Wyatt, J. M., Duncan, K. and Trimpe, M. A. Aging of shoes and its effect on shoeprint impressions. Journal of Forensic Identification, 2005, 55 (2), 181-188. (47) Adair, T. W., Lemay, J., McDonald, A., Shaw, R. and Tewes, R. The Mount Bierstadt study: An experiment in unique damage formation in footwear. Journal of Forensic Identification, 2007, 57 (2), 199-205. (48) Stone, R. S. Footwear examinations: Mathematical probabilities of theoretical individual characteristics. Journal of Forensic Identification, 2006, 56 (4), 577-599. (49) Katterwe, H. Annual report 2003. The Information Bulletin for Shoeprint/Toolmark Examiners, 2004, 10 (1), 8-22. (50) ENFSI Expert Working Group Marks Conclusion Scale Committee. Conclusion scale for shoeprint and toolmarks examination. Journal of Forensic Identification, 2006, 56 (2), 255-280. (51) Taroni, F. and Biederman, A. (2005) Inadequacies of posterior probabilities for the assessment of scientific evidence. Law Probability and Risk, 2005, 4, 89-115. (52) Biedermann, A., Taroni, F. and Aitken, C. G. G. Letter to the editor - conclusion scale for shoeprint and toolmarks examinations. Journal of Forensic Identification, 2006, 56 (5), 685-693. (53) Kerstholt, J. H., Paashuis, R. & Sjerps, M. Shoe print examinations: Effects of expectation, complexity and experience. Forensic Science International, 2007, 165 (1), 30-34. (54) Black, J. P. An interesting case involving footwear distribution information. Journal of Forensic Identification, 2005, 55 (4), 499-502.


Examination of Marks

(55) Black, J. P. Letter to the editor - an interesting case involving footwear distribution information. Journal of Forensic Identification, 2005, 55 (6), 685-686. (56) Brooks Jr., J. M. Identifying and sharing class characteristics of outsole impressions. Journal of Forensic Identification, 2006, 56 (5), 737-743. (57) Bull, P. A., Morgan, R. M., Dunkerley, S. and Wilson, H. E. Multi-technique comparison of source and primary transfer soil samples: An experimental investigation. A comment. Science & Justice, 2004, 44 (3), 173-178. (58) Bull, P. A., Parker, A. and Morgan, R. M. The forensic analysis of soils and sediment taken from the cast of a footprint. Forensic Science International, 2006, 162 (1-3), 6-12. (59) Bright, J. A. and Petricevic, S. F. Recovery of Trace DNA and Its Application to DNA Profiling of Shoe Insoles. Forensic Science International, 2004; 145 (1), 7-12. (60) Hillier, E., Dixon, P., Stewart, P., Yamashita, B. and Lama, D. Recovery of DNA from Shoes. Journal of the Canadian Society of Forensic Science, 2005, 38 (3), 143-150. (61) Ozden, H., Balci, Y., Demirustu, C., Turgut, A. and Ertugrul, M. Stature and Sex Estimate Using Foot and Shoe Dimensions. Forensic Science International, 2005, 147, 181-184. (62) Park, S., Kim, T., Choi, Y. and Chae, S. Analysis of Two Tyre Marks on the Head and Clothing. Japanese Journal of Forensic Science and Technology, 2006, 11 (1), 125129. (63) Schwartz, A. A challenge to the admissibility of firearms and toolmark identifications: Amicus brief prepared on behalf of the defendant in United States v. Kain, crim. 03-573-1 (e.D. Pa. 2004). The Journal of Philosophy, Science and Law, 2004, 4 (December 7), (64) Schwartz, A. A systemic challenge to the reliability and admissibility of firearms and toolmark identification. Science and Technology Law Review, 2005, 6, 1-42. (65) Nichols, R. G. The scientific foundations of firearms and tool mark identification – a response to recent challenges. The CAC News, 2006 (Second Quarter), 8-27 (available also at ). (66) Nichols, R. G. Defending the scientific foundations of the firearms and tool mark identification discipline: Responding to recent challenges. Journal of Forensic Sciences, 2007, 52 (3), 586-594. (67) Nichols, R. G. Firearm and tool mark identification: The scientific reliability and validity of the AFTE theory of identification discussed within the framework of a study of ten consecutively manufactured extractors. AFTE Journal, 2004, 36 (1), 6788. (68) Miller, J. and Neel, M. Criteria for identification of toolmarks part III – supporting the conclusion. AFTE Journal, 2004, 36 (1), 7-16. (69) Buckleton, J. S., Nichols, R. G., Triggs, C. and Wevers, G. An exploratory Bayesian model for firearms and tool mark interpretation. AFTE Journal, 2005, 37 (4), 352361. (70) Deinet, W. and Katterwe, H. Comments on the application of theoretical probability models including Bayes theorem in forensic science relating to firearm and tool marks. AFTE Journal, 2007, 39 (1), 4-7. (71) Collins, E. R. (2005) How "Unique" Are impressed toolmarks? - an empirical study of 20 worn hammer faces. AFTE Journal, 2005, 37 (4), 252-395. (72) Stone, R. S. How unique are impressed toolmarks? AFTE Journal, 2003, 35 (4), 376383.


(73) Stone, R. S. A probabilistic model of fractures in brittle metals. AFTE Journal, 2004, 36 (4), 297-301. (74) Miller, J. & Beach, G. Toolmarks: Examining the possibility of subclass characteristics. AFTE Journal, 2005, 37 (4), 296-345. (75) The AFTE Training and Standardization Committee (editors). Glossary of the Association of Firearms and Toolmark Examiners. 2001, 4th Edition (CD version). (76) Walsh, K. A. J. and Newton, A. W. N. An investigation into the individualization of chainsaw cuts in wood and the general toolmark identification process. AFTE Journal, 2006, 38 (1), 14-40. (77) Miller, J. An evaluation of the persistence of striated and impressed toolmarks encompassing a ten-year period of tool application, and a summary of forensic research on bolt cutters. AFTE Journal, 2006 38 (4), 310-326. (78) Van Beest, M., Migeot, G. and De Kinder, J. Toolmarks left by heat sealing machines. AFTE Journal, 2004, 36 (4), 302-307. (79) Akao, Y., Kobayashi, K. and Seki, Y. Examination of spur marks found on inkjetprinted documents. Journal of Forensic Sciences, 2005, 50 (4), 915-923. (80) Novoselsky, Y., Tsach, T., Volkov, N. and Shor, Y. Matching Vehicle Parts Using Brush Strokes. Journal of Forensic identification, 2005, 55 (5), 624-632. (81) Tsach, T., Shor, Y., Volkov, N. and Novoselsky. Counterfeit NIS 10 coins in Israel. Journal of Forensic Identification, 2005, 55 (4), 433-441. (82) Kuppuswamy, R. Studies on the formation, temporal evolution and forensic applications of camera "fingerprints “. Forensic Science International, 2006; 159 (23), 210-217. (83) Gorn, M. E. and Hamer P. S. The forensic examination of cable ties. Journal of Forensic Identification, 2006, 56 (5), 744-755. (84) Meyers, C. Commentary: Tool marks - "Novel scientific evidence?" (Ramirez revisited). AFTE Journal, 2005, 37 (3), 197-200. (85) Clow, C. M. Cartilage stabbing with consecutively manufactured knives: A response to Ramirez v. State of Florida. AFTE Journal, 2005, 37 (2), 86-116. (86) Sitiene, R., Varnaite, J. and Zakaras, A. Complex investigation of body and clothing injuries during the identification of the assault instrument. Forensic Science International, 2004, 146 (Supplement 1), S59-S60 (87) Alunni-Perret, V., Muller-Bolla, M., Laugier, J.-P., Lupi-Pégurier, L., Bertrand, M.F., Staccini, P., Bolla, M. and Quatrehomme, G. Scanning electron microscopy analysis of experimental bone hacking trauma. Journal of Forensic Sciences, 2005, 50 (4), 796-801. (88) Ostrowski, S. H. Identification of a toolmark on human skull utilizing cattle blade bones as test medium. AFTE Journal, 2006, 38 (4), 348-355. (89) Causin, V., Marega, C. and Schiavone, S. Cuts and tears on a paper towel: A case report on an unusual examination of damage. Forensic Science International, 2005, 148 (2-3), 157-162. (90) Locke, R. L. Characteristics of knife cuts in tires. AFTE Journal, 2006, 38 (1), 56-65. (91) Abe, T. and Matsuda, J. Needle marks on polypropylene film. Japanese Journal of Forensic Science and Technology, 2006, 11 (2), 193-204. (92) Smith, M. J. and Brickley, M. B. Analysis and interpretation of flint toolmarks found on bones from West Tump Long Barrow, Gloucestershire. International Journal of Osteoarchaelogy, 2004, 14, 18-33.


Examination of Marks

(93) Petraco, N., Petraco, N. D. and Pizzola, P. A. () An ideal material for the preparation of known toolmark test impressions. Journal of Forensic Sciences, 2005, 50 (6), 1407-1410. (94) Dutton, G. LEICA FSC comparison macroscope. AFTE Journal, 2004, 36 (4), 256261. (95) Schecter, B., Giverts, P., Siso, R. and Finklestein, N. Creating a temporary liquid lens for amplification of toolmarks. AFTE Journal, 2005, 37 (4), 362-367. (96) Bishop, B., Rosati, C., Leas, R., Ennis, M., Lee, J. and Janeksela, V. Does superglue hinder traditional firearms identification? AFTE Journal, 2005, 37 (1), 3-7. (97) Demoli, N., Sariri, K., Stanic, Z., Mastruko, V. and Milat, O. Toolmarks identification using SEM images in an optoelectronic correlator device. Optik International Journal for Light and Electron Optics, 2004, 115 (11-12), 487-492. (98) De Forest P. R. What is trace evidence? In: Caddy B. (Editor). Forensic Examination of Glass and Paint. London, New York: Taylor & Francis, 2001, 1-25. (99) Bradley, M. J., Keagy, R. L., Lowe, P. C., Rickenbach, M. P., Wright, D. M. and LeBeau, M. A. A Validation study for duct tape end matches. Journal of Forensic Sciences. 2006, 51 (3), 504-508 (Also in: Forensic Science Communications, 2007, 9 (3), 1-7, (100) Tsach, T., Wiesner, S. and Shor, Y. Empirical proof of physical match: systematic research with tensile machine. Forensic Science International, 2007, 166 (1), 77-83. (101) Katterwe, H. W. Fracture matching and repetitive experiments: A contribution of validation. AFTE Journal, 2005, 37 (3), 229-241. (102) Orench, J. A. A validation study of fracture matching metal specimens failed in tension. AFTE Journal, 2005, 37 (2), 142-149. (103) Miller, J. and Kong, H. Metal fractures: matching and non-matching patterns. AFTE Journal, 2006, 38 (2), 133-165. (104) Streine, K. M. An interesting physical fracture match. AFTE Journal, 2007, 39 (1), 68-69. (105) Karim, G. A pattern-fit identification of severed exhaust tailpipe sections in a homicide case. AFTE Journal, 2004, 36 (1), 65-66. (106) Katterwe, H. Restoration of serial numbers. In: Stauffer, E. and Bonfanti, M. (Eds.) Forensic investigation of stolen-recovered and other crime-related vehicles. Academic Press, 2006, 177-206. (107) Burke, K., Lewis, S. W., Bett, J., Southhurst, T. E., Lim, K. F. and Gutowski, S. J. () Preliminary investigations into using Eugenol to recover erased characters on polymers. Journal of Forensic Identification, 2007, 57 (4), 522-529. (108) Kuppuswamy, R. and Senthilkumar, M. Restoration of vehicle identification numbers. Journal of Forensic Identification, 2004, 54 (1) 13-21. (109) Azlan Mohd. Zaili, M., Kuppuswamy, R. and Harun, H. Restoration of engraved marks on steel surfaces by etching technique. Forensic Science International, 2007, 171 (1), 27-32. (110) Hogan, B. E., Smith, D.R. and Hall, B. R. MAPP gas: An alternative to oxyacetylene. Journal of Forensic Identification, 2006, 56 (2), 232-241. (111) Malikowski, S. G. The Restoration of an obliterated serial number and barcode using digital photography and Adobe Photoshop. AFTE Journal, 2004 36 (2), 237238. (112) Utrata, D. and Johnson, J. Development of magnetic particle method for forensic recovery of serial numbers. Review of Quantitative and Non-destructive Evaluation, 2004, 23, 1438-1444. 68

(113) Crowe, G. and Morgan-Smith, R. (2005) Restoration of a jeweller's mark in gold jewellery. AFTE Journal, 37 (4), 379-381. (114) Barratt, E. M. and Smith, Y. Examination of an altered bar code on a vehicle tax disc. Science & Justice, 2005, 45 (3), 135-139.


Forensic Geology

Chapter 4

Forensic Geology

Sugita R, MSc5 Suzuki S, PhD1 Katsumata Y, PhD1 Introduction This review of “Forensic geology” includes not only geological but also related sciences such as palynology and microscopy since geology is basically an integrated science. The number of meetings was increased rapidly during this review period. International Workshop on Criminal and Environmental Soil Forensics was held in Perth, Australia in which nineteen presentations were provided (1-19) and networking of forensic geologists was also discussed. Forensic Remote Sensing and Geophysics Conference organized by the EIGG and the Remote Sensing and Photogrammetry Society in 2004 (20-31). Joint Environmental and Industrial Geophysics Group (EIGG) and the Forensic Science Group Meeting was held on the December 2006 with 15 oral and 2 poster presentations (32-47). Many sessions on forensic geology and related sciences have been held as a part of meetings: palynology session in 17th ANZFSS 2004 (48-57), “Forensic Geology: Practical Geologic Experiences that Helped CSI’s” at the 41st Annual Meeting of Northeastern Section of the Geological Society of America (58-68), “Forensic Geoscience: In Practice and in Teaching” session at the Annual Meeting of the Geological Society of America 2006 (69-83). Moreover, the number of presentations in other general meetings such as the annual meetings of the Japanese Association of Forensic Science and Technology has increased. A special issue of Forensic Science International on palynology and books (84, 85) related to forensic geology have also been published. Analysis of soil There were many studies on the mineralogical and analytical approach to geological evidence such as soil and mineral grains that employed traditional and newly developed methods. Microscopy is the most traditional method and continues to be a powerful method. Basic knowledge on the maintenance of light microscopes was discussed by Speir (86). Hietpas (87) explained the differentiation of calcite and dolomite by using dispersion colors. Soil color analysis by using an instrumental method was evaluated by Croft and Pye (88). Marumo and Sugita (89) presented a simple examination of a coarse fraction of soil by microscopic observation. The importance of particles in soil evidence as indices of discrimination was described by Sugita and Marumo (90). Reports on the usage of a scanning electron microscope (SEM) and an energy dispersive X-ray analyzer (EDX) attached to an SEM were presented by many 5

National Research Institute of Police Science, 6-3-1 Kashiwanoha, Kashiwa-shi, Chiba 277-0882, Japan


researchers (91-93). Bull and Morgan (94) observed quartz by using an SEM and classified it according to the grain type and surface texture. This technique provides exclusionary results and is a powerful tool in the forensic interpretation of soil and sediments. Instrumental analysis has been applied for the discrimination and characterization of quartz. Bernet and Bassett (95) analyzed single-quartz-grain SEM-CL to assume the provenance where the grain originally derived from. A new method for the determination of three-dimensional grain shapes was described by Blott et al. (96) by using a nitrogen gas adsorption technique for provenance analysis. Particle size analysis was another traditional method of soil examination. Pye and Blott (97), Blott et al. (98), and Blott and Pye (99) examined the use of a laser diffraction method for the particle size analysis of soil evidence; the authors also studied the effect of the shape of particles on the application of the laser device. Analyses of elements in soil are often used as an indicator of discrimination of soil evidence. The relation between soil types and agricultural use in Japan was examined on fifty seven soil samples by Takeda et al. (100), and the effect of accumulation of uranium derived from long-term fertilizer application in cultivated Andisol in comparison to noncultivated land was investigated by Takeda et al. (101). Sterckman et al. (102) analyzed trace elements in soils developed on sedimentary materials and described the correlation of the elements with the depth, types of sediments, and anthropogenic influence. Cengiz et al. (103) performed an experiment involving sieved and pressed soil samples by using SEM-EDS for discrimination. Jarvis et al. (104) investigated the element variability of small amounts of soil and sediments by inductively coupled plasma (ICP) optical emission spectrometry (OES) and mass spectrometry (MS). Pye and Croft (105) and Pye et al. (106) performed elemental analysis of soil using ICP-OES and ICP-MS to investigate repeatability and reproducibility were closely investigated for forensic soil examination. Sasajima et al. (107) and Sasajima et al. (108) analyzed soil collected from mountains and rivers of a single prefecture to provide basic information for their discrimination. Scheinost et al. (109) examined Sb species in soil samples of six shooting ranges by using EXAFS. It was found that there were only two species of Sb in all the samples although the geology of the sampling sites was varied. Rawlins and Cave (110) examined elemental data obtained by X-ray fluorescence (XRF) spectrometry through statistical comparison and inferred that statistical comparison could be used to help establish provenance when performed according to a strict protocol. Yoshida et al. (111) used synchrotron radiated XRF for forensic soil analysis. The analysis of the stable isotope ratio in the field of forensic geology is a fairly new method. The application of stable carbon isotope analysis in forensic geology was reported by Croft and Pye (112). A series of presentations by Naganuma et al. (113-115) and Arikawa et al. (116) clarified that a combination of methods could provide regional information reflecting both the geological and vegetation background; these researchers combined the analysis of magnetic minerals using electron probe microanalysis (EPMA) and the observation of plant opal with a microscope. The mineralogical 71

Forensic Geology

analysis of weathered biotite for forensic discrimination was investigated by Sugita and Suzuki (117). Apart from elemental analytical methods, the X-ray diffraction method, thermal analysis, and optical spectroscopy were also studied and applied. By using X-ray diffraction, Ruffell and Wiltshire (118) examined soil samples obtained from tire marks and compared them with soil collected from tire treads. Quantitative and qualitative analyses were performed and the results were compared. Friolo et al. (119) examined the use of thermal analysis for the examination of a crystalline or amorphous phase when the amount of sample was small. By employing Raman and infrared spectroscopy, Kurata (120) performed experiments on synthesized and natural quartz that were relatively large-sized for the nondestructive identification of seal materials. Organic matters in soil were also studied as indices of soil discrimination. Dawson et al. (121) described the use of plant hydrocarbons in forensic soil characterization. Fiedler et al. (122) characterized soil containing adipocere and suggested that there was a need for additional approaches in forensic research. The evaluation and interpretation of the results obtained through multitechniques were enthusiastically studied during the review period. Pye et al. (123) compared different methods by using instrumental analyses performed on 18 samples obtained from two sites. They examined both the distinguishing ability of the methods and the number of samples that should be analyzed to ensure the representativeness of the site under study. Rawlins et al. (124) tested independent and collective interpretations of four different methods, including a mineralogical technique, palynology, and organic analysis, performed by experts. The results indicated that collective interpretation was very effective but anthropogenic redistribution of materials may affect the result. Isphording (125) pointed out several problems pertaining to quality assurance, quality control, and statistical interpretation of geochemical data presented in courts. Morgan and Bull (126) presented two case studies in which difficulties in data interpretation arose. Bayesian analysis was applied for fingerprinting sediments and its suitability was discussed by Small et al. (127). Nocerino et al. (128) emphasized the importance of sampling and subsampling to ensure representativeness. Gilbert and Pulsipher (129) also described the role of sampling designs in the collection of representative data. Geophysical survey Many researches have been performed during the review years on geophysical survey. The determination of burial sites is the main purpose of this survey. The general information and methods were described by Fenning and Donnelly (130). Details of the techniques and progress were also described by Watters and Hunter (131) and Scott and Hunter (132). As already mentioned, the Forensic Remote Sensing and Geophysics Conference was held in London in 2004, which was organized by the EIGG and the Remote Sensing and Photogrammetry Society.


Schultz et al. (133) experimented with a ground-penetrating radar (GPR) to monitor burials of pig cadavers and blank graves under several conditions. Ruffell (134) examined quantitative probe measurements for the search of grave sites. Kalacska and Bell (135) reported an ongoing long-term experiment on detecting clandestine mass graves using remote sensing techniques. Ruffell (136) reported a case in which GPR had been used to search for the IRA “Disappeared” at a location that was suspected to be a burial site. Palynology There was significant development of palynology during the review period. Palynology is a part of geoscience and is very useful in identifying soil types and determining the environment at the scene of a crime by using pollen and spores derived from plants. A special issue of Forensic Science International on forensic palynology was published in 2006. It started with a brief summary of the history and status of palynology as a part of forensic science (Mildenhall et al. (137)) and discussed some important factors to be considered when practicing forensic palynology (138). There were also articles on the current status of forensic palynology in several countries (139, 140), case reports that included criminal and war crime investigations (141–145), examinations to establish a crime pollen calendar for criminal investigations (146). The preparation of pollen samples for a forensic examination was described by Horrocks (147) and a general description of forensic palynology was also given in a chapter of the book “Forensic Botany” by Milne et al. (18). There were also case reports by Mildenhall (149). Other biological materials The application of techniques of molecular biology to soil has slowly but steadily increased the number of reports. Moreno et al. (150) compared the experimental data on microbial communities with elemental analysis by performing ICP-OES with soil samples. The potential for using bacterial DNA for the discrimination of soil was examined by Narihara et al. (151) and Heath and Sunders (152). Kuske et al. (153) reported the result of a survey on four pathogenic bacteria and closely related species in soil and aerosol. They found a large number of Bacillus cereus group bacteria in soil, while other pathogenic and related species were very small in number. Attempts to utilize Bacillus cereus were also reported by Kikkawa (154). Edwards et al. (155) examined archaeological ivory from different ages and provenances and with different taphonomic histories by using FT-Raman spectroscopy. The report also discussed the problems faced in matching the results with the standard spectra. Urban soil, dust analysis, and related matters Urban soil and roadside sediments are important geological evidence in crime investigations. They have not been considered in detail in traditional geology, but have been investigated by forensic and environmental scientists. Roadside sediments from urban and local cities in Kyoto, Japan, were examined using X-ray fluorescence analysis for a forensic application (156); a monograph on 73

Forensic Geology

this topic has also been published in 2005 (157). Aoki et al. (158) studied various methods for the characterization of urban soil. A database of coastal dune sediments, including data on particle size and chemical composition, has been developed for forensic investigations (159). Studies on environmental investigations have high potential of providing useful information to forensic science. Anagnostopoulou and Day (160) examined lead concentrations in roadside dust from streets, national gardens, and school playgrounds. They revealed that the lead concentrations were reduced as compared to the concentrations seventeen years ago, and they also found a significant difference of concentrations between various types of streets. Heavy metals are often examined due to environmental concerns, and therefore there are many studies on the issue. Zanders (161) revealed that freshly collected road sediment contains a large portion of materials that are finer than 250 µm and that the particles in these materials have the highest concentrations of metals. PGE and some other trafficrelated elements in roadside soils of Saõ Paulo, Brazil, were examined by Morcelli et al. (162). They concluded that the concentrations of PGE and traffic-related elements were high in the vicinity of traffic. A low ratio of Pb/PGE indicates the use of gasoline that is considerably less unleaded as compared to Europe. There were quite a large number of reports (164–173, for example) in the issue of urban soil examinations that could provide background information in criminal investigations. The transfer of soil indoors was examined by Hunt et al. (174), and Turner et al. (175) described a standard approach for determining the characteristic composition of common indoor dust by using a polarized microscope. Case report Bull et al. (176) introduced a case report in which soil and sediment obtained from a footprint cast were utilized. This analysis showed the advantage of integrating different independent techniques. Stam (177) reported a case of sexual assault/attempted homicide in which soil was significant evidence. Morgan et al. (178) reported the application of geoscientific examination to wildlife crime detection by employing the analyses of soil, sediment, and pollen. Finley (179), Sever (180), and Murray (181) described the usefulness of forensic geology by showing how it has been applied to real case studies. Miscellaneous Hanson (182) showed the importance of stratigraphy, which is rarely found in forensic geological papers, in criminal investigations. Cameron (183) described the use of diatoms in forensic science, and Horton et al. (184) examined a quantitative reconstruction technique based on diatom analysis and discussed its application to two drowning cases. Hills (185) provided a general outline of cement and concrete, which are often subjected to forensic examinations as a part of geological materials.


The application of a geological technique to study bone minerals was mentioned by Trueman (186). Pye (187) also described the application of isotopes and trace elemental analysis to the examination of human bone and teeth for forensic purpose. References 1.




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Fitzpatrick R, Raven M, McLaughlin M. Forensic soil science: An overview with reference to case investigations and challenges. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 9. Clarke R, Brmner G . The use of heavy mineral analysis to establish the provenance of suspect shellfish. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 11. Stam M. Soil as evidence in a Southern California forensic case and the development of a searchable soil profile database. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 12. Raven M, Fitzpatrick R. Overview of x-ray methods and application to forensic soil examinations with case studies. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 13. Verrall M. Mineral identification using the AutoGeoSEM. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 14. Forrester S, Fitzpatrick R, McLaughlin M, Janik L. Mid–Infrared spectroscopy (MIR): Overview of methods for rapid soil analyses in forensic soil examinations. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 15. Tibbett M. Forensic Taphonomy and decomposition processes in Gravesoils. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 16. Nobes D. Clay vs Silt vs Sand: Does geophysical surveying of burials work all the time? Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 17. Moffat I, Wallis L, Mill P, Keane B, Woogwer Valley Aboriginal Corporation. Geophysical investigations at the Alleged Woolgar Massacre site, NW Queensland. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 18. Fitzpatrick R, Baker A. Magnetic susceptibility and low altitude aerial photography using a helium balloon: Applications to forensic soil examinations. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 19. Nobes D, Bateman L, Butland C, Flintoft M, Geiger F, Lea J et al. From Kaikoura to Kaitorete: Non-invasive geophysical imaging of Maori burial sites. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 21.


Forensic Geology



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Zarcinas B, McLaughlin M, Ohmsen G. Case study involving lead and cadmium contamination around a lead smelter. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 22. Scheckel K. Distinguishing, anthropogenic and geogenic impacts of environmental contamination. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 23. Andrew A. Isotopes in soils: application to forensic science. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 24. Walker S. Very wet soil. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 25. Fitzpatrick R, Baker AKM, Raven M, Rodgers S, Degens B, George R et al. Terrestrial environmental forensic investigation: Case Study of elevated levels of metals in drains in the WA wheatbelt. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 26. Horswell J, Parkinson R, Macdonald C, Cordiner S, Speir T,Chambers G et al. DNA Fingerprinting Soils - dirt, death and DNA. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 27. Waters JM, Chan HJA, Rodgers CDG, Burgoyne L, Catcheside DEA. Profiling and diversity estimations with soil DNA. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 28. Dawson L, Macdonald LM. Identification of crime scene origin through use of soil organic evidence. Program and Book of Abstracts of International Workshop on Criminal and Environmental Soil Forensics 2006; April 8-9: 29. Cheetham P. Geophysics and the locating of clandestine graves - out of its depth? Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Hunter JR, Simpson B. Geophysics in the wider context of forensic search. Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Wilson P, Ruffell A. Searching for the IRA ‘disappeared’: groundpenetrating radar survey of cemetery graves, N. Ireland. Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Cheetham P. Review of recent work in forensic geophysics at Bournemouth University Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Graham C, Meneely J. Cyrax Laser Scanning aids criminal, built environment and archaeological investigations. Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Smith P, Hunter J, Baber C, Woolley S, Cross J. The integration of wearable computer technology into forensic archaeological practice. Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16.



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Challis K, Henderson J. Extending the remote sensing record: Using declassified intelligence satellite imagery for landscape reconstruction in the Middle East. Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Wagstaff B, Dyer D. Bedfordshire police and photogrammetry. Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Fowler MJF. Archaeological uses of satellite imagery: lessons for forensic remote sensing. Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Sykes J. Current MOD remote sensing techniques, including photogrammetry for rapid response operations. Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Boyd G. Use of thermal helicopter video transmitted to hand held devices and dogs for criminal tracking, and body searching. Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Harrison M. Current practice in body search & recovery. Abstract Booklet of Forensic Remote Sensing and Geophysics Conference; 2006; December 16. Pringle JK, Cassella, JP, Middleton H, Rogers D, Summers R, Cassidy N. Multi-disciplinary studies and taught site material on a simulated clandestine grave site. Programme and Abstracts of Geoscientists at Crime Scenes, Joint EIGG & Forensic Geology Group Meeting 2006 December 20. Hunter J, Reddick A, Sterenberg J. Integrated approach to mass grave detection. Programme and Abstracts of Geoscientists at Crime Scenes, Joint EIGG & Forensic Geology Group Meeting 2006 December 20. Tempest AL, Cheetham PN. An assessment of geophysical methods for locating animal mass graves and observations pertinant to their use in locating human mass graves. Programme and Abstracts of Geoscientists at Crime Scenes, Joint EIGG & Forensic Geology Group Meeting 2006 December 20. Smith AS. Geomaterials from civil to criminal law; one small step for the Geoscientist. Programme and Abstracts of Geoscientists at Crime Scenes, Joint EIGG & Forensic Geology Group Meeting 2006 December 20. Harrison M. Search methodologies. Programme and Abstracts of Geoscientists at Crime Scenes, Joint EIGG & Forensic Geology Group Meeting 2006 December 20. McKinley J, Keaney A. Different scales of spatial sampling in forensic investigations: case studies from the macro to micro scale. Programme and Abstracts of Geoscientists at Crime Scenes, Joint EIGG & Forensic Geology Group Meeting 2006 December 20. Sablock J. Using The non-quartzose components of local sands for forensic comparison. Programme and Abstracts of Geoscientists at Crime Scenes, Joint EIGG & Forensic Geology Group Meeting 2006 December 20. Bergslien E, Bush P, Bush M. Application of field portable X-ray Fluorescence (FPXRF) spectrometry in forensic and environmental geology. Programme and Abstracts of Geoscientists at Crime Scenes, Joint EIGG & Forensic Geology Group Meeting 2006 December 20.


Forensic Geology

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177. Stam M. Soil as significant evidence in a sexual assault attempted homicide case. In: Pye K, Croft DJ editors. Forensic Geocience: Principles, Techniques and Applications. Geological Society Special Publication 232. London: Geological Society; 2004. p. 295-299. 178. Morgan RM, Wiltshire P, Parker A, Bull PA. The role of forensic geoscience in wildlife crime detection. Forensic Science International 2006; 162: 152-162. 179. Finley JA. Geologic materials as physical evidence. FBI Law Enforcement Bulletin 2004; 73(3). 180. Sever M. Murder and mud in the Shenandoah. Geotimes 2005; January:. 181. Murray R. Collecting crime evidence from earth. Geotimes 2005; January:. 182. Hanson ID. The importance of stratigraphy in forensic investigation. In: Pye K, Croft DJ editors. Forensic Geocience: Principles, Techniques and Applications. Geological Society Special Publication 232. London: Geological Society; 2004. p. 39-47. 183. Cameron NG. The use of diatom analysis in forensic geoscience. In: Pye K, Croft DJ editors. Forensic Geocience: Principles, Techniques and Applications. Geological Society Special Publication 232. London: Geological Society; 2004. p. 277-280. 184. Horton BP, Boreham S, Hillier C. The development and application of a diatom-based quantitative reconstruction technique in forensic science. Journal of Forensic Sciences 2006; 51(3): 643-650. 185. Hills LM. From rocks to skyscrapers: the life of a cement grain. Microscope 2005; 53(2): 89-93. 186. Trueman CN. Forensic geology of bone mineral: Geochemical tracers for post-mortem movement of bone remains. In: Pye K, Croft DJ editors. Forensic Geocience: Principles, Techniques and Applications. Geological Society Special Publication 232. London: Geological Society; 2004. p. 249-256. 187. Pye K. Isotope and trace element analysis of human teeth and bones for forensic purposes. In: Pye K, Croft DJ editors. Forensic Geocience: Principles, Techniques and Applications. Geological Society Special Publication 232. London: Geological Society; 2004. p. 215-236.


Chapter 5 Paint and Glass Maureen J. Bradley, PhD6 Andria L. Hobbs, MS Diana M. Wright, PhD Robert D. Koons, PhD Introduction An estimated 1000 articles and presentations with potential interest to the forensic science community concerning the areas of paint and glass have been published since mid-2004. Articles selected and included in this review provide a good representation of the technical fields covered and were deemed to be either of the most importance or of the most interest to paint and glass examiners. There has been considerable change in the distribution of literature among topics since the last report. The distribution of papers among technical topics reflects the level of active research and publication and not the level of importance or frequency of utilization of methods by crime laboratories. For example, there are many papers describing elemental characterization of glass, but few detailing methods for refractive index measurement, although the latter is more frequently used by the forensic community. Similarly, Raman spectroscopy is widely reported in the literature for the analysis of paint, although, at this time, relatively few forensic laboratories utilize the technique. Also, the number of studies concerning paint and glass analysis in the fields of art and archaeology far exceeds the forensic applications, although these disciplines have much in common. Therefore, art and archaeological applications are included in this review. Conferences focused on specific topics provide in-depth coverage of their respective fields. Proceedings and abstracts from these conferences may serve as additional resources to determine what techniques are being explored, what studies are being undertaken, and by whom. However, abstracts often contain too little information and do not always capture the totality of the materials presented. Therefore, only a few conference presentations have been included in this review. This review is divided into two distinct sections, paint and glass, with further subject headings used within each section to assist the reader in delineating pertinent areas of interest. Paint Formulations and Technology Two underlying themes were apparent when reviewing relevant articles in paint and coating trade journals; reduce both cost and the negative impact paint formulations have on the environment. The industry is being directed away from solvent borne formulations toward waterborne, high solids, and powder coatings. Paint suppliers are faced with meeting these challenges, while trying to fulfill or exceed customer expectations. 6

Federal Bureau of Investigation Laboratory, Quantico, Virginia, U.S.A. 22135


Paint and Glass

Automotive Paints Paint application is historically the most expensive and time consuming step in the automobile assembly process and requires the largest energy consumption. Compounded by the push to lower volatile organic compound (VOC) emissions and reduce solvent borne formulations, automobile manufacturers’ paint suppliers are developing new technologies that are being implemented in assembly plants. Typically, the basecoat and clearcoat are a wet-on-wet application. This means that after the basecoat is applied, it is “flashed off”. Lower temperatures and shorter times are used to set the basecoat rather than fully curing it prior to application of the clearcoat. Once the clearcoat is applied, the vehicle is passed through a drying zone or oven to fully cure the top coats. Ford Motor Company’s new “Paint Shop of the Future” is being pilot tested at its Ohio assembly plant (1). It consolidates the application of the primer surfacer, basecoat, and clearcoat in a single step (wet-onwet-on-wet). This eliminates the need for separate applications, spray booths, and ovens. Typically, because they are wet-on-wet applied, basecoats and clearcoats have comparable chemistries. It is not evident from this article whether this will also be the case for the paints applied in a wet-on-wet-on-wet process. In a 2005 article, Spielman (2) wrote about how increasing environmental regulations have an effect on developments in automotive paint formulations. BASF’s SlurryGloss, a solventless clearcoat, is given as an example. CathoGuard500 and Powercron 8000, from BASF and PPG, respectively, are also provided as examples. These are both lead- and chromium-free, low VOC electrocoats. Schoff (3) stated in his 2005 paper that the use of electrodeposition coatings containing lead will be replaced with lead-free versions. He also predicted that wet-on-wet-on-wet applications will become more common in the industry. Another way to reduce costs is to modify the processes to reduce or eliminate layers while still maintaining quality. In Spielman’s 2005 article cited above, BASF’s Integrated Process II was mentioned. It is discussed in further detail in Pianoforte’s 2007 article (4). Basically, one layer replaces the basecoat and primer surfacer layers. The layer is specially formulated to combine the function of both layers, including stone chip protection and ultraviolet resistance. The new system has been successfully implemented in the Mini production line at the BMW Group’s Oxford, UK plant. Since the primer application and oven sections are no longer needed, they have been converted to a second basecoat/clearcoat line to increase production capacity at the plant. This article also reports on a wet-on-wet two-tone process developed by DuPont that was implemented at Ford’s Kentucky truck plant. This has increased capacity and lowered production costs. DuPont has also developed EcoConcept, a primerless waterborne top coat system. This system also eliminates an entire step in the paint application process; the basecoat is applied directly to the electrodeposition coat. The system is in place at two Volkswagen (VW) facilities; one of theVW Jetta paint lines in Puebla, Mexico, and in the VW paint shop in Pamplona, Spain. In 2007, BASF introduced a transparent cathodic electrodeposition coating (5). It differs from conventional electrodeposition coatings in that it is not pigmented. The article did not specify whether or not this product would be used in automotive original equipment manufacture (OEM) production.


Pretreatments Changes may be in store for surface pretreatment as well. Giles reported that many pretreatment companies have invested huge research dollars to develop a coating that limits the dependence on zinc, a regulated heavy metal (6). Gichuhi et al. (7) discussed how zinc phosphate is a low cost alternative to lead- and hexavalent chromium-based corrosion inhibitors. The article stressed that many health authorities classify zinc, strontium, and barium (excluding barium sulfate) as heavy metals and consequently may be regulated. The focus of the remainder of the paper was the use and performance of organic corrosion inhibitors as viable alternatives. Laminated Films on Plastics As an alternative to the way paint is traditionally applied to a vehicle, manufacturers are exploring dry paint films (8, 9). Paint films are laminated and applied to plastic substrates such as thermoplastic olefins (TPO), acrylonitrilebutadiene-styrene copolymers (ABS), and polycarbonate (PC). In a 2006 article, Chouinard (8) elaborated on how the films are manufactured and stated that current paint chemistries are not used to make the laminated films. In contrast to a traditional painting operation, the films start with the clearcoat being cast on a heat stabilized polyester carrier. The colourcoat can then be applied in a second pass as a wet-on-wet application. An appropriate adhesive or “primer” allows the laminated film to then be applied to the plastic part. The thermoplastic nature of the film provides significant improvement in chip resistance and allows it to conform to any shape. Soliant, a manufacturer of exterior durable films, estimated that between 2001 and 2006, over 40 million exterior automotive components have been surfaced with dry paint film with explosive growth expected over the next three to five years. Current applications include, but are not limited to, rocker panels, fascias, body side moldings, grilles, and bezels. Acura, Audi, Chrysler, Ford, General Motors, Honda, Mercedes, Saab, Toyota, and Volvo are cited as currently using this technology. In Whitfield’s article (9), the SMART roadster is noted as creating momentum in the marketplace. It has a filmed plastic roof which demonstrates this technology can be used to create larger body parts. The advantage of plastic over traditional steel is that it is half the weight and can be molded into shapes that defy a stamping press, translating into better fuel economy and more aggressive exterior styling and curves to differentiate product lines. Pigments and Additives In a 2006 article on pigments, Challener (10) reported that the largest application for pigments is in paints and coatings, followed by inks. Wright (11) corroborated this statement in a 2007 article summarizing metallic pigments. The article stated that the highest demand for aluminum pigments continues to be the automotive industry for use in paints, plastics, and wheel rims. The ‘liquid metal’ effect can be produced by utilizing vacuum metallized aluminum flake. Vacuum metallized pigments (VMP) are produced by deposition of vaporized metal, in this case aluminum, onto a smooth surface. The thin layer is then stripped from the surface and broken down into particles of suitable size for their use as a pigment in surface coatings. Unlike conventional aluminum flake, the resulting flakes are extremely smooth resulting in a mirror-like finish. Venturini et al. stated in their US patent (12) that the VM 91

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aluminum flakes are on the order of one tenth the thickness (0.01µm – 0.05 µm) of conventional aluminum flake (0.1 µm – 0.5 µm). Both Venturini et al. as well as Yates and Mitchell (13) discussed that the use of VMP aluminum pigments at lower loads than conventional aluminum flake resulted in films with higher reflectivity and higher opacity. Yates and Mitchell went on to report that this type of pigment is currently used on Giant bicycles. Pianoforte’s 2007 article (14) on high performance pigments reported that Mercedes is the first car manufacturer to utilize the liquid metal effect in a waterborne paint system. Traditionally, aluminum pigment manufacturers supplied their product in the form of a paste containing 60-80% pigment in a mixture of hydrocarbon solvents. However, in order for it to be compatible with new paint formulations, modifications including application of a surface treatment, dispersement of the pigment in a resin rather than a solvent, and silica encapsulation needed to be made (15,16). The type of modification depends on whether the formulation is waterborne, high solids, or a powder coating. A pigment available from EMD chemicals that will find its widest application in automotive and other OEM coatings is Xirallic® crystal effect pigment. These pigments are based on aluminum oxide platelets coated with metal oxides. They provide more glitter effect and stronger colour saturation than traditional effect pigments (10). New pigments available from Ciba and BASF include reflective, opaque organic reds, and transparent oranges and blues. Huebach also introduced Tico™ and Bitan products, which combine properties of different pigment chemistries such as hiding power and colour. Brussaard and Genn stated that using a Tico™ (titanium colour pigment) as opposed to blending titanium dioxide (TiO2) with coloured organic pigments resulted in less pigment loads with more vibrant colours achieved (17). Heubach also introduced a yellow azo pigment that is designed for polymer applications. It has a temperature resistance of 320oC. The company has also introduced a green shade of bismuth vanadate for use in industrial and automobile coatings. Another product available from Heubach is micronized rutile yellow (18). It was reported that when used in place of conventional high-performance TiO2, less organic pigment load is necessary. In addition to saving costs on both organic pigments and TiO2, higher hiding power and better weatherability were achieved in the cured films. As reported by Wilker (19), a new yellow organic pigment, Hostaperm Yellow H5G (Pigment Yellow 213), has been accepted by all major automotive OEM paint manufacturers and can be used in waterborne and high solids formulations. Traditionally, aluminum flake of the cornflake type has been used as the substrate for effect pigments. In a 2004 article, Schmid and Mronga (20) reported that BASF was working on a new generation of effect pigments by coating aluminum flakes of the silver dollar type with iron oxide. The resulting golden, orange, and red pigments produced high chroma, hiding power, and sparkling effects. They went on to report on the development of iron oxide plates; effects such as opacity, colour, and level of sparkle can be altered by varying the thickness of the resulting flakes. An excellent overview of diffractive pigment technology was provided in Parker’s 92

article (21). It included theory, definitions, compositions, and photomicrographs depicting the grating structure present on their surface. A US patent issued in 2005 covers novel black pigments that are prepared by mixing carbon black with particular organic pigment intermediates and pigment derivatives (22). The resulting black pigments are suitable for use in paints and inks and produce a deep colour characteristic that cannot be achieved with carbon black alone. BASF launched Near Infrared (NIR)-transparent black pigments in 2006 (23). These pigments have been designed to reduce the solar heat buildup of darkcoloured or black-coloured construction elements by up to one-half. Aside from their use in construction, potential applications for these pigments include the coatings and printing inks industries. A similar product is reported on by Hope (24); specially engineered additives, termed Total Solar Reflectance (TSR) technology, keep painted and coated surfaces cool by reflecting infrared energy leading to lower energy costs and increased life of the substrate. These additives can be integrated into current product lines for industrial maintenance coatings and coatings applied to wood, automobiles, and concrete. Recent developments in nanotechnology have enabled paint formulators to create more advanced coatings. So called “smart” architectural coatings have been developed that use nanosized particles of TiO2 to trigger photo catalytic activity that reduces air pollution (25,26). Nitrogen oxide gas permeates the paint and is converted to nitric acid when exposed to sunlight. It is then neutralized and washed away with rain. Researchers at PPG applied for two patents in 2003 in which they utilized aluminum silicate nanoparticles in their automotive coatings to achieve better chip and scratch resistance (27). In addition, Nanophase Technologies Corp. has developed two grades of alumina nanoparticles that can improve scratch resistance significantly (28). The addition of hollow glass microspheres as an extender in a paint or coating can improve the paint’s properties, cut down on the VOCs and decrease the amount of TiO2 needed (29). Due to their size (18-30 µm) and shape, they reduce the coating’s viscosity, which was generally controlled by the addition of solvent. They also impart some opacity to the paint thereby reducing the amount of TiO2 needed. Research conducted by Shinkareva and Safonova demonstrated that metalized hollow microspheres, made possible by advances in plasma technology, can be incorporated into coatings to serve as conductive and heat insulating fillers (30). A number of new ultraviolet (UV) absorbers [hindered amine light stabilizers (HALs)] that meet the continually stringent demands of coating formulators are reported by Rogers (31). Advantages achieved by using these new UV absorbers included their non-migratory nature, compatibility with waterborne formulations, and improved UVresistance at thinner coating thicknesses. Formulators use smectite clays, such as Bentonite, in coatings to develop certain rheological and performance properties. In his article, Bradford discussed the synthesis of a new grade of smectite clay, and its utility as both a thickener and to control metal flake orientation in automotive paint formulations (32). Microspheres, HALs, and smectite clays are just three of the classes of additives defined in Paint and Coatings Industry’s Additives Guide (33). Updated and 93

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published annually, this guide is an excellent resource. It includes definitions and examples of various additives in a format that is easily understood regardless of the readers’ paint experience. Automotive Colour Popularity Silver continued to be the top automotive colour choice globally over the last three years. White/white pearl and black were among the top three, while blue, red and light metallic neutrals (shades of beige, champagne, gold, and copper) jockeyed for fourth and fifth position (34-37). Colour designers and forecasters from DuPont, PPG, and BASF all report that brighter, more vibrant colours such as red and blue are expected to grow in popularity within the next three to five years. They also report on the new colours being offered that infuse colour, such as blue and red, or other metallics like copper and gold, to silver to add diversity to this popular colour choice. Developing new colours is not the only way paint companies alter or enhance their products. As previously reported, specialty formulated pigments can provide a ‘liquid metal’ effect (14). In contrast, BASF Coatings introduced a matte clearcoat which provides a satin-finish to the surface (37). Marine and Maintenance Coatings Although not encountered frequently in case work, the forensic scientist should be aware of changes occurring in marine and industrial maintenance coatings. Antifouling paints are applied to structures and areas of a vessel that are submerged in water. These paints are designed to release a biocide to kill organisms before they become permanently attached to the surface. If left untreated, fouling organisms such as algae, barnacles, and mussels attach to the surface thereby affecting the weight and fuel efficiency of the vessel. Concerns, regulations, and legislation regarding the environment do not only affect paint suppliers to the automotive and architectural markets. A resolution adopted by the International Maritime Organization (IMO) in 1999 banned the application of tributyl-tin (TBT) paints on all vessels by 2003. This treaty also called for the elimination or effective containment of organo-tin compounds from all ships’ hulls by January 2008 (38, 39). Therefore, most global antifouling paint suppliers discontinued paint products containing TBT between 2003 and 2005. Most antifouling paints used today are copper-based. However, they may face the same future as their tin-based predecessors. In two separate citations (39, 40), the authors reported that dissolved copper levels in the water collected close to boatyards and marinas exceeded both state and federal allowable levels. International Paint’s marine and protective coatings unit has developed a silicone based foul release coating. This product does not use biocides but rather relies on the slippery, low friction surface to which fouling organisms have difficulty adhering. They also introduced a fluoropolymer coating in February 2007, which had been applied to 20 vessels as of May 2007 (38). Other technologies being explored are silica encapsulation of the copper biocide (41) and the use of natural materials such as algae and tubeworms (42). In a 2004 estimate, over $1.5 billion/year was spent on marine and industrial maintenance coatings (43). Approximately 80% of industrial maintenance paints 94

applied to steel and concrete structures are solventborne, with epoxy, polyurethane, and alkyds being the most predominant resins. Regulatory pressures will continue to move industrial coatings toward waterborne, high solids solventborne, and other technologies that comply with recent standards. Procopio, et al. (44) reported on an acrylic latex formulation developed for industrial maintenance use. Based on the results presented, the specially-engineered polymer developed showed promise in this application. Borst and his colleagues (43) reported on the use of epoxyfunctional silicone resins as a suitable replacement for polyurethanes. Their findings are reinforced in Kukachova’s paper (45) where it was reported that rather than the traditional application of an epoxy layer followed by a polyurethane topcoat, these two layers can be replaced by one epoxy-silane coating. This resulted in significant cost savings and increased corrosion- and UV-resistance. Paint analysis in art and archaeology As was reported in the last review of paint literature that was compiled for the Interpol Forensic Science Symposium in 2004, over 50 articles concerning art and archaeological materials analysis were found in the relevant scientific literature. A two part series of articles written by Skelton in 2004 describe the history of pigments used in the Western art world from prehistoric times through modern day (46, 47). These publications provide context for both inorganic and organic pigment development and usage and collectively include over 400 citations. Adriaens compiled a good overview of European research conducted in the first half of this decade for non-destructive analysis of art and archaeological artifacts (48). Van Grieken and Janssens also edited a book entitled Cultural Heritage Conservation and Environmental Impact Assessment by Non-Destructive Testing and Micro-Analysis (49), which covers a broad range of art conservation methods and techniques. Paint, as well as glass, bronze, gold, and marble, are featured surfaces discussed in the chapters of this book. Much of the remaining published literature is specific to a given work of art or type of analysis. In general, these articles provide a good foundation for the continuing use and prevalence of non-destructive techniques in disciplines similar to forensics. Consideration of these methods may no longer be beyond the scope or resources of forensic laboratories. Therefore, the applications of the analytical methods presented herein may be applicable to objects known as “evidence” as well as those termed “artifacts.” The following table lists a wide range of techniques described for the analysis of pigments, binders, and resins in historical art works and archaeological artifacts. The relevant citations are also provided for easy reference.


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Techniques Pigments Raman Spectroscopy Energy Dispersive X-ray Fluorescence (EDXRF) Scanning Electron Microscopy with Energy Dispersive X-ray Fluorescence (SEM/EDS) IR spectroscopy Particle (or proton) induced X-ray Emission (PIXE) Laser Ablation – Inductively Coupled Plasma Spectrometry (LA-ICPMS) Pyrolysis-Gas Chromatography Mass Spectroscopy (Py-GCMS) X-ray diffraction (XRD) Chemical testing Fibre Optic Diffuse Reflectance Spectrometry High Resolution Electron Microscopy Laser Induced Breakdown Spectroscopy (LIBS) Light Microscopy Neutron Activation Analysis (NAA) Polarized Light Microscopy (PLM) Secondary Ion Mass Spectrometry (SIMS) Total Reflection X-Ray Fluorescence (TRXF) X-Ray Photoelectron Microscopy Binders GCMS IR Spectroscopy Secondary Ion Mass Spectrometry (SIMS) Thermally Assisted Hydrolysis and Methylation (THM GCMS) Direct Temperature Resolved Mass Spectrometry (DTRMS) Electrochemical Impedance Spectroscopy (EIS) HPLC with Fluorescence Nanotechnology NMR Raman Spectroscopy Size Exclusion Chromatography (SEC) - FTIR XRF Resins GCMS Pyrolysis-Gas Chromatography Mass Spectroscopy (Py-GCMS) Capillary Electrophoresis (CE) Matrix Assisted Laser Desorption Ionization Time of Flight Mass Spectroscopy (MALDI-TOF)

No. of Citations


23 13 14

5 2

(50-72) (51,73-85) (53,56,65,82,83,8694) (70,81,83,84,86,87, 89,93) (65,66,84,95,96) (77,97)

2 2 1 1 1 1 1 1 1 1 1 1

(100,113) (77,93) 53 98 71 99 91 65 53 91 74 101

5 5 2 2 1 1 1 1 1 1 1 1

(102-106) (65,70,107-109) (91,110) (107,108) 90 73 106 111 112 72 109 79

6 4 1 1

(103-106,114-116) (92,100,113-114) 117 118


In addition to these individual discussions of science applied to art conservation and restoration, Schnell et al. published a chapter in Volume 100 of Lasers in the Conservation of Artwork describing analytical testing using such techniques as environmental SEM (ESEM), XRD, FTIR and NMR to determine the energies at which pigments were discoloured by exposure to lasers during cleaning techniques (119). In this work, inorganic pigments and organic binding media were tested using laser irradiation set at 1064 nm.


Kendix and colleagues applied micro-Raman spectroscopy to embedded cross sections of architectural paints in an examination of the interior decoration of a historical building (120). When complemented by SEM/EDS analysis of the same samples, both the elemental distribution and the molecular structures of the pigments used were able to be discerned. In a separate study of historic architectural design using Raman spectroscopy, Castro et al. presented an overview of the use of FTIR and Raman in the analysis of nineteenth century wallpaper (54). The combination of vibrational techniques allowed for the evaluation of the pigments, binders, and degradation of the cellulose substrates. The authors noted that the wallpaper industry was a reflection of the prosperity of the era and as such depicted a timeline for the introduction of new pigments into society in the same way other craft-oriented objects would. Both antique (carbon back and red oxides) and more modern (synthesized) pigments such as copper arsenic and ultramarine blue were able to be characterized in this study. Castro and collaborators also published a 2005 paper regarding development of spectral databases for cataloguing and searching fine art pigments using both dispersive Raman and FT-Raman spectroscopy (55). Both sets of data are loaded into an e-vibrational spectroscopic database (e-VISART), which contains spectra, pigment names in multiple languages with chemical compositions, reference numbers, period or year of first use, compatibility with other pigments or media, and applications. The user can also obtain access to previously reported FTIR data at this site as well. The databases can be accessed via the internet using the website address as follows: The login for the site is: spectra. The password is: database. Both dispersive and FT-Raman spectra were collected to offset problems from fluorescence encountered with the 785 nm laser employed for the dispersive Raman data collection. FT-Raman measurements obtained for pigments such as kaolin were made possible using a 1064 nm laser excitation source. Edwards and Chalmers edited a text in 2005 regarding the use of Raman spectroscopy in archaeology and art history (58). This book, which was favorably reviewed by Ariese in 2005, contains 25 chapters that have been authored by over forty scientists (121). It covers basic theory, the usefulness of Raman spectroscopy in the fields of art and archaeology, the comparison of Raman to other microscopic and spectroscopic techniques, and the core chapters of the book, which are divided into four application areas. There is a section dedicated to dyes and pigments, which includes a case study by Bersani, Lottici, and Casoli of frescoes analyzed by micro-Raman and GC/MS and another section by Withnall, Shadi, and Chowdhry on the analysis of dyes by surface enhanced resonance Raman spectroscopy (SERRS). Chapters in the third section are devoted to analysis of artifacts. An overview by Vandenabeele and Edwards as well as the case study of museum objects by Burgio seem most relevant to topics discussed herein. Other specific applications of Raman spectroscopy for the analysis of regional pigment use were documented by Wang et al. (71) for an ancient Chinese tomb, by Ambers (50) for Egyptian objects and 97

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paintings dated between 2600 to 2300 BC, and Hernanz et al. (62) on Spanish prehistoric rock paintings. Chen et al. (57) also published research regarding the application of a surface enhanced Raman scattering (SERS) technique for the characterization of anthraquinone dyes used in artwork. This latter study determined that a 50 nm layer of silver nanoparticles coated on an alumina substrate could detect alizarin dye at about 7 x 10-15 femtograms. The concept was effectively tested when alizarin was identified in a solution extracted from a silk textile known to have been dyed with an alizarincontaining compound. Vandenabeele and coauthors published multiple articles in recent years on the use of a mobile fiber optic based Raman instrument capable of in situ analysis of museum artifacts (52, 67-69). One of these studies demonstrated the ability to characterize an indigo pigment not previously associated with Bronze Age Greek painted plaster (67). Another describes the instrument design and capabilities in detail, including the use of a portable computer for ease of transport and a fiber optic probe in conjunction with a variety of positioning tools and stages to best effect focus and sample-to-instrument distancing. The 2005 and 2007 papers by Vandenabeele’s group (68, 69) describe the practical challenges associated with in situ analysis of artifacts in their display setting or a conservation laboratory. In the former, research can be conducted without gratuitous handling or movement of the object or painting. However, museum visitors’ safety and curiosity become factors for consideration in addition to the positioning of the fiber optic probe in relation to the object’s surface. For example, in the analysis of a painting, the angle of the probe had to be adjusted in accordance with the angle at which the art had been hung. The display angle had been chosen to maximize the viewing experience and minimize aesthetic and destructive effects of the room’s lighting conditions. The authors report that manipulation of the versatile probe design allowed for effective, noninvasive analysis despite this situation. Analysis in the conservation laboratory proved challenging as well, due in part to the excessive ambient lighting conditions which tended to overwhelm the background signal. Similar work was also reported by Andrikopoulos et al. (51). However, this study utilised an instrument capable of both Raman and XRF analyses. Data was collected from the same spots on the painting in order to provide complementary information for pigment elucidation, even in areas where over-painting had been introduced to the original artwork. In addition to the aforementioned text, Edwards and colleagues also published about specific uses of Raman spectroscopy in art characterization and authentication (59, 60, 63, 64). Of note, Edwards, Wolstenholme, and others report on their use of Raman spectroscopy to characterize pigments used in black, blue, gray, green, red, and white paints associated with a noted church architect, Sir Ninian Comper (59). This work determined the chemical composition of the pigments used to create colours known as Comper red and Comper green, which had not previously been reported in the scientific literature. For the characteristic strawberry red colour of the former, a mixture of vermilion, hematite, and barites were used. The dark green Comper green effect was achieved by the combination of Prussian blue with chrome yellow, also known as lead (II) chromate. Edwards also co-authored two papers that call into question the use of titanium, particularly anatase, as an indicator of modernity in artworks purported to be of 98

ancient design and construction (60, 64). Raman spectroscopy identified the presence of anatase in Roman pottery that predates known uses of titanium dioxide as a whitening pigment. While the amounts are small enough to be considered a natural but not deliberate addition to kaolinitic clay, the authors state that its presence cannot be disputed. The second paper by Edwards on this topic yields findings that the authors state are strongly indicative of anatase as a pigment in Europe approximately two thousand years ago. They further suggest that its presence cannot be attributed to impurities within the raw materials used in construction or sedimentary accumulation on the artifact after its burial. Weis, Jiang, and Grant published a paper on the use of second derivative preprocessing of Raman spectra in order to diminish interference from fluorescence (72). Partial least squares regression algorithms were applied to pigment libraries as well as to the analysis of oils commonly used as binding media (linseed, walnut, and poppyseed oils). The findings led the authors of the study to conclude that this approach can identify pure pigments, pigments present in dilute quantities in binding media, and fatty acids of similar chemical compositions. An NMR publication (112) described analysis as applied to the study of aged binding media used in paintings. The study was carried out in attempt to determine the amount of degradation of aged binders and to verify the ability of NMR to differentiate binding media. Stated advantages of NMR include speed, simplicity, non-destructiveness, and minimal sample preparation. Through NMR the state of hydrolysis and oxidation of linseed and egg tempera binders was successfully established. Further, the copolymer composition of acrylic media was determined and the presence of various additives included in their formulation was established. The use of multiple techniques in the analysis and restoration efforts being pursued in conservation research is highlighted in separate articles by Pavlidou, Higgitt, and others (53, 65, 83, 89). Pavilodou et al. (83) described micro-FTIR, optical microscopy, TXRF, and SEM/EDS in the analysis of paint samples from wall paintings in churches throughout Albania and Greece which have been attributed to the artist Onoufrios. Pigments such as red and yellow ochre, carbon black, green earth, and calcium carbonate were used in all of the churches from which samples were taken. Deterioration, both from environmental air pollution and lichens, is also noted in the article. In Higgitt’s paper, it is reported that paintings at the United Kingdom’s National Gallery are developing small white inclusions on the surfaces of paintings of different types and from different periods (89). The common denominator in these works has been identified as the use of two lead-based pigments, namely red lead (Pb3O4) and lead-tin yellow (PbSnO4). Analysis of these inclusions was conducted using SEM/EDS and FTIR. Further work indicated that zinc-based pigments also result in the same type of small white inclusions, which have been identified as metal carboxylates that form as a result of reaction between these metal-based pigments and drying oils in the paint formulations. However, these inclusions seem to be self-contained such that the marks have not been observed to get progressively larger or more prevalent with time. Ortega-Avilés and colleagues discuss attempts to date and authenticate an unsigned Mexican painting through pigment analysis (65). Their work concluded that the painting in question was created in the mid-18th century or early decades of the 19th century. SEM/EDS was also used by Haswell 99

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and colleagues to quantitatively analyze extender pigments used in oil paintings as a means of determining the extent to which priming of the canvas influenced the quality of the actual paints used (88). This research is a preliminary step in analysis of Van Gogh’s work that is being conducted in the Netherlands. SEM/EDS initially was used to determine that lead white mixtures were typical with chalk, barium sulfate, gypsum, and clay as bulking agents. This research sought to examine the capability of SEM/EDS to determine quantities of these components within the mixtures. The authors concluded that relative amounts of pigment and extenders in canvas preparation layers could be determined with a relative accuracy of 10% or less. This analysis has significance for authenticity and dating studies of artwork. It also allows conservationists and art historians to construct reference samples for the investigation of artistic painting techniques. White et al. (94) used an ESEM for in situ hydration studies of pigment discolouration processes caused by the interaction of cadmium yellow (CdS) with malachite (CuCO3Cu(OH)2). The commingling was visually observed to produce either a dark-coloured interface between the two pigments or an overall darkening of a mixed pigment layer. Moisture seemed to hasten this process, giving rise to the concept of studying the reaction using ESEM. These researchers determined that copper sulfide resulted from the cadmium sulfide and copper-based pigment interaction. The process is thought to occur when copper ions from the malachite pigment diffuse into the cadmium yellow pigment layer when in the presence of linseed oil and water. The reaction occurs at the interacting surface to produce copper sulfide, the darker layer observed at the interface between the coloured pigments. SEM/EDS was one of many techniques used by van Loon and Boon in characterization of degradation products observed in 17th-century Dutch paintings located in the central hall of The Hague (93). Areas of paintings known to contain pigments used to impart a black or dark brown colour were observed to contain whitened “crust-like” surfaces on top of the original painted layer. This phenomenon was previously thought to have only appeared on frescoes. Crosssections of the affected areas were sampled and compared to “healthy” areas of the same surface. Visible, UV-fluorescence, SEM/EDS, and specular reflectance FTIR were all used to then image the samples being compared. Transmission FTIR and XRD were also used to analyze the white material. Imaging of the layered paint surfaces revealed that the canvas pre-treatment was undertaken with an oil-based lead carbonate (2PbCO3Pb(OH)2) ground that included brown umber particulates, an earth pigment comprised of hydrated iron oxide, and manganese dioxide. The next layer was light-brown and semi-transparent, containing white, red earth, and brown pigments. It served as a primer for the regions where dark hair was depicted in the painting. The topmost layer of dark brown or black paint was quite thick in relation to the underlayers and was composed primarily of bone black pigment with very little red earth. DTMS was used to determine that the binder for this layer was linseed oil. UV fluorescence imaging also provided information as to the true depth of the white 100

degradation product. In addition to being a thin layer on the top of the surface, it was observed within some regions of the bone black layer. SEM/EDS confirmed the presence of calcium (Ca), phosphorous (P), carbon (C), and oxygen (O), as well as some lead (Pb) and magnesium (Mg) in the “healthy” and white degraded areas of the painting’s dark brown/black surface layer. The bone black pigment is an aromatic matrix containing charred bone fragments which impart colour and composition via calcium phosphates and carbon black. The bone as a starting material also results in a small amount of magnesium, roughly an atomic mass ratio of 1:18 with respect to calcium. The lead is thought to be present as a result of lead driers used to absorb the oil within their porous structure and decrease the drying time of black pigments, which as anti-oxidants can slow down the drying process of oils. This finding for the lead use was confirmed with DTMS. SEM/EDS in conjunction with FTIR and XRD analyses of the inorganic species within the topmost layer do not support the notion that changes to the calcium phosphate composition were the cause of the colour change observed for the dark brown/black regions of the painting. While the calcium and phosphorous were evenly distributed throughout the topmost layer, the lead and carbon were not. SEM/EDS revealed that the carbon was slightly less at the surface and the lead more concentrated there. The observed lead intensities correspond to the white areas on the surface as well as in cracks within this topmost layer. FTIR also noted that phosphate was the dominant peak in spectra collected for the black and white samples and showed a marked difference in intensity bands in the “aromatic network” region for the black versus white samples. It is suspected from this data that the lead from the added driers migrated to the surface and acted as a catalyst for UV photo-oxidation of the black layer, thereby causing the discolouration to white. Therefore, preservation of the organic binder might serve to prevent the migration of the lead and diminish the effects of UV and oxidation forces on the painted surface. Van Ham et al. (110) attempted to measure the molecular composition of pigments in paintings using static SIMS with a time of flight mass spectrometer (TOF-MS). The primary conclusion of the authors is that for such a sensitive analytical technique, more refined sample preparation procedures are needed than what has historically been used. A possible advantage of the technique, claimed the authors, is the potential ability to characterize and image both inorganic and organic analytes. Since the last review, Keune and Boon have continued their use of SIMS for the study of pigment degradation in works of art (91). In 2005, they published a study of the combined use of static SIMS data with light and electron microscopy as well as X-ray analysis to identify and localize the various reaction products of degraded vermilion. This work has allowed them to hypothesize an alternative depiction of the reaction mechanism that produces the photodegradation of vermilion. When exposed to light, the vermilion (HgS) in an artwork degrades into elemental mercury and sulfur. The chlorine naturally present in the vermilion acts as a catalyst for this reaction, in which the now elemental mercury deposits as nanoparticles on the surface of the remaining vermilion, turning it from red to black. Exogenous chloride begins to accumulate in the black layer allowing the metallic mercury and the remaining HgS to continue the reaction until a resultant white powder of HgCl2 is 101

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formed on the surface of the artwork. This proposed degradation path was concluded to be an accurate depiction of the colour changes in vermilion on two different paintings created by different painters and housed under different storage conditions. Further, light microscopy provided images of the white degradation product above and around the black product. Most of the black product was observed as a top layer over a red underlayer. Both the black and the red colours remained true under UV light observation. SEM/EDS also provided elemental distribution data and information about the structural changes between the three coloured phases, including confirmation of the presence of elemental mercury nanoparticles through visualization of “hot” spots smaller than 100 microns via back scatter electron imaging (BSI). SIMS detected traces of chloride in the native vermilion, which were not noted in the EDS analysis. SIMS imaging also enabled identification of the white product as mercuric chloride, which has not been reported in previous studies of vermilion degradation in paintings. Just as nanoparticles were observed as a byproduct in the Keune and Boon study, they can also be created for use as a restorative layer in conservation of paintings and de-acidification of historic paper and wood products (111). Baglioni and Giorgi report that the traditional approach to restoration of wall paintings can be enhanced by nanoparticulate technology. Wall paintings that have undergone severe degradation of the calcium carbonate binding as a result of exposure to sulfur need to be treated chemically in order to revert the resulting sulfate salts back to carbonate in order to halt their migration to other areas of the artwork. Following this process with an application of a nanoparticulate dispersion restores the binder to its original condition. The example cited in the study describes in situ restoration of wall paintings in the Yucatan peninsula in Mexico. In this region, there is relatively high humidity year round and short periods of rain. These conditions accelerate degradation processes of the wall art, particularly those which have previously been treated with non-compatible polymeric materials. Several paintings exhibited fissures and powdered paint layers that needed to be reconstituted. An application of calcium hydroxide nanoparticles were gently brushed onto the surface as a dispersion ten to thirty times more concentrated than conventional lime water. The treated area was kept wet for a period of 8 hours in order to maintain conditions favorable to the slow carbonation of hydroxide. After a second treatment of the nanoparticle dispersion, the treated area’s colour passed testing that determined the restoration was successful. Thus, nanotechnology has been demonstrated to provide significant contribution to wall painting restoration with minimal effort and cost expenditures. Analysis of pigment use and recipes by LA-ICP-MS was the subject of two recent independent publications that studied specific populations and the pottery they manufactured. Duwe and Neff reported on the viability of TOF-LA-ICP-MS in studies of east-central Arizona Pueblo IV period ceramics (97). Results indicated that of the sherds tested, three distinct paint recipes could be distinguished within the community studied based on levels of iron, copper, antimony, and lead. These researchers concluded that careful sample selection and analysis of homogeneity in pigment use over the entirety of a vessel’s surface are critical in order to best describe pigment recipes used within communities of potters. Moreover, elemental analyses of these recipes and the subsequent inferred existence of pottery-making 102

familial communities could then be used to differentiate households, and allow for a more thorough understanding of the Pueblo social organization. In the second LAICP-MS study, Green and Watling continued Watling’s previous work in authentication studies via trace element analysis (77). This study used trace element fingerprinting of Australian ocher to establish provenance and subsequent authentication of Aboriginal art. Growing appreciation for indigenous art has spawned increased demand and pricing as well as the need for authentication techniques to combat the rise in fraudulent sales of copies. Aboriginal art usually incorporates a naturally occurring mixture of iron oxide and clay, namely ocher, which varies in colour from white to dark brown. The researchers state that ocher mixtures are often specifically associated with regional artists who use the material from an area of cultural or ancestral significance. Therefore, sourcing facilitates determination of authenticity. The authors report that the analytical reproducibility achieved in this work sufficiently proves that a single sample of ocher from a specific site is all that is needed to derive an analytically robust trace element profile of that area. Therefore, a single sampling from a questioned artwork would be sufficiently homogenous to determine authenticity. This work initiated the creation of a database of ocher samples for future use in authenticity studies. Detection of forgeries was also reported on by Hynek and colleagues in a 2004 article that described the analysis of a 19th-century painting by MALDI-TOF in order to determine the binding media used (118). While attempts to verify authenticity by analytical means is of great importance to the relevant scientific community, far more work has been published on conservation and restoration methodologies. As an example, Erhardt described work by Carretti et al. also in 2004 involving the use of “rheoreversible” gels which remove surface contaminants without altering the original design layer (116). The gelled solvent mixture reported on by Carretti and colleagues reverts to a free-flowing liquid when a few microliters of a dilute acetic acid solution are added to it. This process of liquefying the gel makes it much easier to remove from the surface along with the contaminants it has enveloped. Analysis of the gel by FTIR and SEM/EDS after removal from a painted surface showed that none of the binder or pigmentation had been transferred from the original artwork. This work was noted by Erhardt to be significant progress in the restoration field. Additional papers of note that have been published since the last review in relation to paint analysis of art works include the use of a three dimensional micro-XRF technique for analysis of in-situ paint layers (79) and two papers in the journal Applied Physics A from 2006. In the first, Krug and colleagues present the use of synchrotron-based K-edge absorption imaging as applied to paintings in order to develop elemental mapping profiles over large areas (80). This technique is also referred to as dichromography, which is the process of taking two images ideally acquired with a monochromatic X-ray beam and logarithmically subtracting one from the other to obtain two orthogonal images. One of the resulting images is the mapping of a specific element, while the second contains the map of the background. This approach allows for the detection of a specific pigment throughout the paint layer system. For example, paintings can be imaged such that each brush stroke may be examined through use of the high atomic number elements in the pigments. Common elements in historic artists’ pigments such as 103

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cadmium, mercury, lead, barium, antimony, and tin can be examined in this way. Colour information on individual paint layers can then be determined nonintrusively by art historians and conservators. The described approach is noted to allow for quick data acquisition and elemental sensitivity throughout the paint stratigraphy. In the second article from this journal, Dupuis and Menu described the use of fiber optic diffuse reflectance spectroscopy (FORS) for the non-invasive, quantitative identification of artistic reference paint mixtures (98). This paper describes initial work in this area with testing of the methodology on genuine artworks to be presented in future studies. The purpose of this preliminary research was to determine if reflectance measurements of paint mixtures could yield identification of individual components, which was accomplished to the authors’ satisfaction. Another application of fiber optic reflectance spectroscopy as applied to in situ analysis of paintings makes use of FTIR in conjunction with XRF (81). Principal components analysis (PCA) was used to discriminate patterns in the initial FTIR data collected from a Renaissance era fresco located in a church in Italy. Of the initial 65 reflectance spectra, a group of 56 data points was subjected to a further PCA algorithm in order to better differentiate the results. From this work, it was observed that the painting surface had at some point in time been subjected to a layer of casein, probably as a protective finish. Other areas contained a protein based binder such as animal glue or egg tempera. The FTIR and XRF techniques were used in concert to evaluate pigment composition. The FTIR analysis allowed for identification of mixtures of blue and green pigments such as malachite and azurite. When combined with XRF for elemental information, a complex mixture of green colourants containing malachite, green earth, and smalt (potassium glass containing cobalt ions) was able to be identified without any sampling of the fresco. The authors concluded that this work demonstrates the abilities of noninvasive techniques to provide an abundance of chemical information as well as the possibility of limiting the extent to which an artwork should be considered for further invasive testing. Several studies published in recent years discuss the use of portable XRF spectrometers for in situ analysis of painted surfaces. Bonizzoni et al. reported on the use of energy dispersive XRF to determine chemical composition of pigmented layers in sequence (75). In combination with visible and/or near-infrared reflectance spectroscopy analysis of lighter elements in the surface layer, which cannot be detected by XRF methods, is also made possible. Angelini and colleagues analyzed a red decorative pigment (iron oxide in natural clay or as the mineral hematite) using a portable XRF instrument (73). They also conducted surface analyses with this same technique in an attempt to discover if environmental contaminants were affecting the stonework under examination. Cesareo et al. identified the pigments used by the artist, the potential for deterioration of the surface by contaminants such as chlorine and sulfur, and previous restoration areas as noted by the presence of cadmium, zinc, and titanium in the golden haloes depicted in a painting completed in the 14th century (76). Of course, the allure of transportable equipment to authenticate artwork in real time has numerous applications in forensic work as well. A partnership of these two fields most often occurs in authentication studies, 104

particularly after a suspected forgery has been purchased at genuine prices. Szökefalvi-Nagy and associates in Budapest conducted authentication paint analyses on three suspected forgeries (85). The authors stated that titanium white has only been available since 1920, whereas the disputed artworks were said to have been created by artists who predeceased this timeline. Therefore, the presence of titanium in any of the suspected paintings would clearly indicate that they were not authentic. Recent work by Edwards and colleagues raises questions as to the use of titanium as a marker for forged (i.e., nonancient) artwork (60). Nonetheless, for the disputed paintings attributed to Géza Mészöly, titanium was readily observed using a portable XRF spectrometer with a 55Fe ring source in the two questioned works, but not in the known painting by this artist. A painting reported to have been by Tivadar Csontváry Kosztka was also under suspicion as a forged work. The owner of the painting allowed multiple examinations by these authors to settle the question of authenticity, first using microsamplings from the painting’s surface and then in situ with a portable XRF. Both analytical methods were used in order to determine if the presence of barium influenced a previous determination that titanium was present in the painting. Using the same excitation source as was used on the other paintings, it was determined that detection of titanium was being influenced by the L-lines of barium. Moreover, numerous attempts to isolate the K-lines of titanium were reported as unsuccessful. Therefore, the authors reported that XRF could not confirm the presence of titanium in the microsamplings. Subsequent in situ measurements taken at 12 points on the painting, in both white and coloured areas, revealed that the best curve fit for the detection of either barium or titanium was achieved when both were accounted for in the equation. The authors conclude from this study that analysis of titanium in authenticity examinations can be very effective and readily achieved with a portable X-ray spectrometer equipped with a 55Fe excitation source provided that barium is not also present in the pigments used. If barium is suspected, the Klines for this element can be confirmed with an 241Am source. Given the evidence that portable XRF equipment is greatly facilitating the in situ examination of art and artifacts, it is noted that Ida and Kawai have published an article on the use of a portable X-ray spectrometer equipped with a pyroelectric Xray generator which allows for quantitative analysis of Fe down to 180 parts per million in an aluminum foil sample (78). The geometry of the current design also has the potential to be further improved such that the size of the spectrometer could be further reduced, possibly allowing for even greater portability and versatility in the examination of large or irregularly shaped objects. PIXE has been utilized by conservators and archaeologists as a complement to electron based X-ray analytical techniques, such as EDS, because it offers better peak to noise ratios and consequently much higher trace element sensitivities ( As such, it is described in analyses of pigments in three paintings and on a multicoloured wooden altarpiece (66, 95, 96). In Pagès- Camagna and Calligaro’s article (66), PIXE was used by the authors to confirm pigment results obtained by microRaman analysis. Grassi describes the use of differential PIXE measurements using different beam energies or incident angles on the same analytical spot in order to 105

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obtain depth assessments of inhomogeneous layered paint samples (95). In the third paper in this set, Reiche and colleagues (96) were able to report on the existence of both zinc and tin-containing pigments from works not previously determined to contain these elements. The authors conclude that their findings raise the question as to whether these works are authentic. If so, these paintings could provide evidence that zinc pigments were already in use in India before their known synthesis and application in Europe around 1850. Two articles published in 2005 by Chiavari’s group at the University of Bologna describe reactive pyrolysis methylation and silylation procedures used with GC/MS applications (100, 113). Methylation-pyrolysis and silylation-pyrolysis are two derivatization techniques whose purposes are to provide information on carboxylic acids and other polar compounds not typically observed in conventional pyrolysis. The first paper by Chiavari examined the use of pyrolysis methylation and silylation in identifying indigo dyes in a particular work of art (100). In this study, indigo was able to be positively identified by reactive Py-GC/MS along with some binder information. The presence of the dye was also confirmed by Raman spectroscopy. In the second paper (113), the effect of three inorganic pigments, namely cinnabar (HgS), lead white (2PbCO3Pb(OH)2), and zinc white (ZnO) in linseed oil layers, were examined with respect to the analysis of fatty acids by pyrolysis with in situ derivatization. Both applications were found to be affected by the presence of these pigments, causing a significant decrease in the relative content of an analyte of interest, azelaic acid. It was surmised that zinc white and lead white might also be problematic for analysis of siccative oil in egg tempura. A 2004 publication principally authored by Mazzeo was also a product of work performed in Chiavari’s group (92). In this study, multiple techniques were used to analyze decorative materials on ancient Chinese wooden architecture. Both the inorganic pigments, such as clay and lime, and the binding media, which was concluded to be a siccative oil, were analyzed using optical microscopy of paint cross-sections, SEM/EDS, XRD, and Py-GC/MS with methylation conditions. According to the authors, the obtained data confirms historical information and provides a base of knowledge for future conservation efforts of Chinese artworks. Reports of advances in the analysis of binding media for artistic and historic artworks unilaterally contain discussion of the use of GC/MS in one form or another. For example, synthetic resins used in binding media of two 20th century paintings were studied by Cappitelli using thermally assisted hydrolysis and methylation (THM) GC/MS) in conjunction with FTIR (107). This work served as a precursor to later research by Cappitelli and Koussiaki in which both synthetic and natural binders were identified in three works by Picasso using THM-GC/MS and FTIR (108). This research demonstrated that Picasso experimented with mixing artists’ paints with other materials such as animal fats and alkyd resins, the latter combination being unusual for that era. Pitthard published two articles describing direct chemolysis using (mtrifluoromethylphenyl) trimethylammonium hydroxide (TFTMAH) as a starting point for the analysis of drying oils in works of art by GC/MS (103, 104). The first of these articles includes some history on the various derivatization techniques for the analysis of fatty acids, including methylation-pyrolysis as well as analysis of 106

partially degraded drying oils. This work was followed by a paper in 2006 in which specific applications of binding media ageing and degradation analysis at the Kunsthistoriches Museum in Vienna were reported by Pitthard, Griesser, and Stanek (105). Other publications of note in art conservation and analysis of binding media or the starting resins used to make them also involved GC/MS with methylation, direct chemolysis, and/or pyrolysis. Andreotti and colleagues described the identification of animal glue, egg, linseed oil, beeswax, Pinaceae resin, dammar, and shellac in three “old paint” microsamples (115). Using a combination of a multi-step pretreatment of solvent extractions and microwave-assisted chemolysis prior to GC/MS analysis, the authors were able to describe these materials as original or restoration agents within the samples analyzed. Scalarone and Chiantore reported on their comparative analyses of Py-GC/MS data for acrylic emulsion paints to SECFTIR results for the same samples (109). The authors contend that while the latter approach is not as sensitive as GC/MS, it does allow for the simultaneous identification of polymeric components and additives in emulsion paints using calculated molecular weights and extensive FTIR libraries without thermal degradation caused by the GC/MS procedure. Prikryl et al. described the merits of HPLC-fluorescence detection (FD) and GC/MS analyses of proteins in binding media (106). Both techniques required prederivatization steps and involved long analysis times, high cost, and/or safety concerns with respect to the methyl chloroformate (MCF) derivatization agent. However, the paper gives researchers guidance into alternative approaches to identifying proteins in works of art. Further uses of GC/MS in studies of binding media include papers by Kouloumpi et al. (102) and De la Cruz-Cañizares et al. (114). An exception to the use of GC/MS to analyze binding media was published by Harrison et al. in 2005 (117). In that paper, the use of CE is described in the identification of long-chain fatty acid constituents of drying oils and their degradation products, short-chain dicarboxylic acids. Plant and animal glues were found to interfere with other methods of analysis, but even as much as a ten-fold excess of this type of material with respect to the oils sampled on a ceremonial mask were not found to cause interferences when analyzed by CE. Forensic Analysis Of Paint Ryland’s review article (122) is an excellent reference for trends in the forensic examination of paints and coatings, including how coatings evidence is encountered in a forensic laboratory and a detailed outline of the technical approach used for their analysis. The analytical approach used by most United States laboratories includes a combination of microscopic, microchemical, and instrumental techniques, of which microspectrophotometry (MSP), FTIR, Py-GC, SEM/EDS, XRD, XRF, and LA-ICP-MS are discussed. An evaluation of evidential significance, including the use of databases in make, model, year investigations, is included. This publication is a good primer for new and experienced paint examiners alike desiring an overview of current practices in forensic paint analysis. Saferstein (123, 124) published both the 8th and 9th editions of his popular Criminalistics textbook in 2004 and 2007, respectively. The chapter on paint gives a brief but accurate description of the layers comprising an automotive paint chip, instrumental techniques, and resources utilized in make-model-year determinations. It also provides case examples and a current bibliography. Although no substantive changes to this chapter were made 107

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between the two editions, the colour photographs, figures, and overall layout of the present edition are notable improvements over its predecessors. Also of note is Kubic and Petraco’s chapter (125) entitled “Microanalysis and Examination of Trace Evidence” in a different introductory forensic science textbook. It provides an excellent overview of all types of trace evidence as well as the various microscopic techniques and instrumentation used to analyze these different types of materials. Topics include paint, glass, fibers, polarized light microscopy (PLM), FTIR, SEM, MSP, and Py-GC/MS. Significance Two references regarding the interpretation of paint evidence were published that had been described in the previous Interpol report, though at the time were referenced as conference presentations. Edmondstone (126) reported on a study to assess the distinctiveness of automotive paints in order to determine their evidential value, and Buzzini (127) examined the interpretation of the results of examinations involving crowbar and household paints in burglary cases. Case Reports Zieba-Palus and Trzcinska (128) provide three case examples illustrating the usefulness of the applied methods and the difficulties that may occur in the interpretation of results. Multiple scientific techniques are mentioned (stereomicroscopy, polarization microscopy, fluorescence microscopy, IR, UV/Visible microspectrometry, and SEM/EDS); however, only microscopy and IR are specifically mentioned in the case examples. Case 1 described an automotive paint comparison, in which only the top layer was consistent between samples. The conclusion was that it could not be excluded as the striking vehicle. Several questions arose, which could only be addressed by undertaking a population study. Case 2 involved an analysis to determine whether a car had been repainted. Based on the examinations, it was concluded that the questioned vehicle had been repainted. The example emphasizes adequate sampling from multiple areas of a vehicle. Case 3 discussed how two vehicles’ paints had been damaged: a paint stripper had been poured on them. Giang et al. (129) reported on a case in which they were asked to compare red paint transfer found on a motorcycle to two different suspect trucks. Based on the limited amount of paint smear, the only techniques utilized were stereomicroscopy and micro-FTIR, in both transmission and attenuated total reflection (ATR) modes. Based on the examinations conducted, one suspect vehicle was eliminated as the source of the paint transfer whereas the other vehicle could not be eliminated. This case report provided an example of how limited sample size, and therefore, utilization of a reduced number of analytical techniques, can affect the overall strength of an association. Additionally, the usefulness of FTIR in such instances is demonstrated. In a separate study, Buzzini and Massonnet collaborated with Sermier to report on forensic paint applications of Raman spectroscopy (130). In that paper, six case studies were presented: two automotive paint cross-transfer examples, architectural paint transfer to a burglar’s tool, spray paint graffiti analysis, paint-to-fabric transfer, and paint transfer to leather shoes worn by a suspected vandal. Each example provides support to the author’s claim that Raman and FTIR analysis are 108

complementary techniques for non-destructive micro-analysis of suspected paint transfers. Lawrence of the San Diego County (California, USA) Sheriff’s Crime Laboratory reported on a case in which he was asked to determine if an unknown material was hull paint (40). In order to familiarize himself with marine coatings, Lawrence obtained a number of antifouling paints that contained 50% by weight cuprous oxide as their antifouling agent. In the article, the preparation and microscopic techniques used to confirm the presence of cuprous oxide are described. Additionally, the presence of copper was confirmed using a microchemical test and SEM/EDS. Spectroscopic Methods Ziuba-Palus (131) reported on the examination of spray paints on a variety of substrates by micro-ATR. The advantage of the ATR technique over transmission FTIR was that the paint could be examined in situ. The author analyzed spray paints on metal, glass, foil, fabric, and plaster, and consistently found that the thicker the applied spray paint, the better the ATR spectra. In instances where the spray paint layer was thinly applied, the substrate had an effect on the quality of the spectra, due to absorption, reflection, and scattering of the light by the sample. The best results were obtained on metal surfaces and the most difficulty was encountered on fabrics and various plaster surfaces. For those plaster surfaces, transmission FTIR was recommended. FTIR and NMR were used by Ahmad et al. (132) to elucidate the structure of siloxane-modified epoxy resins they synthesized in an attempt to improve various properties of epoxies. Based on their study the authors recommended the use of siloxane-modified epoxies as anticorrosive paint systems for high temperature applications. For forensic scientists this study provides an example of paint analysis via NMR spectroscopy, a technique that is not used routinely in forensic laboratories. Suzuki (133) published the seventh article in his series on the IR analysis of pigments in automobile original finishes. In this article, he described the FTIR and XRF analysis of Nickel Titanate and Chrome Titanate, two inorganic pigments that can be used to formulate hues formerly produced by Chrome Yellow. Although the analysis was performed on automobile systems from the 1974 to 1989 era, the paint industry still utilizes these pigments in some yellow and orangeyellow topcoats. These titanate pigments are based on the rutile titanium dioxide structure, and only minor differences can be discerned between the infrared absorptions of the titanates with rutile, and even then only with extended-range FTIR. However, when analyzed with XRF for trace element content, identification is possible: elements comprising these pigments include nickel and antimony for Nickel Titanate and chromium and antimony for Chrome Titanate. Other elements detected included zirconium, niobium, and lead. Despite the information obtained from XRF, Suzuki acknowledged that the potential is not likely to be frequently seen. Reasons include the common use and availability in forensic science laboratories of SEM/EDS, which does not permit detection at these elemental levels, and sample sizes requirements for XRF that are much larger than normally encountered in casework. In a second report on XRF analysis (134), the technique was used in an unconventional way, in that organic modifications in paints were 109

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detected. While XRF is traditionally used for inorganic applications, this study showed the possibility of evaluating organic information, due to other possible interactions between the incident X-ray beam and the sample. Applications included evaluation of the degradation of organic compounds for paint quality control purposes. Buzzini and Massonnet conducted a paint analysis study of 40 commercially available green spray paints utilizing both FTIR and Raman spectroscopy (135). The FTIR data was used to discriminate the binders and some extender pigments while Raman provided identification of the primary organic pigments in the formulations. Eleven of the purchased paints were for automotive usage. The remaining 29 were designated for household applications, both indoor and outdoor use, for decorative applications, and appropriate for substrates ranging from wood to metal and plastics. The authors reported that both shaken and unshaken samples were analyzed in order to determine if differences could be detected between the two preapplication conditions. Given the low priority of proper application techniques during the commission of a crime, it is reassuring that the authors reported no differences between shaken and unshaken samples by either FTIR or Raman spectroscopy. The main binder types identified by FTIR for these paints were acrylic, orthophthalic alkyd, isophthalic alkyd, and nitrocellulose-orthophthalic alkyd. Two sub-groups of six samples each could not be differentiated beyond classification as an orthophthalic alkyd with barium sulfate as the extender pigment or as a nitrocellulose-orthophthalic alkyd binder, respectively. The authors reported the discriminating power for this analysis as 0.95 for the 40 paints with 40 undifferentiated pairs remaining. Using a He-Ne laser at 632.8 nm, 15 groups were distinguished by Raman spectroscopy amongst the 40 analyzed samples. The discriminating power for this set was reported as 0.91 with 68 undifferentiated pairs. When an Argon laser set at 514.5 nm was used, Raman yielded eight groups with a discriminating power of 0.62, whereby 300 undifferentiated pairs remained for the 40 spray paints. The authors then attempted to determine the extent to which further discrimination between groups could be achieved if the three reported methods were used in concert. Following the analytical sequence FTIR, then Raman He-Ne, then Raman Ar+, 26 individual classes were obtained with a calculated discriminating power of 0.98 with 19 undifferentiated pairs for the 40 green spray paints. Conclusions drawn from this work included the assertion that a combination of FTIR and Raman techniques provides the best discriminating capability for spray paint samples. Since the green Argon laser operated at 514.5 nm induced fluorescence for most of the samples in the study, Buzzini and Massonnet recommend use of a red He-Ne excitation source at 632.8 nm for green paints. In an ancillary pigment study within this paper, it was reported that the He-Ne laser identified primary green and blue phthalocyanine pigments within the spray paints. Moreover, despite fluorescence difficulties in many samples, use of the Argon laser did detect two yellow pigments in the paints studied. Thus, the combination of FTIR and Raman, particularly with different excitation sources, provides a robust analytical protocol for spray paint analysis. Bell, Fido, Speers, and Armstrong have also published follow-up articles to their Raman work described in the previous review. The first study entailed the analysis of architectural finishes by Raman spectroscopy (136), in which 51 “lilac” coloured 110

paints were examined using three different excitation wavelengths. The authors note that the colour choice was arbitrary in that it was based on availability of an extensive sample set. However, the decision to analyze single layer paints within a visually consistent colour space was deliberate, since the importance of chemical discriminating ability is more critical in these types of comparative samples. Of the 51 paints in the sample set, the manufacturer, finish (e.g., gloss, matte, satin), and hue were all variables. Raman spectra were collected on all 51 samples at an excitation wavelength of 785 nm. A smaller subset of the paints was also analyzed using visible excitations at 514 and 457.9 nm. However, discriminating features of the individual samples were masked at these wavelengths by the overwhelming bands produced by a component common to all of the paints. The use of the far red wavelength excitation energy at 785 nm allowed for both the pigments and nonresonance enhanced components to be evaluated using a conventional silicon-based charge coupled device (CCD) detector. A complicating factor in this discrimination study was the batch variation observed between nominally identical paint formulations. The authors concluded that further studies would be needed to address this issue. Nonetheless, PCA was able to provide good characterization and discrimination when major features of the spectra such as the presence of rutile and copper phthalocyanine pigments were used in conjunction with minor constituents. This approach allowed for the use of a library search methodology, since the analysis time was less than one minute and no sample preparation was needed. The authors further reported that when 20 samples were prepared and analyzed against a library created almost one year earlier, the “correct” sample was the top hit in 16 cases, the second top hit in two cases, and the fifth top hit in two additional cases. This work provided further validation of Raman spectroscopy as a forensic tool in architectural paint analyses. Two subsequent publications by Bell et al. (137, 138) compared the merits of FTIR and Raman spectroscopic analyses on both the resinous binders and white paint formulations used in architectural finishes. In both papers, Raman spectroscopy was reported to provide slightly better discrimination capabilities with little sample preparation. In Part 1 of this series, 11 oxidizing resins, 20 modified alkyd resins, and 8 emulsion resins of varying manufacture, oil length, and modifier were analyzed. The authors noted that FTIR is commonly used to discriminate between resin types because it provides adequate comparative information in forensic casework. However, the ability to classify and further characterize resins within a given population is achievable with Raman spectroscopy particularly if background differences are corrected prior to measuring band intensities. While manual background subtraction is a simple exercise, the authors used a first derivative approach taking 11 points in a Savitzky Golay model in an attempt to eliminate bias and human error. The study concluded that for the 39 resins studied, Raman and FTIR provided similar discrimination between resin classes. Further differentiation could not be achieved with the FTIR data, however, because within-group variation was comparable to the experimental uncertainty of the technique. Using Raman spectroscopy, the relative band intensity differences were small for a given resin type, yet were still greater than the experimental uncertainty of the technique. In Part 2 of their study of architectural finishes by FTIR and Raman these authors examined samples classified as nominally “pure white.” Experimental conditions for the Raman analysis followed those of the lilac paint sample study described earlier. 111

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Fifty-one white paints of varying manufacture and finish were recorded at 785 nm, with additional attempts at analyzing a subset of 10 paints at both 514 and 532 nm. Fluorescence levels at the shorter wavelengths proved to be unacceptable, so this work was halted. The remaining analyses were all performed using the 785 nm experimental conditions. Of the 51 samples analyzed, Raman spectroscopy differentiated the paints into seven groups, where each spectrum within the group contained the same bands but not necessarily with the same intensity ratios. There were also six single samples that did not align with any other paint grouping. FTIR analysis yielded six distinct groups and four individual spectra. Additionally, the authors noted that twelve samples that comprised a single FTIR group were differentiated into three groups and two individual spectra by Raman. Both the binding media and inorganic pigments and extenders contributed to the discrimination capabilities in the study, but were more readily identified using Raman since there was little band overlap in these spectra. The authors reported that approximately half of the white paints could be discriminated even within a given group. The other half of the samples were sufficiently consistent to be classified as a single group by both techniques. However, intensity differences in some bands provided a basis for concluding that the rutile-to-resin ratio had enough variability within this group to make it a discriminating parameter for further consideration. As a result of this series of papers, the authors make a strong case for complementing traditional FTIR paint analysis with Raman spectroscopy, particularly when more specific binder or pigment discrimination or identification is needed. In a paper by DeGelder, Vandenabeele, Govaert, and Moens (139), Raman spectroscopy is augmented by FTIR in the analysis of cross-sectioned automotive paints. All layers (e.g., clearcoat, basecoat, primer surfacer, and primer electrocoat (e-coat)) of a typical OEM finish were analyzed in this study. Metallic finishes containing pearlescent and metallic effect pigments in the basecoat were chosen for analysis over non-metallic colourcoats. Both the clearcoat and e-coat were found to lack sufficient distinguishing chemistries by FTIR or Raman techniques to differentiate paints using either layer on its own. However, the primer surfacer was found to be a good discriminating layer with FTIR and Raman spectroscopy based on the presence or absence of calcium carbonate or barium sulfate. Raman could further discriminate paints by identifying the rutile form of titanium dioxide. Moreover, the basecoat was shown to be the most discriminating layer, particularly when Raman was used to characterize its organic pigments. Flakes of the individual topcoat layers were also analyzed by Raman spectroscopy with promising results that would further reduce the need for sample preparation on small samples. In a similar study, Ziuba-Palus and Borusiewicz (140) examined multilayer paint samples by IR, Raman, and XRF spectroscopies, where FTIR was used to determine the binder, Raman identified the pigments, and micro-XRF confirmed the Raman results. Ito et al. (141) produced a paper describing the use of FT-Raman spectroscopy in conjunction with multivariate data analysis for rapid and quantitative determinations of the viscosity of waterborne automotive paint systems. This work is directed at on-line manufacturing processes but provides a foundation for 112

consideration with respect to forensic analyses. Colour Three separate articles written by Cramer (142), Nadal (143), and Takagi (144), respectively, address the importance of measuring the colour of coatings containing pearlescent or interference pigments at different angles of reflection. Each author discussed that due to the presence of these pigments, the colour measurement will differ depending on the angle of illumination and the aspecular angle. Although intended for quality control and assurance of manufactured products, the subject of these articles emphasizes the importance of observing and comparing painted specimens under the same lighting conditions. Kopchick and Bommarito (145) reported on the use of MSP on achromatic automotive paint samples. Samples whose colours are black, gray, or white are considered achromatic because they either reflect or absorb all wavelengths of visible light approximately equally, and therefore, achromatic samples are typically not analyzed via visible MSP in forensic laboratories. The authors, however, provided examples of black and gray/silver colourcoats in which MPS provided additional discrimination over that obtained via PLM. Such samples may contain secondary chromatic pigments added to the achromatic paint formulation resulting in MSP spectral variation. No spectral variation was found between white topcoat paints or in gray undercoats. Based on the results of this study, the authors recommended that when MPS is regularly included in the forensic analysis of automotive paints, it should be included in analytical schemes involving black and gray/silver topcoats. Chemical Imaging In chemical (hyperspectral) imaging, spatial and spectral information are gathered simultaneously. The technique combines macro/microscopic imaging with spectroscopy, resulting in a three-dimensional representation of a sample. A variety of spectroscopies can be applied, and two publications were found during the time period of this review for the technique’s application to forensic paint samples. Payne et al. (146) investigated the use of chemical imaging for a variety of materials but specifically evaluated multi-layered paint chips through visible and fluorescence chemical imaging. It was found that in comparison to traditional MSP, chemical imaging is more efficient, and that fluorescence chemical imaging can be performed on the same equipment without removing the sample. It was also found that the technique is powerful in presenting data to the layperson. However, traditional MPS is able to scan over a larger energy range. Flynn et al. (147) analyzed multi-layered paints by infrared chemical imaging and, like Payne, found two key advantages of the technique: thousands of spectra are compared with thousands of spectra in a short time, and chemical imaging data can be displayed in ways that are easy for a layperson to visualize and understand. However, a main disadvantage was described in that the infrared spectral range is more restricted than for a conventional infrared microscope, specifically in the inorganic fingerprint range. Elemental Analysis Schreiner, Melcher, and Uhlir published a review on SEM/EDS and its applications in the field of cultural heritage (148). Although an analysis is performed on a multilayered painting, the review is still quite relevant to forensic paint analysis, in that the authors discussed the potential, advantages, and disadvantages of 113

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SEM/EDS. An ESEM was used: the main advantage is the examination of nonconducting samples (e.g., paint) without application of a coating. Light microscope, UV fluorescence, BSI, and X-ray mapping images were shown demonstrating the complementary pigment and layer structure information obtained from each. Despite the information available from such techniques, the authors stated that it should be kept in mind that many inorganic materials and pigments can occur in different crystalline structures, highlighting the use of XRD. Conventional XRD, however, is not suitable for the analysis of single layers in a multi-layered crosssection, but a recent study on synchrotron X-ray micro diffraction demonstrated the analysis of paint layers down to 1 or 2 microns (149). Two articles were reviewed on the analysis of forensic paint samples by LA-ICPMS. Deconinck et al. (150) performed depth profiling analysis of multi-layered automotive paints, which provided detailed information on the trace elemental composition of individual layers without the need for any separation from adjacent layers. The data was displayed in two ways: as depth profile plots (intensity versus time) and as bar graphs of elemental ratios, both of which allow for qualitative comparisons of samples. Quantitative analysis would potentially lead to a statistical evaluation of the results, which would be particularly important in comparing results of an unknown sample to a database. However, at this time quantitative analysis is still being developed. Also in this work, two mass spectrometers were used and compared (a quadrupole-based and a sector field instrument) and the advantages and disadvantages of both were discussed. It was demonstrated that LA-ICP-MS is very promising for layer-specific elemental characterization of multi-layered automotive paints but that further optimization is needed. In a second LA-ICP-MS publication, Smith et al. (151) analyzed works of art for the detection of art forgeries. The work has potential applicability to the field of forensic paint analysis in that it includes an investigation into the possibility of identifying differences in elemental concentrations between brands, manufacturers, countries, and binders of artists' paints. In this work, the data was displayed in plots of intensity versus isotope, which as in Deconinck's study, showed visual differences between samples. It was also found that the binder could have an effect on the fit of a database search and should be taken into account. A new procedure was proposed by Lopez-Molinero et al. (152) for the determination of metals in paint driers, which are catalysts used in paint formulations to accelerate drying effects and film formation. Common metals include barium, calcium, cobalt, lead, manganese, and zinc, but rare earth and transition metals can also be used. The procedure involved decomposition and mineralization of the organic matrix using microwave digestion and flame atomic absorption (FAAS) and/or emission (FAES) spectroscopy, resulting in no significant difference between concentrations calculated with these techniques and reference values. Although this study was for industry quality control purposes, it provides background information on paint driers to forensic scientists. Jancik et al. (153) described the use of a miniaturized Mossbauer spectrometer for monitoring the colour quality of copperas red pigments (FeSO4 •7H20) and as a control device in the manufacture of titanium dioxide from ilmenite. Although the target audience is the paint industry, the report demonstrated the potential of a unique technique for pigment analysis. 114

Pyrolysis The pyrolysis technique is older than GC and MS, yet very little is published from practical or service laboratories. Therefore, in 2004 Wampler (154) wrote an editorial that provided examples of how pyrolysis is used in practical applications. Examples included forensics in general as well as the paint industry. Paint laboratories, for instance, use the technique to identify and measure the components in paint formulations and to analyze their competitors' products. The article noted that although paint may be marketed as polyurethane, it may only be present as a minor component. Pyrolysis is effective at characterizing these types of materials. The article also stressed that pyrolysis provides analytical information about a complex solid material, such as paint fragments submitted as items of evidence. Pyrogram libraries can be used to identify the components of an analyzed sample. Wampler also published two short notes (155, 156) that show how Py-GC/MS was used to differentiate automotive paint samples. In both references, the two paint samples compared are primarily acrylic in composition and are discriminated by pyrolysis; however, it is not stated whether the paint samples could be differentiated by FTIR. Wampler reiterated that since inorganic fillers do not interfere with pyrolysis analysis, Py-GC/MS is a powerful tool for the analysis of complex filled and treated automotive paints. In the first publication, more detail is provided on paint formulations, which depending on the components identified, may allow one to establish the approximate age of the car. Burns and Doolan (157), on the other hand, did examine automotive paints that had previously been found indistinguishable following FTIR analysis. These authors were approached by the European Paint Group (EPG, a group of scientists involved in paint analysis from multiple European forensic science laboratories) to collaborate in a study to evaluate the potential discrimination ability of Py-GC/MS for automotive paints. Approximately 75 automotive paint samples were analyzed by FTIR and Py-GC/MS to evaluate whether Py-GC/MS could discriminate samples that FTIR could not. In multiple instances, they did find that samples that could not be discriminated by FTIR were discriminated by pyrolysis, and on occasion, consideration of minor components was beneficial. Furthermore, they found that the reproducibility of the pyrograms was good for both the compounds detected and in the relative peak heights. However, it was not stated over what time frame the reproducibility was evaluated. However, reproducibility was further studied and discussed by the authors in a subsequent publication (158), in which the pyrograms showed excellent chromatographic reproducibility. The aforementioned article ends with a question: "what is the degree of discrimination that Py-GC/MS can provide between large numbers of samples of a particular class...all from within a single FTIR group?" The authors attempted to answer this question in a following article (159) involving the analysis of automotive paint clearcoats. In that portion of their study, Burns and Doolan analyzed 300 clearcoats by Py-GC/MS to investigate the discriminating power of the technique. The 300 samples included groups of 4, 7, 9, 36, 49, 55, and 140 that could not be distinguished by FTIR analysis alone. The pyrolysis data was compared between groups, confirming the individuality of the FTIR groupings. In most cases, Py-GC/MS was able to further subdivide the groupings, substantiating an increased discrimination following the analysis.


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White exterior paints were also analyzed by Py-GC/MS by Burns and Doolan (160). Since FTIR can identify classes of paint but it is not as good at differentiation within each class, 28 different white exterior paints were analyzed by Py-GC/MS to evaluate the technique's potential for discrimination. An evaluation of FTIR to discriminate the samples was not mentioned, but a majority of the samples could not be discriminated by Py-GC/MS analysis. Since the paints were mostly purchased locally, it is possible that despite the apparent variation in paint brands, many of the samples could still come from the same manufacturer. Also in this study, two of the samples were sampled twice: once before and once after stirring; no discernible differences were noted in the pyrograms. The authors mention developing a system for automating the acquisition and evaluation of data, in order to save time and to avoid problems in the subjective visual comparison of pyrograms, which is then reported on in a previously mentioned study (158). Jansson et al. (161) described a Py-GC/MS technique for analyzing polymer additives, such as plasticizers, antioxidants, light stabilizers, flame retardants, and other modifiers, in which two or more low temperature (sub-pyrolysis) runs were performed prior to pyrolysis, a technique previously described by Wampler (162). This allowed for additional separation and further elucidation of components present in complex polymeric materials. Two light stabilizers found in paints (Tinuvin 622 and Chimassorb 944) were included in the discussion and were successfully identified and distinguished. For additives present in the parts-permillion range, selected or extracted ion mass spectrometry was the most informative. Other Mass Spectrometry Techniques Stachura et al. (163) reported on the laser desorption mass spectrometry (LDMS) analysis of automotive coatings in order to identify the organic pigments. LDMS has previously been demonstrated to be effective at analyzing colourants in inks and other matrices, but this study demonstrated the technique's utility for the analysis of automotive paints. LDMS has multiple advantages: it is fast and relatively nondestructive, is capable of analyzing small samples, has generally low detection limits, and can simultaneously detect inorganic and organic pigments at low concentrations in the presence of binders. Reidy et al. (164) reported on a preliminary investigation into using 13C-isotope ratio mass spectrometry (IRMS) for the forensic analysis of white architectural paints. Despite the promising applications of IRMS to other forensic materials (165) (refer to reference number 165 for a good synopsis of IRMS instrumentation and application), validation of the technique for paint analysis had not been attempted prior to this study. Since carbon is one of the most abundant elements in paint, this study investigated the influence that paint application, ageing, and homogeneity might have on the results obtained and the conclusions drawn from the technique. The authors warned that, at this point in the research, interpretation of the significance of the results should be approached with caution. Recommendations were also made about additional research that should be explored. However, the preliminary results are promising. Updates on Databases Since the last review, the Bundeskriminalamt (BKA) requested that the European Paint and Glass Group (EPG) of the European Network of Forensic Science Institutes (ENFSI) expand its activities to include the forensic analysis of tapes and security 116

dyes. As a result, the EPG initiatives now include management of an adhesive tape database and establishment of a European database on security dyes. In 2007, the first collaborative exercise for sourcing adhesive tapes was administered, the purpose of which was to validate the utility of the adhesive tape database. The BKA and Gendarmerie Nationale in France also continue to share responsibility for maintenance of the European Collection of Automotive Paints (EUCAP), which is the EPG’s automotive paint database. EUCAP is available to non-ENSFI forensic laboratory partners upon request. Lastly, a new Raman database is being established for automotive paint samples, and an infrared database populated with a variety of routinely examined materials is also under development. Both the paint and glass sub-groups expect to establish best practice manuals for their individual disciplines before the end of 2007. These documents are likely to include discussion of the use of databases in casework. The Paint Data Query (PDQ) database maintained by the Royal Canadian Mounted Police (RCMP) has continued to expand its partner laboratories during the past three years. Six laboratories have joined since the last review article and one inactive member has re-joined after several years of non-participation. In addition to a number of Canadian laboratory partners, PDQ has over 100 international participants. These include fifty-three American laboratories, thirty European laboratories, representing seventeen countries, eleven laboratories representing Australia or New Zealand, one in Japan, and one in Singapore. Approximately 500 samples continue to be added to PDQ annually with a new release of the software sent out to member laboratories each October. The version released in October 2006 contained 14853 samples which collectively were comprised of 54882 individual paint layers. The spectral libraries contain sixty-eight libraries containing 40893 individual spectra. PDQ catalogs both the Munsell colour and the chemistry of the primer layers. An article that addressed colour variations of electrodeposition coatings (166) is of interest to the forensic paint examiner, particularly when relying on comparisons of e-coat colours to either a known or reference sample or to data compiled in a database. The author discussed a number of factors that have an effect on the resulting colour of an electrodeposition coat. Factors included film build, improper mixing of the paint, iron or bacteria contamination in the tank, and less than optimal oven (curing) conditions. The author reported that the primary effect is yellowing of the dried film. Further, he stated that colour shifts can occur with as little as 0.1 mil difference in dry film thickness, and lighter colours are generally affected to a greater extent than dark colours. The intent of the article is for someone in the paint industry to resolve problems they encounter regarding controlling colour, but it is beneficial to the forensic paint examiner to understand the extent to which it occurs. Glass Overview Several previous review papers and conference proceedings have covered some of the topics included within this review. Almirall and Trejos (167) published a Forensic Science Review paper concerning forensic analysis of glass fragments. This tutorial article emphasizes the basics of glass examination with acknowledgement of current 117

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methods and potential future improvements. The authors emphasize analytical methods, particularly elemental analysis, but also touch on other topics including sampling and recovery of glass fragments, optical and physical examination methods, and statistical interpretation of the results. This article is not a typical review of the literature in that a number of the recommendations, particularly in the areas of sampling and statistics, are made by the authors from their own experience with limited citation of references. Of the references listed, only about 10% are from the last three years and none are more recent than 2005. The American Chemical Society publishes semiannual reviews covering a number of analytical fields in the journal, Analytical Chemistry. Of these, the most directly related to forensic glass analysis are the two on Forensic Science (168,169). These reviews provide a list of articles with little commentary. While the coverage of forensic science is extensive, only a single paragraph and a few references are devoted to glass. Other review articles in Analytical Chemistry concern specific analytical methods, some of which are applicable to glass. The Royal Society of Chemistry publishes similar analytical reviews both of analytical methods and materials analyzed in the Journal of Analytical Atomic Spectrometry. Their updates concerning Industrial Analysis: Metals, Chemicals and Advanced Materials (170,171) contain sections on glasses and ceramics. These reviews contain critical discussion as well as a summary of the published articles. Emphasis is on methods utilizing atomic spectrometric techniques. Applied Spectroscopy Reviews is a highly-rated journal containing instrumental developments of spectroscopic methods including applications. During the review period, articles appeared in this journal on the topics of TXRF, LA-ICPMS, direct analysis of solids, and spectroscopic methods for cultural heritage conservation. An overview article by Adriaens (172) presents the development of analytical methods associated with a European network COST Action G8 for the preservation and conservation of cultural heritage materials, including glasses and ceramics. Specific examples are discussed emphasizing instrument modifications utilized for specific studies. An interesting aspect of this review is a discussion of the need for collaboration between analytical scientists and those familiar with the cultural heritage materials. Conference proceedings, although lacking the detail of published papers, may also serve as reviews of active research. Conferences focused on specific topics also provide the advantage of bringing many research papers together in a single source. Contact information for the presenters is provided in most conference programs, thereby giving a source for obtaining more detailed scientific information. Several conferences that may be of interest to glass examiners are the Winter Conferences on Plasma Spectrochemistry (2005 Budapest, 2006 Tucson, 2006 Bangkok, 2007 Taormina), American Academy of Forensic Sciences (AAFS 2005 New Orleans, 2006 Seattle, 2007 San Antonio), International Association of Forensic Sciences (IAFS 2005 Hong Kong), European Academy of Forensic Science (2006 Helsinki), Euro-Mediterranean Conference on LIBS (2007 Paris), and LIBS2006 (2006 Montreal). The programs and, in some cases, abstracts of the presentations can be found on the Internet. The emphasis in this review is on the characterization of soda-lime glasses, since this class of glass is of most interest to the forensic examiner. However, some glasses of other compositions are included when they are of historical interest or the methodology utilized represents a significant advance. There are a large number of additional papers not included in this review 118

concerning topics such as the physics and chemistry of glass production or the characterization of specialty materials, such as glass used for storage of radioactive waste. Manufacturing Trends The production of glass for architectural, automotive and specialty uses is a continually evolving process. The chemical composition of both float and container glass has been fairly consistent over the past 30 years or more. However, manufacturers are constantly making small changes to the generic formulas of glass to effect desirable end-use properties at the lowest production costs. Although these changes appear to be relatively minor, they may result in significant changes in measured properties that are forensically important in that they may affect both analytical measurement methodologies and interpretation of the significance of the resulting data. Another significant trend is the increasing globalization of production. A number of new float glass plants are under construction, several of them in Russia, India, and China. The utilization of new sources of raw materials and updated production processes, as well as the production of new product lines by these plants may result in novel materials presented to the glass examiner. There is a large body of literature concerning the relationships between the composition and the properties of float glasses. Although the process of glass production is well-understood, a number of minor alterations have taken place to improve the quality of the glass or decrease the cost of production. For example, Arbab et al. (173) reported that the Fe content of automobile glass is being increased in order to produce a thinner glass without reducing its strength or ability to block UV radiation. The resulting weight reduction improves automobile fuel efficiency. They report that current average window thickness is approximately 4 mm, compared with 6.5 mm 30 years ago. A similar effect can also be accomplished by altering the glass redox ratio while decreasing the Fe content. A shift in the redox ratio produces glass with a more bluish tint. Another example, reported by van Mol et al. (174) is the vapor phase addition of tin oxide coatings to the “non-float” side of glass while in the float chamber. These coatings impart high transparency to visible light, high hardness, decreased electrical resistivity, increased reflectivity of IR light, and improved environmental stability. An important aspect of this practice for forensic glass examiners is that Sn coatings will occur on both sides of a float glass treated by this process. In another study, Hoffmann et al. (175) studied the diffusion of ions from glass into sol-gel dip-coatings of SiO2 and Na2O-SiO2. They report that Ca and Mg diffuse into the films to satisfy electroneutrality requirements, while several other ions do not migrate. Processes such as these may provide additional points of comparison for glass examination. These points are only given as a few examples. Many other changes occurring in the flat glass industry are documented on several web sites. A couple of most interest include: • – the web site of the GANA, the Glass Association of North America, provides links to many other sites. • – the web site of NGA, the National Glass Association (mainly U.S.). • – industry news concerning flat glass. • – forum for exchange of information in the international 119

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glass industry. A similar situation exists within the container glass industry. Although the chemical composition of container glass is quite consistent, modifications in this composition are occurring because of the increased incidence of recycling and the desire to reduce melting temperatures to save heating costs and to meet increasingly stringent environmental regulations concerning gaseous emissions. In a research laboratory environment, Bingham and Marshall (176) measured the effects of relatively small changes in the composition of a benchmark soda-lime-silicate glass (UK average composition) on its physical properties. They believe that a 20% to 40% decrease in nitrous oxide emissions can be obtained through fairly minor reformulations. Decreases in sulfur oxides, particulates, and heavy metals could also result from these reformulations. Although additional work is needed before these changes become economically practical in a production line environment, the glass examiner should be aware that compositional changes and the associated changes in physical and optical measurements are a continuing possibility. Ercole (177) puts these considerations into perspective by discussing the complicated relationships between composition and the workability of container glass melts. Another aspect of container glass production is the recycling of other waste materials as cullet in glass making. In one example from Russia, Vlasova and Brylina (178) indicate that a ferrochromium industrial slag can be used in the production of green container glass. In a final example, container glass may be strengthened by dip-coating in a halide base Li solution. An optimum thickness of the exchange layer needed to counteract surface flaws in the glass is 20 to 70 µm. Surface layers produced by dip coating and other processes should be observable using several of the methods discussed further in this review. Glass Examinations Physical and Optical Measurements Fracture matching The unique morphology of a fracture surface and the ability to match adjoining fracture surfaces unambiguously have long been a well-accepted principle of glass examination. Several studies were conducted that reinforce the idea of uniqueness of fracture matching by studying the mechanisms of crack formation and propagation under a variety of conditions. Guin and Wiederhorn (179) studied cavity formation during crack growth in silicate glasses using atomic force microscopy (AFM). There is no evidence of cavity formation, making it so that fracture surfaces matched to a resolution of better than 0.3 nm normal to the surface and 5 nm parallel to the surface. They conclude that glass fracture is completely brittle. In another study Guin et al. (180) found that when cracking of a soda-lime glass occurred under water, some corrosion of the crack tip occurs due to hydroxyl ion exchange along the crack surface. However, fracture surfaces still matched to an accuracy of much better than can be observed by optical microscopy. Wang (181) explains crack propagation and many other properties of silica glasses in terms of long-range density fluctuations (on a nm scale) that arise in the glass-forming liquid. According to this theory, cracks propagate around areas of high density, thereby giving each fracture a unique path. 120

Refractive Index (RI) There are presentations at nearly every AAFS and IAFS meeting concerning the variations in physical or optical properties, particularly RI, both within and among glass objects. In one such presentation, Roux et al. (182) reported the discrimination capability of thickness, RI, microspectrophotometry, and visible fluorescence for differentiating among 86 new and 104 used wine bottles, including several from the same product line. Using all of the tests, they found 99.2% of the bottles could be discriminated, including all bottles of the same type. Newton et al. (183) verify the utility of laboratory annealing as a technique in forensic glass examination. Differing from previous studies that observed complete separation of toughened and laminated samples, they found a continuum of ΔRI values across their set of 356 glass samples. Rather than attribute the results of older studies to sampling errors as they do, an alternative explanation for the continuum of results observed by Newton et al. results from the fact that they considered all laminated glasses to be untoughened. However, they failed to note that some of these glasses are likely made by newer processes, such as pressbending and chemical strengthening, which result in partial strengthening of the glass products. Thus, the changes observed during laboratory annealing, particularly with the short schedule used in their study, take on a more continuous range than those reported in previous studies. The authors’ recommendation that ΔRI values should be treated as continuous in attempts to classify glass seems to be a good one when considering all glasses made by current and older processes. Becker and Dücking (184) presented the results of a study of changes in RI caused by laser heating (at 213 nm) of glass fragments when they are subjected to laser ablation (LA) for elemental analysis. They only provided preliminary results, but did report that in the immediate crater region, the laser interacts with the glass to produce an edge for which RI cannot readily be measured. For edges near the crater, the variability in RI increases, but the mean is unaffected. Outside of the immediate vicinity of the crater, changes in RI are too small to be considered significant within the precision of measurement. Elemental Composition It is now widely accepted that quantitative chemical analysis is a powerful tool for both the classification and discrimination of small glass fragments in forensic and archaeometric investigations. Continuing the trend reported in previous reviews, the use of elemental composition has been shown to supplement other more traditional measurements and is taking on increasing importance. The number of publications concerning development and evaluation of analytical methods for elemental determination far exceeds those concerning other forms of glass examination. In a series of papers, Smrcek (185-187) presented and discussed the changes in major element composition of flat, container, and pressed glasses over the period 1830 to 1990. He utilized data culled from the published literature and manufacturer’s archives to assess differences in composition related to manufacturing processes, countries of production (U.S. and Europe only), and production dates. Although some of the trends are partially obscured by opportunistic sampling and variations in data quality over the 160 year time period and large portions of the world are not included in the compilation, Smrcek’s papers present much information that is 121

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useful to the glass examiner. The general compositional variations noted provide some insight into the interpretation of compositional data, particularly as it relates to attempts to source a glass fragment. The examiner is well reminded to consider that potential sources for a recovered glass fragment may be an object produced by one of these older production methods. Jackson et al. (188) discussed attempts to link the compositions of ancient and historic glasses to the birch, oak, and bracken ash used as the alkali source in their production. The variability in the compositions of these ashes and changes in the element distribution that occur during manufacture add to the complexity of classification of historic glasses to specific geographic locations or manufacturing methods. Papers concerning development of methods for measurement of and forensic interpretation of major, minor, and trace element concentrations in glass have been divided into four categories based on the general type of instrumentation used. X-ray Methods Methods based on measurement of x-rays continue to be popular for forensic applications, primarily because of their nondestructive nature, minimal sample handling, ability to provide multielemental data on small, irregularly shaped fragments, and relative speed. X-rays can be induced by electron beams (e.g., SEMEDX), particle beams (e.g., PIXE), and x-rays (e.g., XRF). Traditional x-ray methods for glass analysis are well-developed and accepted and, as a result, few recent papers have been written concerning their use. However, there have been many publications concerning applications in the archaeology and art fields where nondestructive analysis is most important. X-ray methods, particularly XRF, remain routine methods for monitoring glass chemistry for industrial glass formulation studies and during float glass production. Publications dealing with glass production are, for the most part, not included in this review because the utilization of large sheets of glass is not pertinent to most forensic applications. Comparative Studies Falcone et al. (189) compare the analytical sensitivity and accuracy of WDXRF, EPMA, and SEM/EDX for the analysis of small irregularly shaped fragments using a single commercial container glass standard. Their aim was to determine which method provided the best data for source classification of fragments of various sizes. With their instrumental setup, they concluded that WDXRF provides accurate results for most major and minor elements and some trace elements using beads made from a heated mixture of Li2B4O7 flux and powdered glass having a mass greater than 50 to 100 mg. At lower masses, the accuracy becomes “unacceptable”, but classification is still possible. EPMA was performed only on embedded polished samples down to 0.3 mm in size, for which major and minor elements could be reliably detected. The accuracy was too poor when using nonembedded particles. SEM/EDX gave good accuracy for the main elements and Fe and Cr for embedded samples, but could not reliably measure elements present at concentrations lower than 500-1000 ppm of oxides. Nonembedded particles were analyzed by SEM/EDX, requiring 20 repeat analyses to correct for variations in surface geometry. The accuracy is quite poor, but still allowed a glass fragment of 100 µm in size to be recognized as belonging to a “class” that contains the green soda-lime glass used in this study. These results appear to be fairly typical of those routinely achieved by 122

forensic laboratories that have used these techniques. In a similar study, GomezMorilla et al. (190) compared the precision and accuracy of PIXE (2 methods), µSRXRF, and EPMA using a BCR-126A glass reference material. They used normal operating parameters for the four instrumental setups, but with similar beam spot sizes of 25 µm2 except for the EPMA which had to be defocused to avoid alkali element migration in the samples. Each technique provided its own challenges that could be addressed by adjusting operating parameters. Overall, the four methods gave similar results in that the precision based on multiple area measurements on the glass was typically better than 3.5% for most elements. The various deviations can be accounted for by the operating principles of each method. The authors conclude that the four techniques each have advantages and disadvantages, but they complement each other. X-ray Fluorescence As stated in the 2004 review, recent commercial introduction of micro XRF spectrometers (µ-XRF) has spurred interest in their use for forensic characterization of small particles. Continuing this trend, Miller et al. (191) used a polychromator µXRF instrument with a spot size set at a nominal 60 µm to characterize single glass reference spheres of various sizes and a defocused beam of approximately 360 µm to characterize bulk samples. By monitoring the Si intensity from borosilicate microspheres of various sizes, they determined that if individual particles are separated by a distance larger than the beam diameter, particles can be detected down to a mass of 0.04 ng and a mean particle diameter of 0.06 µm. With this instrument, they were able to observe the presence of Mg, Al, Si, Ca, Ti, and Fe in larger particles and bulk samples of several reference glasses. Most µ-XRF studies to date have utilized qualitative data, because quantitation is made difficult by the lack of knowledge of the energy distribution of the excitation spectrum resulting from the use of capillary x-ray focusing lenses. Padilla et al. (192) attempted to solve this problem by using a standardless calculation based on a fundamental parameters calculation. They demonstrated the application of their program using glass certified reference materials. Lankosz et al. (193) also used a fundamental parameter calculation with an x-ray microbeam of 30 µm to quantify elements in polished slabs of glass standard reference materials. The results of these studies and others presented at forensic conferences indicate that benchtop µ-XRF systems based on capillary optics provide some opportunity to use x-ray spectra qualitatively for forensic glass comparison, but quantitative results have large errors in accuracy and to a lesser degree precision. There is a strong interest in developing portable µ-XRF systems for field use in the analysis of materials of interest in the cultural heritage and forensic fields. A prototype portable polycapillary-based system capable of focusing the primary xray beam down to 70 µm is described by Vittiglio et al. (194). This instrument is capable of detecting the presence of a number of elements present at above the 10- 100 ppm level in glass matrices. Another portable XRF was developed and utilized for classification of Islamic glasses in Egypt (195,196). This instrument utilizes two x-ray sources and operates with an air path limiting it to detection of elements heavier than Na. Using this instrument the researchers were able to classify the alkali sources of a number of glass objects using intensities and their ratios, including Sr, Ti, Sr/Zr and K/Ca.


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Total reflection x-ray fluorescence spectrometry (TXRF) has been found to be effective for discriminating among similar glasses. Nishiwaki, et al. (197) utilized a TXRF instrument with a Mo target x-ray tube operated at 40 kV and collimated to a 1 cm beam width for x-ray excitation. They followed the interesting protocol of dissolving a fragment weighing less than 0.5 mg and condensing it to 10 µL, which was then dried onto a quartz disk for analysis. They detected 13 elements in most glasses with relative standard deviations of less than 8.1%. Using the ratios of five elements to Sr, they were able to differentiate several glass samples having indistinguishable RIs. One drawback to traditional TXRF instruments is that they are expensive large-scale systems. Rosnach (198) demonstrated the potential utility of a benchtop TXRF system by analysis of soils and sediments and hypothesized that it should be effective for trace element measurements in glass. In a forensic application, synchrotron radiation XRF (SRXRF) was assessed to determine the level of additional discrimination among sheet glasses that could be obtained over RI alone (199). In this study, triplicate fragments smaller than 1 mm in maximum dimension from 11 sheets were compared in a pairwise manner using cluster analysis of Ca, Fe, Sr, Zr, Ba, and Ce measurements by SRXRF. Using the combined procedure, 515 of 528 pairs could be correctly discriminated. Implementation of this technology in forensic laboratories is limited by the accessibility of synchrotron sources. An interesting new development during the period covered by this review is the introduction of new instrumentation for performing XRF using the energydispersive x-ray detector in a scanning electron microscope. In one development paper, Bjeoumikhov et al. (200) describe a microfocus x-ray source that is directed through capillary optics to provide x-ray excitation in the same region of a sample as that impacted by the electron beam used for imaging in an SEM. Because of the large reduction in Bremsstrahlung background with x-rays compared to electron beam excitation, a two order of magnitude improvement in detection limits is realized. With a motorized stage, elemental maps can be generated that coincide with scanning e-beam images. Two commercial applications of this technology have recently been introduced (201). Since most forensic laboratories already have SEMs with existing x-ray detectors, this approach offers the simultaneous capabilities of high resolution imaging and improved sensitivity for minor element detection without the requirement of acquiring a separate XRF instrument. Electron Beam Excitation Scanning electron microscopy, particularly combined with energy dispersive x-ray microanalysis (SEM/EDX) is widely used in forensic laboratories for elemental comparison of evidentiary materials including glass fragments. This is a previously well-characterized technique, so little new literature has appeared on improvements in methodology or application to forensic glass comparisons. A review article by Schreiner et al. (202) describes the use of SEM/EDX for the characterization of cultural artifacts within several European programs designed to utilize science and technology to improve the preservation and conservation of their cultural heritage. Examples are given of the use of SEM/EDX measurements for the classification of ancient archaeological glass fragments from Ephesos/Turkey and for investigation of the chemical processes that occurred during the weathering of glass window panels and Medieval glass paintings. SEM/EDX analysis of glass in controlled studies has been used to determine chemical/physical models for weathering and 124

contamination of glasses in Europe. Melcher and Schreiner (203) studied two K2OCaO-SiO2 model glasses exposed at 26 test sites throughout Europe. Using SEM/EDX and other methods, they were able to relate the degree of weathering product formation on the surface of the samples with weathering factors, such as the temperature, the relative humidity, and the amounts and composition of acidifying gases in the environment. Carbo et al. (204) studied the degradation of buried glass from different archaeological sites in the Valencian region of Spain using a combination of SEM/EDX and square wave voltammetry. Lombardo et al. (205,206) exposed soda-lime-silica float glass samples to a polluted urban environment (Paris) for up to two years and studied leaching of alkalis and deposit of soot and soluble salts on the tin bath and top surfaces of the glass. Each of these studies took advantage of the spatial imaging capability of SEM combined with the analytical evaluation of multiple layers of varying thickness and composition using EDX. For the forensic glass examiner, these studies introduce the possibility that analysis of the surfaces of glass objects, including modern float glass, may provide data that could be used to form opinions as to their potential sources. Researchers in Belgium used electron probe x-ray microanalysis (EPMA) in several archaeological studies of glasses obtained from archaeological sites throughout Europe to determine the origin of glass fragments from the 15th through 17th centuries (207-209). They were able to measure elements present at the percent level in the glasses with enough accuracy to allow classification into production groups or manufacturing methods. Particle Induced X-Ray Emission A number of studies have been conducted using proton induced x-ray emission (PIXE), either alone or in combination with other analytical methods, for the analysis of glass of archaeological interest. The principal advantage of PIXE is that it is nondestructive. Weber et al. (210) review a number of applications of PIXE and proton induced γ-ray emission (PIGE) under variable ion beam incident angles. By tilting the sample, they were able to eliminate the integration effect of x-rays or γrays produced at different positions in the beam path and resolve layers in multilayer structures. They applied this approach to measuring silver yellow on a stained glass window with PIXE and measuring the degree of sodium migration in the first 50 µm of glass thickness resulting from surface corrosion on a Roman glass sample with PIXE and PIGE. In another study, Weber et al. (211) used PIXE to measure the Na concentration near the surface and PIGE to measure the Na concentration in the bulk of stained glass pieces. The age of the glass could be correlated with the two concentration measurements. Mäder and Neelmeijer (212) reviewed the use of PIXE, PIGE, and Rutherford backscattering spectrometry (RBS) to study the atmospheric degradation of historic glass objects. By analyzing the bulk composition of a glass object through a thin surface corrosion coating, they were able to determine museum storage conditions required to prevent further degradation. Zhang et al. (213) studied early glasses unearthed from tombs in south China dating from 475 BC to 220 AD. Using external beam PIXE results and cluster analysis, they were able to attribute the glasses to two systems, PbO-BaO-SiO2 and K2O-SiO2. In a follow-up study (214), they combined PIXE and ICP-AES to expand upon the number of systems that could be characterized and also used the combined data to hypothesize as to sources of some of the raw materials used to make glass in the 125

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south of ancient China. Combinations of PIXE, PIGE, and RBS were also used for analysis and partial source classification of 5th century AD Roman glass fragments (215) and 20th century AD U.S. and Austrian Art Nouveau glasses (216). In both cases, the information obtained is used to compare glasses of widely different types and to observe layering structures and weathering features. These studies take good advantage of the nondestructive nature of PIXE, but also demonstrate the interpretive limitations imposed by relatively low sensitivity and quantitative inaccuracy that characterizes PIXE compared to other analytical methods. Mit, et al. (217) provide an excellent demonstration of the comparative and combined sourcing power of PIXE/PIGE and laser ablation-inductively coupled mass spectrometry (LA-ICP-MS) in a study of glasses that had been recovered from Ljubljana and Slovenian castles. PIXE with a 2 MeV proton beam in air was used to determine elements Si and heavier; PIGE at 3.2 MeV was used for Na, Mg, Al, and Si; and the results were normalized using Si. The LA-ICP-MS provided quantitative results for Zr, Hf, and the rare earth elements (REE). The PIXE and PIGE results are used to demonstrate that the glasses were made according to the Venetian style. The REE fingerprinting indicated that different local sources of silica were likely used for the various glasses. Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) Background Studies Solution-based ICP methods utilizing either optical emission spectrometry (OES) or MS detection have been utilized by crime labs for the analysis of glass fragments for over 25 years. Recently, ICP-MS coupled with laser ablation (LA-ICP-MS) has received great interest as a method for analysis of glass fragments. Appealing features of LA-ICP-MS include its quantitative multielement capability, its wide linear dynamic ranges, its good accuracy and precision, and its ability to analyze small glass fragments without dissolution or other sample pretreatment. Very few publications concerning solution-based ICP methods for glass analysis have appeared in the recent literature. In contrast, several hundred publications and presentations during the review period present results of fundamental studies and applications of LA-ICP-MS to the analysis of glass. Despite the growing appeal and current utilization of LA-ICP-MS in forensic laboratories, there remain some fundamental questions concerning processes collectively referred to as elemental fractionation. Fractionation refers to differences in behavior among the various elements and ions resulting from the collective processes of matrix-dependent ablation efficiencies, efficiency of aerosol transport, vaporization and ionization properties of particles within the ICP, and ion extraction yield into the MS. The significance of fractionation is that it can have a significant influence on matrixmatching requirements of standards for calibration (i.e. accuracy) and also on measurement precision and detection limits. Most researchers who are studying the fundamental properties of LA-ICP-MS utilize glass reference materials, such as U.S. National Institute of Standards (NIST) Standard Reference Material, SRM 610 for their work. Glass SRMs are appropriate for these studies because they contain known concentrations of many trace elements and are relatively homogeneous even on the cubic micrometer scale of ablation volumes.


While these studies are not designed for the development of forensic protocols, per se, the fact that glass is used makes the results applicable to the forensic interpretation of LA-ICP-MS data. Therefore, a few examples selected from the many papers published during the review period are briefly mentioned. Günther and his coworkers continued their studies into the causes of elemental fractionation in LA-ICP-MS. Of particular pertinence to glass analysis is the doctoral dissertation work of Kuhn. Kuhn and Günther (218,219) collected aerosol particles produced by LA of various materials including SRM 610 glass and examined them by SEM imaging. Using laser wavelengths of 193nm and 266nm and helium and argon transport gases, nanoparticles were formed and condensed during aerosol transport, reaching the plasma as micrometer-sized clusters. The size and structure of the clusters is matrix dependent, thereby supporting the need for using matrix-matched standards or making mass transport corrections for analysis of unknown materials. In the case of glass, the availability of nominally matrix-matched standards having a wide range of compositions simplifies the analysis. Kuhn and Günther (220) further developed this approach into an analytical protocol in which 1% of the particle stream is separated for particle size measurements, which are used to form correction factors for mass measurements. The remainder of the aerosol was used for ICP-MS analysis with NIST SRM 610 glass as an external calibration standard. Using this method, they obtain results agreeing within 10% of those obtained by internal standardization across a variety of matrices including SRM 612 and 614 glasses. Wang, Hattendorf, and Günther (221) measured the distribution of 36 atoms and 2 oxide ions across and along the main axis of the ICP in a LA-ICP-MS as functions of laser wavelength (193nm and 266nm) using helium and argon transport gases. They produced spatial intensity maps that provide information that can be used to define optimal operating conditions for the use of internal standards in making matrix corrections. For example, He produced lower variability in elemental intensity ratios than Ar, but measured signals were lower because of a wider radial spread of the ions. Tunheng and Hirata (222) describe two devices that when placed between the LA chamber and the ICP, serve to smooth the measured MS signal. They claim that these devices improve precision and lessen fractionation effects for small crater sizes and low laser firing rates. They attribute this signal improvement to the removal of large particles from the ablation aerosol stream. Koch et al. (223) used near-infrared femtosecond laser ablation of NIST 1412 glass to study the fractionation of Ca, Sr, Ba, and Pb relative to Zn (all present at nominally 4.5 oxide percent in this material). They showed using their LA setup that elemental fractionation is most significant for laser fluxes below 5 Jcm2. At higher fluxes, particle sizes were more tightly grouped in the 10–100nm range. They also observed conglomerates similar to those reported by Kuhn and Günther. Gonzalez et al. (224) studied the temporal response of the MS signal using 213nm laser ablation in LA-ICP-MS. Their central conclusion, which has been widely replicated and has been implemented into most forensic protocols, was that single spot sampling provided better accuracy and precision than a scanning strategy, particularly when the first 15 seconds of sampling time is eliminated from the data analysis. Gonzalez et al. (225) showed that precision can be improved using double pulse ablation. The first pulse removes a mass of particles from the sample.


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After a variable time delay, a second pulse breaks the particle mass into a finer aerosol. The intent of this approach is to minimize matrix-induced fractionation. The use of double pulse ablation has not found widespread use in glass analysis because the consistency of glass matrices minimizes the problems associated with matrix matching seen with other materials. Gonzalez et al. (226) measured precision of measurements within a spot and between spots on SRM 610 and 612 samples using repetitive fs and ns 266nm laser ablation. Femtosecond laser sampling provided improved precision because it generated more consistent particle size distributions. They attribute the primary errors in LA to systematic effects (i.e., particle sizes) rather than random counting statistics. Luo et al. (227) attempted to follow the EURACHEM/CITAC Guide for estimation of a budget for the sources of uncertainty for measured Co, La, and Th in NIST and USGS glasses. They utilized commercial LA-ICP-MS systems operating at 193nm with a 60 µm spot size at a 10 Hz rep rate. They conclude that overall uncertainty is dominated by reference value errors, providing good support for the use of this method for forensic glass comparison. Forensic Applications The NITE-CRIME Thematic Network completed its inter-laboratory studies for development and evaluation of a LA-ICP-MS protocol for determination of 41 elements in a glass fragment (228). It presented the first compositional data for the FGS1 and FGS2 standards that were produced by Schott Glas under the guidance of the BKA for its use in instrument calibration. Results obtained by most labs and elements presented for the BKA’s FG10-1 float glass agreed to within 10% of the accepted values. A similar protocol was also published by Smith et al. (229). Both protocols recommend use of 29Si as an internal standard and the use of single spot ablation made with a spot size of approximately 50 µm. The NITE-CRIME study utilized fragments embedded in a resin and polished, while the Smith procedure merely required placing the cleaned fragments in an ablation cell and the use of helium as a transport gas. Neufeld (230) demonstrated the application of a similar procedure to the determination of 20 elements in 4 SRMs and 3 glass headlamp lenses. The NFI was the first crime laboratory to validate a LA-ICP-MS protocol according to the ISO/IEC 17025 standards. Berends-Montero, et al. (231) reported the results of their validation including measurements of the variation of measured element concentrations as a function of fragment size and across a large pane of glass. The NFI protocol consists of measuring the concentration of 10 elements (others were considered to be less forensically useful) in embedded glass fragments (unless fragments were too small, and then they were not embedded) using a 213nm laser in the spot mode and helium carrier gas. A full validation report authored by Montero is available on the NFI website (232). Additional laboratories, including the BKA are in the process of completing validation studies for protocols that are very similar to those already published. As these methods have become more widely accepted, several researchers have begun to look at the distributions of measured element concentrations in a variety of glass objects with the goal of establishing match criteria. Some of these studies are discussed later in this report under the heading of Interpretation.


Previous studies by ICP-OES lead to the general conclusion that glass was homogeneous enough that real variations in element concentrations could not be detected using the mg-sized samples for dissolution techniques. It has been hypothesized that the smaller sample sizes from crater pits in LS methods could reveal heterogeneity not previously seen, thereby leading to a need for new match criteria in glass fragment comparisons. Trejos and Almirall (233,234) utilized LAICPMS to evaluate the microheterogeneity of element concentrations in common containers and automobile and architectural windows. They could not detect spatial heterogeneity in float sheets using a 266nm laser at a spot size of 50µm. They also could detect no particle size effects for free standing particles of a homogeneous standard reference glass from the size of a bulk sample down to a particle size of 0.2mm. However, bottle glass exhibited heterogeneity that was measurable under their analytical conditions. Umpierrez et al. (235) provided data to support the widely-advertised advantage of use of a collision cell to diminish the mass spectral interferences on Fe isotopes. They reported roughly a 100-fold improvement in the detection limits for Fe in glass, down to 0.03 mg-kg-1.using LA-ICP-collision cell MS with methane as the collision gas. LA-ICP-MS for the determination of lead isotopic composition of several glasses was also reported. Ehrlich et al. (236) used a multiple collector MS to make high precision Pb isotope measurements in NIST SRM 610 glass. Schultheis et al. (237) used a similar LA-ICP-MS with a high resolution sector field MS to determine Pb isotope ratios in several art nouveau glass samples. The glasses were high leadborosilicate glasses produced by the U.S. manufacturer, Tiffany. The three samples were readily distinguished by both 208Pb/206Pb and 207Pb/206Pb ratios. No mention was made as to whether the glasses were distinguishable by other methods, although, at least one pair was of different colours. Laser Induced Breakdown Spectroscopy (LIBS) LIBS has emerged in the past ten years or so as a promising technique for elemental and molecular characterization of a wide variety of materials, including glass. LIBS is a method based on collection of optical spectra emitted by a material following excitation by a high intensity pulsed laser. The potential advantages of LIBS that have stimulated interest in the forensic community are that it is quick, is practically nondestructive (at least, less so than laser ablation), is capable of measurement of both organic molecules as well as elements, can be constructed in a portable package, and is less expensive and complicated than LA-ICP methods. Studies of LIBS have demonstrated the ability to detect the presence of major constituent elements in several glass types. Almirall et al. (238) presented some preliminary data comparing the discrimination capability of LIBS with those of SEMEDS, XRF, and LA-ICP-MS and they conclude that LIBS has potential utility in forensic analysis of glass samples. In a review article, Giakoumaki et al. (239) discuss the prospects for use of LIBS in archaeological applications and provide several examples involving glass and pottery. Commercial LIBS systems are advertised as applicable to both laboratory and in-line manufacturing plant environments for characterization of defects in glass as well as sorting and quality control applications (240,241). Bridge et al. (242) compare the use of LIBS to that of LA-ICP-MS for discrimination of glass sources in a crime laboratory. Unfortunately, in part because 129

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of MS stability problems, they utilize intensity ratio measurements rather than providing element concentrations. The only data provided are the discrimination percentages. They compared pairs of 23 separate glass sources and found that using LIBS alone 82 to 93 percent of sample pairs could be discriminated depending upon the level of significance compared with 83 to 87 percent for RI and 100% for LA-ICP-MS at all significance levels. In combination, LIBS and RI were capable of discriminating between 96 to 99 percent of the pairs. A number of studies reported the results of exploratory studies of application of LIBS to glass and comparison with other techniques. Galiova et al. (243) compare the use of LIBS with LA-ICP-OES using a 266nm laser for both glass and soil samples. They obtained good calibration responses for Si, Na, Mg, and K in glass. Carmona et al. (244) explored the possibility of using LIBS to study the surfaces of unweathered and artificially corroded glasses. The soft ablation of the laser allowed successive analyses of the corrosion layers, to include major elements and chromophores, such as Co, Cr, Cu, Fe, and Mn. In their study, they highlighted the advantages of LIBS ablation by comparing results with those obtained by SEMEDX, XRF, and UV-Vis spectroscopy. In a more recent study, Carmona et al. (245) demonstrated the use of LIBS with a 266nm laser to differentiate among three types of leaded glass (10 to 30 wt% PbO) both before and after acid and alkaline attack. Melessanaki et al. (246) demonstrated the use of a transportable LIBS instrument to characterize glass beads and similar samples of archaeological interest. Lal et al. (247) reported the effects of various setup parameters on the results obtained using LIBS for analysis of pelletized powders of glasses used for vitrification of radioactive wastes. Despite its relative simplicity and ease of use, LIBS has not yet attained the same level of interest as LA-ICP-MS for forensic comparison of small glass fragments. The reasons generally cited for this are the historical problem of poor accuracy, particularly for small, irregularly shaped particles, and the poor sensitivity, which limits coverage to major elements. Novel approaches, such as the use of double pulsed laser systems as reported by Gautier et al. (248), may have the potential to improve the analytical capabilities of LIBS. In the Gautier study and others, it has been observed that two laser pulses with optimized time delay and energy levels result in a significant increase in emission intensities; however accurate quantitation remains problematic. Other Methods ICP-OES has been used successfully for forensic analysis of dissolved glass fragments for over 20 years. However, because it is such an established method, few publications using it have appeared recently. Zachariadis et al. (249) optimized the acid composition and other digestion parameters for microwave assisted dissolution of glass for ICP-OES analysis. Their protocol was optimized for ancient Byzantine glass samples, but can also be applied to modern glass. They report good analytical results for 7 elements using 12 wavelengths for NIST SRM 621 and 12 elements at 20 wavelengths in archaeological glass. Wang et al. (250) report an ICP-OES method for determination of sulfur at 181.972 nm and phosphorous at 177.434 nm in glass following dissolution. Their reported detection limits and analytical precisions are good enough that the method could be applied to characterization of glass 130

fragments. However, the forensic utility of these elements for glass source comparison is not known. Bian et al. (251) coupled a near-IR femtosecond laser with ICP-OES for analysis of glass without dissolution. They found that this arrangement reduces the level of fractionation to the extent that accurate quantitative results could be obtained without the need for matrix-matched standards. Most of their work was for Cu and Zn measurements in brass, but in one worst-case example, they showed linearity of calibration curves for Zn/Cu ratios across the brass and glass matrices. Pisonero et al. (252) describe the development of a radiofrequency glow-discharge source that they coupled to a time-of-flight mass spectrometer (TOFMS) for direct analysis of nonconducting samples such as thick glass shards. They compared two instrumental configurations using homogeneous glasses to determine optimum design and operational characteristics. They detect major and minor elements and isotope ratios within approximately 1% accuracy using a TOFMS with a moderate mass resolving power of 700. Secondary ion MS (SIMS) continues to show promise in studies of glass of archaeological interest. Dowsett and Adriaens (253) review the application of SIMS to solution of a variety of problems in the area of cultural heritage. Advantages of SIMS are its ppm to ppb sensitivity using very small sample volumes. SIMS can provide surface-specific information when used in the static mode and depth profile analysis in the dynamic mode. These authors discuss specific glass applications including source authentication, determination of origin and provenance, and evaluation of weathering processes. In a nontechnical overview, Rutten et al. (254) describe the advantages of TOF-SIMS for characterization of several glass samples of historical interest. Of particular interest is the advantage of using SIMS to characterize small opacifying inclusions in glass beads and a decorated vessel from the 10th and 14th centuries. It is hypothesized that the data obtained in these studies will provide new insight into whether Egypt made glass from local materials or imported ready-made raw glass from Mesopotamia. Fearn et al. (255) used lowenergy SIMS to study the corrosion of glass in a museum environment in an attempt to optimize the storage environment to prevent deterioration of glass objects on display. In a comprehensive review article, Johnson and Johnson (256) summarize the large number of studies utilizing Mossbauer spectroscopy to measure tin and iron distributions in float glass and relate these distributions to the chemistry occurring during the float process. In addition to an overview of the Mossbauer principle and its application to silicate glasses, they also provide convincing data to show that Sn2+ and Fe3+ act as conditional glass formers, while Sn4+ and Fe2+ act as modifiers. The oxidation of Sn from the +2 to +4 state as a function of depth from the float surface at different temperatures allows calculation of the oxygen diffusion coefficient. In tinted glasses containing percent levels of iron, the Fe3+ oxidizes the Sn2+ to Sn4+. Colomban et al. (257) established a Raman procedure for on-site evaluation of the degree of weathering of stained glass windows. They divided stained glass into four categories based on the Na-K-Ca distributions. Using ion exchange in the laboratory and confirmation of the Raman results with those obtained by IR spectroscopy, optical microscopy, and SEM/EDX, they correlated different weathering rates with the glass type and the changes occurring in the microstructure. The potential demonstrated for measuring the degree of weathering of glass in situ may have 131

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application in a few forensic situations. Interpretation, Statistics, And Significance Transfer and Persistence The number of studies concerning transfer and persistence of glass fragments on the clothing of participants in crime scenarios and the number of particles in the noncriminal environment has dropped from past reporting periods. However, this information is needed for determination of the significance of recovering indistinguishable fragments. Therefore, these studies are being conducted in a few forensic laboratories under case-specific circumstances. Zadora (258) presented the results of such a study in which the number of fragments were measured in a repeated simulated break-in scenario. In this study, the number of fragments recovered depended upon the breaking scenario and the time between breaking and recovery of fragments as expected. Generally, a greater number of fragments were recovered from upper garments of the breaker than on other garments, regardless of the retention ability of the fabrics. This result indicates that distance from the window is the most significant factor in determining number of fragments retained. In another part of this study, the researchers found that 14% of a population of garments not intentionally exposed to glass fragments contained one or two fragments of glass. The authors offer no explanation as to why this result is higher than those reported in most of the previous studies. One difficulty that has plagued studies of glass transfer is the extreme variability observed in particle recovery under any dynamic test that represents a realistic crime scenario. Hicks et al. (259) attempted to minimize this variability by performing a study to develop models for predicting the number of particles transferred to the upper garments of persons in the vicinity of the breaking window by correlation with the number of fragments recovered from a cardboard square of fixed size on an area on the floor at their position. The controlled variables included glass thickness, glass type, method of breaking, and ammunition type for breaking by shooting. Despite the inherent variation in the breaking process, they were able to show at least within the limited range of their variables, that they could make a reasonable estimate of the number of particles transferred to a shooter at a fixed location at time=0 using linear regression models. This study has many limitations, such as not taking into account the variability of collecting fragments from the ground in a fixed area around the breaker’s suspected position. However, it is a good first step in attempting to generalize the calculation of the number of recovered fragments, information that is needed for assessing activity level propositions in some approaches for interpretation of evidence. Further work is needed and anticipated by the authors to consider a wider range of breaking parameters, the effects of garment type, and the effects of post-breaking activity. Statistical Studies David Lucy’s book entitled “Introduction to Statistics for Forensic Scientists” (260) provides an excellent introduction to the concepts related to forensic comparison of samples, presented in a readily understandable manner. Lucy presents the advantages of various approaches for evaluating the value of specimens having similar characteristics, as well as the often difficult requirements placed on the examiner as to selection of databases and number of measurements required. Near 132

the end of the book, Lucy gives a good, but brief, summary of how to treat the continuous, multidimensional data that results from modern methods of glass examination. As in prior reviews, statistical studies can be readily divided into two categories, those based on traditional hypothesis testing and those based on calculation of likelihood ratios (LR). The use of a full Bayesian analysis with calculation of likelihood ratios has been criticized when applied to multivariate data (element concentrations) because of the unavailability of appropriate databases and the large sampling requirements of a multivariate problem. In response, Aitken and his colleagues have produced several papers describing approaches to diminish the complexity of the multivariate problem. Aitken and Lucy (261) used XRF data from 62 windows taken from a single house (5 measurements from each window) to compare five methods of assessment of the value of the evidence. Their data consisted of the log ratios of Ca/Fe, Ca/K, and Ca/Si. The five tests were a multiple t-test, a multivariate significance test based on Hotelling’s T2, and three LR tests. The three LRs consist of the ratio of a Hotelling’s T2 statistic to a univariate kernel density estimate, the convolution of two multivariate normal densities, and a within group probability density function to a between group multivariate kernel density estimate. Of the five approaches, the one using the multivariate kernel density estimate of the between group variation is recommended. One consideration in this result is that different window panes are considered to be “different groups” although, since taken from a single house (even from a single window, in some instances), they could have a single origin. Aitken et al. (262) attempted to reduce the parameterization of a full LR model for multivariate elemental data while still retaining much of the dependence structure. They evaluated the derived models using log ratios of Na, Mg, Al, Si, and Ca to oxygen as determined by SEM/EDX on 130 sheets of float glass. The three-level model that they used resulted in a large proportion of false negatives (nearly 50%) and what they termed a small proportion of false positives (8%), both much worse than the two-level approach of Aitken and Lucy. Aitken, et al. (263) continued their study of the two-level model. Their data consisted of the log concentration ratios of 7 elements to oxygen as determined by SEM/EDX in replicate measurements from 200 glass objects. Because the number of elements exceeded the number of measurements, they used a graphical method of estimating the dependency structure among the variables, thereby reducing the dimensionality of the problem. They showed improved performance of this two level model compared with previous models, giving 15.2% false positive and 5.5% false negative rates. These three studies demonstrate the need to reduce the dimensionality that results from measurement of element concentrations in order to calculate LRs. For multiple pairwise comparisons, Pawluk-Kolk et al. (264) propose the use of a false discovery rate (FDR) procedure to set significance levels in order to minimize both Type I and Type II errors. Using RI measurements for 72 automobile window glasses, they claim that the Welch modification to the t-test with the FDR correction to the significance level results in fewer total errors than do more traditional hypothesis tests. Their approach may not be applicable in most case work glass comparisons because the number of pairs is typically small, but, nevertheless, they 133

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present another method of setting match criteria that may distribute Type I and II errors in an acceptable manner. The increasing interest in measurement of element concentrations in glass, particularly by LA-ICP-MS has also lead to consideration of match criteria for multivariate comparison of glass fragments. Montero (232) used the variations measured in a sheet glass to establish match criteria in the NFI validation study. The NFI match criteria are that 9 or more of 10 measured elements must have ranges that overlap or have end members that are within two times a standard deviation measure. Becker and Weis (265) reported that the BKA studied various match criteria and found that the best success is obtained when the mean values of 6 measurements for each of 19 elements must agree to within four times an instrumental standard deviation determined by long-term analysis of a standard reference material. Aeschliman et al. (266) used principal components analysis (PCA) of 32 elements in spectra of glass samples obtained by LA-ICP-MS to differentiate 4 “similar” glass samples. They did not utilize concentration measurements made using standards, but instead performed a 2-dimensional PCA plot of the multivariate results. They used 266nm ablation in a line scan at a rate of 50 µm/sec across a fairly large sample surface and low resolution sector field mass spectrometry (SFMS). Bajic et al. (267) used the PCA procedure for comparison of groups of samples having indistinguishable refractive indices. They used a 193nm laser and argon carrier gas with a SFMS instrument in the low resolution mode. They used the full spectrum without calibration for the PCA. All sample pairs were discriminated at a very high level of significance. In both of these studies, no element concentration data are given, so one cannot assess how different the compared samples are. However, the high discriminating power of LA-ICP-MS is strongly indicated and the simplicity of PCA is touted. International Activities SWGMAT published its guidelines for glass examinations in Forensic Science Communications (268). The seven published guidelines provide a general overview of glass collection and examination, but only limited protocol details. Notably missing from the SWGMAT glass guidelines is one concerning interpretation of results. ASTM Method E2330-04, Standard Test Method for Determination of Trace Elements in Glass Samples Using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was approved and published (269). This method is applicable to determination of 15 elements in glass, but can readily be modified to include additional elements. It is applicable to measurement of element concentrations in solution following dissolution of small irregularly shaped glass fragments as small as 200 µg. As discussed previously, several LA-ICP-MS protocols for analysis of glass fragments were produced by international organizations or were validated under international guidelines. The NITE-CRIME committee published the results of their interlaboratory studies and recommended a method for LA-ICP-MS of glass fragments (228). The NFI completed the validation of their LA-ICP-MS protocol under ISO 17025 guidelines and published the results on their website (232). As this review is being written, the ENFSI EPG best practice guidelines for glass examination are being voted on at their meeting in September 2007. These guidelines consist of six documents concerning the topics: general introduction to glass, determination of refractive index, microscopic techniques for glass examiners, elemental analysis by XRF, elemental analysis by SEM/EDX, and elemental analysis 134

by LA-ICP-MS. As with SWGMAT, the EPG guidelines for evaluation of analytical data and statistical treatment of source level questions is not ready for a group vote at this time. Acknowledgements The assistance of Jane Garrison and Yvette Trozzi in performing literature searches and acquiring references is gratefully acknowledged. Appreciation is also expressed to Maureen Bottrell and JoAnn Buscaglia for assistance in reviewing the manuscript. References 1 Ford Earns EPA Award. Coatings World 2007; (April):16. 2 Spielman S. 2005 Automotive Report. Industrial Paint & Powder 2005; 16(9):81-87. 3 Schoff CK. Organic coatings: the paradoxical materials. Progress in Organic Coatings 2005; 52:21-27. 4 Pianoforte K. Automotive Coatings Market. Coatings World 2007; (March):30-32. 5 BASF Introduces 1K Cathodic Electrodeposition Coating. Coatings World 2007;(May):28. 6 Giles TR. Emerging Technologies in Pretreatment. Coatings World 2006; (October):52-61. 7 Gichuhi T, Novelli W, Erbsloh C, Adams A, DeGroot M, Sapp M, Thorn A. High Performance Organic and Inorganic Zinc-Free Corrosion Inhibitors. European Coatings Journal 2005; 17:47-56. 8 Chouinard T. Changing The Way We Colour Our World. Paint and Coatings Industry 2006; (June):26-30. 9 Whitfield K. Who Needs Paint? Automotive Design & Production 2004; (October). 10 Challener C. Pigment Market Still Performing but Challenges May Impact Intensity of Growth. Journal of Coatings Technology 2006; (October):96101. 11 Wright T. Metallic Pigments. Coatings World 2007; (June):30-33. 12 Venturini M, Liu W, Sullivan W. Aluminum Effect Pigment Blends. US Patent Appl. US 2005/0252416 A1, Nov. 17, 2005. 13 Yates MJ, Mitchell, J. Optimising formulations. Polymers Paint Colour Journal 2006; (December):24-26. 14 Pianoforte K. High Performance Pigments. Coatings World 2007; (August):28-31. 15 Cooper RJ, Camp PJ, Henderson DK, Lovatt PA, Nation DA, Richards S, Tasker PA. The binding of phosphonic acids at aluminium oxide surfaces and correlation with passivation of aluminum flake. Dalton Trans. 2007:1300-1308. 16 Kerr S. Surface-Treated Metallic Pigments. Paint and Coatings Industry 2006;(August):72-78. 17 Brussaard Y, Genn B. High-Performance Titanium Colour Pigments. Paint and Coatings Industry 2004; (October):34-40. 18 Frischmann L, Klose S. Does Yellow Beat White? Paint and Coatings Industry2007; (July):106-108. 19 Wilker G. Progress in the Field of Yellow Organic Pigments. Paint and 135

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Luo Y, Gao, S, Longerich HP, Günther D, Wunderli S, Yuan H-L, Liu X-M. The uncertainty budget of the multi-element analysis of glasses using LAICP-MS. Journal of Analytical Atomic Spectrometry 2007; 22(2):122-130. Latkoczy C, et al. Development and evaluation of a standard method for the quantitative determination of elements in float glass samples by LA-ICP-MS. Journal of Forensic Sciences 2005; 50(6):1327-1341. Smith K, et al. A guide for the quantitative elemental analysis of glass using laser ablation inductively coupled plasma mass spectrometry. Atomic Spectroscopy 2006; 27(3):69-75. Neufeld LM. Application of laser ablation ICP-MS to the analysis of forensic glass samples. Spectroscopy (Springfield, Or.) 2005; 20(7):31-36. Berends-Montero S, et al.. Forensic analysis of float glass using laser ablation inductively coupled plasma mass spectrometry (LA-ICP MS):validation of a method. Journal of Analytical Atomic Spectrometry 2006; 21(11):1185-1193. Montero S. Forensic float-glass analysis using laser ablation inductivelycoupled plasma mass spectrometry (LA-ICP-MS), method validation. 2005, NFI, Den Haag Trejos T, Almirall JR. Sampling strategies for the analysis of glass fragments by LA-ICP-MS. Part I:Micro-homogeneity study of glass and its application to the interpretation of forensic evidence. Talanta 2005; 67(2):388-395. Trejos T, Almirall JR. Sampling strategies for the analysis of glass fragments by LA-ICP-MS. Part II:Sample size and sample shape considerations. Talanta 2005; 67(2):396-401. Umpierrez S, et al. Determination of iron in glass by solution and laser ablation DRC-ICP-MS. Atomic Spectroscopy 2006; 27(3):76-79. Ehrlich S, Ben-Dor L, Halicz L, Precise isotope ratio measurement by multicollector-ICP-MS without matrix separation. Canadian Journal of Analytical Science and Spectroscopy 2004; 49(3):136-147. Schultheis G, et al. Characterisation of ancient and art nouveau glass samples by Pb isotopic analysis using laser ablation coupled to a magnetic sector field inductively coupled plasma mass spectrometer (LA-ICP-SF-MS). Journal of Analytical Atomic Spectrometry 2004; 19(7):838-843. Almirall J, et al. Forensic elemental analysis of materials by laser induced breakdown spectroscopy (LIBS). in Sensors and Command, Control, Communications, and Intelligence (C3I) Technologies for Homeland Security and Homeland Defense IV. 2005:Proceedings of the International Society for Optical Engineering (SPIE). Giakoumaki A, Melessanaki K, Anglos D, Laser-induced breakdown spectroscopy (LIBS) in archaeological science-:applications and prospects: archaeometry. Analytical and Bioanalytical Chemistry 2007; 387(3):749-760. Craparo JC, Weisberg A, DeSaro R, New technique developed to measure glass batch, sort cullet. American Ceramic Society Bulletin 2006; 85(3):33-37. Bridge CM, et al. Characterization of automobile float glass with laserinduced breakdown spectroscopy and laser ablation inductively coupled 149

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plasma mass spectrometry. Applied Spectroscopy 2006; 60(10):11811187. Galiova M, et al. Study of laser-sample interactions of glasses and soils using laser-induced breakdown spectrocopy and optical emission spectroscopy with inductively coupled plasma. Chemicke Listy 2006; 100(3):204-209. Carmona N, et al. Analysis of corroded glasses by laser induced breakdown spectroscopy. Spectrochimica Acta Part B:Atomic Spectroscopy 2005; 60B(7-8):1155-1162. Carmona N, et al. Lead determination in glasses by laser-induced breakdown spectroscopy. Spectrochimica Acta Part B:Atomic Spectroscopy 2007; 62(2):92-100. Melessanaki K, et al. Analysis of archaeological objects with LMNTI, a new transportable LIBS instrument. Springer Proceedings in Physics 2005;100:443-449. Lal, B., Yueh, F.Y., Singh, J.P., and Ramsey, W.G., May 2003, The Monitoring of the Composition of Glass Batch of Simulated Glass Waste Using LIBS, Technical Report to Radioactive Immobilization Consortium Project, Diagnostic Instrumentation and Analysis Laboratory, Mississippi State University. Gautier C, et al. Applications of the double-pulse laser-induced breakdown spectroscopy (LIBS) in the collinear beam geometry to the elemental analysis of different materials. Spectrochimica Acta Part B:Atomic Spectroscopy 2006; 61B(2):210-219. Zachariadis G, et al. Optimized microwave-assisted decomposition method for multi-element analysis of glass standard reference material and ancient glass specimens by inductively coupled plasma atomic emission spectrometry. Talanta 2006; 68(5):1448-1456. Wang H, et al. Determination of sulfur and phosphorus in glass by inductively coupled plasma emission spectrometry. Fenxi shiyanshi 2007; 26(1):112-115. Bian QZ, et al. Non-matrix matched calibration of major and minor concentrations of Zn and Cu in brass, aluminium and silicate glass using NIR femtosecond laser ablation inductively coupled plasma mass spectrometry. Journal of Analytical Atomic Spectrometry 2006; 21(2):187191. Pisonero J, et al. A radiofrequency glow-discharge-time-of-flight mass spectrometer for direct analysis of glasses. Analytical and Bioanalytical Chemistry 2004; 379(4):658-667. Dowsett M, Adriaens A. The role of SIMS in cultural heritage studies. Nuclear Instruments and Methods in Physics Research Section B:Beam Interactions with Materials and 2004; 226(1-2):38-52. Rutten F, Henderson J, Briggs D. Unlocking the secrets of ancient glass technology using TOF-SIMS. Spectroscopy Europe. 2005; 17(1):24-30 Fearn S, McPhail DS, Oakley V. Room temperature corrosion of museum glass: an investigation using low-energy SIMS. Applied Surface Science 2004; 231-1:510-514. Johnson JA, Johnson CE. Mossbauer spectroscopy as a probe of silicate glasses. Journal of Physics-Condensed Matter 2005; 17(8):R381-R412. 150

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Colomban P, Etcheverry M-P, Asquier M, Bounichou M, Tournié A. Raman identification of ancient stained glasses and their degree of deterioration. Journal of Raman Spectrocopy 2006; 37(5):614-626. Brozek-Mucha Z, Zadora G, Zidba-Paulus J, Parczewski A. Persistence ofglass fragments after break-in through multiply glazed windows. Presentation T115 at 4th European Academy of Forensic Science Conference (EAFS2006), Helsinki Finland. Hicks T, Schutz F, Curran JM, Triggs CM. A model for estimating the number of glass fragments transferred when breaking a pane: experiments with firearms and hammer. Science and Justice 2005; 45(2):65-74. Lucy D. Introduction to statistics for forensic scientists. 2005, Chichester, West Sussex, England:John Wiley & Sons Ltd., 251 pp. Aitken CGG, Lucy D. Evaluation of trace evidence in the form of multivariate data. Applied Statistics 2004; 53(1):109-122. Aitken CGG, Lucy D, Zadora G, Curran JM. Evaluation of transfer evidence for three-level multivariate data with the use of graphical models. Computational Statistics & Data Analysis 2006; 50(10):2571-2588. Aitken CGG, Zadora G, Lucy D. A two-level model for evidence evaluation. Journal of Forensic Sciences 2007. 52(2):412-419. Pawluk-Ko_c M, Zi_ba-Palus J, Parczewski A. Application of false discovery rate procedure to pairwise comparisons of refractive index of glass fragments. Forensic Science International 2006; 160(1):53-58. Becker S, Weis P. Laser ablation ICP-MS in forensic glass analysis: a decade of experience. Presented at Trace Evidence Symposium, Clearwater Beach, Florida, August 16, 2007. Aeschliman DB, et al. Multivariate pattern matching of trace elements in solids by laser-ablation inductively coupled plasma mass spectrometry:sourc attribution and preliminary diagnosis of fractionation. Analytical Chemistry 2004; 76(11):3119-3125. Bajic SJ, et al. Analysis of glass fragments by laser ablation-inductively coupled plasma-mass spectrometry and principal component analysis. Journal of Forensic Sciences 2005; 50(5):1123-1127.


Section 2-Drugs and Toxicology Technical co-ordinator: Mr. Thomas Janovsky, Drug Enforcement Agency, USA

Chapter 6 Drugs7 Jeffrey Comparin8 Routine and Improved Analysis of Abused Substances Issue: Improved methods of analysis, i.e., faster, more discriminatory, more sensitive, less costly, etc., are needed for all abused substances. Additionally, standard analytical data are required for previously unknown or rarely encountered substances and/or new homolog or analog (i.e., "designer"-type) drugs. Solution: Drug seizures and clandestine laboratory operations are continuously monitored to provide a comprehensive overview of new developments. Ongoing research in the forensic community, as well as in the general field of analytical chemistry, provides new and/or improved methods of analysis for both routine and specialized analyses of seized drugs. Reports providing standard analytical data for new drugs of abuse and/or improved analytical protocols for known drugs of abuse are generated for the forensic and enforcement communities. References: Reviews: Ahuja SS. Assuring quality of drugs by monitoring impurities. Adv Drug Deliv Rev, Jan 2007; 59(1): 3-11. Almirall JE. Forensic chemistry education. Analytical Chemistry 2004;77(3):69A. [Microgram Editor’s Notes: An overview, including projected future needs. Contact: Department of Chemistry and Biochemistry, Florida International University, University Park, Miami, FL 33199.] Almirall JR, Trejos T, Hobbs A, Perr J, Furton KG. Mass spectrometry in forensic science. Advances in Mass Spectrometry 2004;16:167. [Microgram Editor’s Notes: A review of the title topic, includes some applications of mass spectrometry to the analysis of drugs of abuse (unspecified in abstract). Contact: International Forensic Research Institute, Florida International University, Miami, FL 33199.] Anastos N, Barnett NW, Lewis SW. Capillary electrophoresis for forensic drug analysis: A review. Talanta 2005;67(2):269.


All categories are subdivided by topic or category, then alphabetically by the first author’s name. Where appropriate, a short explanatory note is added to the citation to provide additional detail concerning the reference. Note that the following references are law enforcement restricted, and not available to the general public: Microgram and Microgram Bulletin prior to 2003, and the Journal of the Clandestine Laboratory Investigating Chemists Association (all years). 8 U.S. Department of Justice, Drug Enforcement Administration, Office of Forensic Sciences, Alexandria, Virginia, USA.



Anderson C. Presumptive and confirmatory drug tests. Journal of Chemical Education 2005;82(12):1809. Argentine MD, Owens PK, Olsen BA. Strategies for the investigation and control of process-related impurities in drug substances. Adv Drug Deliv Rev, Jan 2007; 59(1): 12-28. Banken JA. Drug abuse trends among youth in the United States. Current Status Of Drug Dependence / Abuse Studies: Cellular And Molecular Mechanisms Of Drugs Of Abuse And Neurotoxicity (Series: Annals Of The New York Academy Of Sciences) 2004;(1025):465. Bogusz MJ, Carracedo A. Forensic analysis. Journal of Chromatography Library 2004;69B:1073. [Microgram Editor’s Notes: A review on the forensic analysis of drugs. Contact: Department of Pathology & Laboratory Medicine, King Faisal Specialist Hospital and Research Center, Riyadh, Saudi Arabia 11211.] Bogusz MJ. Liquid chromatographic/mass spectrometry in forensic toxicology. Advances in Forensic Applications of Mass Spectrometry 2004:63. [Microgram Editor’s Notes: An extensive review of the title topic, focusing on toxicological applications. Contact: Department of Pathology and Laboratory Medicine, King Faisal Specialist Hospital and Research Centre, Riyadh, Saudi Arabia.] Botsford DR. Speed, Ecstasy, Ritalin: The Science of Amphetamines. JAMA, Dec 2006; 296: 2859 - 2860. Boyer EW, Shannon M, Hibberd PL. The Internet and psychoactive substance use among innovative drug users. Pediatrics 2005;115(2):302. Calfee R, Fadale P. Popular Ergogenic Drugs and Supplements in Young Athletes. Pediatrics, Mar 2006; 117: e577 - e589. Chen Z, Huang K. Drug Problems in China: Recent Trends, Countermeasures, and Challenges. Int J Offender Ther Comp Criminol, Feb 2007; 51: 98 - 109. Chen L, Luo G, Wang J, Liu K, Wang Y. Recent advances in abused drug analysis. Yaowu Fenxi Zazhi 2005;25(7):881. [Microgram Editor’s Notes: A review. This article is written in Chinese. Contact: Department of Chemistry, Tsinghua University, Beijing, Peop. Rep. China 100084.] Chung H, Park M, Hahn E, Choi H, Choi H, Lim M. Recent trends of drug abuse and drug-associated deaths in Korea. Current Status Of Drug Dependence / Abuse Studies: Cellular And Molecular Mechanisms Of Drugs Of Abuse And Neurotoxicity (Series: Annals Of The New York Academy Of Sciences) 2004;(1025):458. Cole M. The Analysis of Drugs of Abuse: A Systematic Approach. (Text) John Wiley & Sons Inc., Chichester, UK: 2003.


Cole M. Drugs of abuse. Crime Scene to Court 2004;293. de Boer D, Bosman I. A new trend in drugs-of-abuse, the 2C-series of phenethylamine designer drugs. Pharmacy World & Science 2004;26(2):110. [Microgram Editor’s Notes: A mini-review of a 3-year survey of unusual designer drugs (tablets) obtained at Dutch “smartshops”. Primary drugs included 2C-B, 2C-T2, and 2C-T-7. Includes social commentary and recommendations. Contact: Laboratorio de Analises de Dopagem e Bioquimica, Instituto Nacional do Desporto, Lisbon, Port. 1600-190.] Devaney ML, Reid G, Baldwin S, Crofts N, Power R. Illicit drug use and responses in six Pacific Island countries. Drug Alcohol Rev, Jul 2006; 25(4): 387-90. Duyndam A. XTC: The game and marbles. Chemisch2Weekblad 2005;101(11):20. Fitsev IM, Blokhin VK, Budnikov GK, Fitseva NA. Chemical analytical diagnostics in criminalistic examination of materials, substances, and products. Zavodskaya Laboratoriya, Diagnostika Materialov 2004;70(4):3. [Microgram Editor’s Notes: Includes discussion of (unspecified) drugs and psychotropic substances. This article is written in Russian. Contact: Russia (no further addressing information was provided).] Fitsev IM, Blokhin VK, Budnikov GK. Chromatographic techniques in forensic chemical examinations. Journal of Analytical Chemistry (Translation of Zhurnal Analiticheskoi Khimii) 2004;59(12):1171. [Microgram Editor’s Notes: A minor review. (Unspecified) psychoactive drugs are discussed. Contact: Forensic Examination Center, Ministry of Internal Affairs of Tatarstan, ul. Dzerzhinskogo 19, Kazan, Tatarstan 420503, Russia.] Galarini R, Piersanti A, Falasca S, Salamida S, Fioroni L. A confirmatory method for detection of a banned substance: the validation experience of a routine EU laboratory. Anal Chim Acta, Mar 2007; 586(1-2): 130-6. Halpern JH. Hallucinogens and dissociative agents naturally growing in the United States. Pharmacology & Therapeutics 2004;102(2):131. Haroz R, Greenberg MI. Emerging drugs of abuse. Medical Clinics of North America 2005;89(6):1259. Gossop M. Classification of illegal and harmful drugs. BMJ, Aug 2006; 333: 272-273. Jenkins AJ. Hallucinogens. Principles of Forensic Toxicology (2nd Edition) 2003:267. Kelesidis T, Kelesidis I, Rafailidis PI, Falagas ME. Counterfeit or substandard antimicrobial drugs: a review of the scientific evidence. J. Antimicrob. Chemother., Jun 2007; 10.1093/jac/dkm109.



Kulsudjarit K. Drug problem in Southeast and Southwest Asia. Current Status Of Drug Dependence / Abuse Studies: Cellular And Molecular Mechanisms Of Drugs Of Abuse And Neurotoxicity (Series: Annals Of The New York Academy Of Sciences) 2004;(1025):446. Krueger RJ. Forensic Botany. Principles and Applications to Criminal Casework, Edited by H.M. Coyle Department of Public Safety, Meriden, CT. CRC Press Boca Raton, FL 2005. (Journal of Natural Products) 2006. Mazerolle L, Soole D, Rombouts S. Drug Law Enforcement: A Review of the Evaluation Literature. Police Quarterly, Jun 2007; 10: 115 - 153. McCambridge J, Winstock A, Hunt N, Mitcheson L. 5-Year trends in use of hallucinogens and other adjunct drugs among UK dance drug users. Eur Addict Res, Jan 2007; 13(1): 57-64. Noppe H, Voelmans S, Verheyden K, De Brabander H, Van Hoof N. Current studies in residue analysis methodology. Vlaams Diergeneeskundig Tijdshrift 2005;74(5):340. Reid G, Devaney ML, Baldwin S. Drug production, trafficking and trade in Asia and Pacific Island countries. Drug Alcohol Rev, Nov 2006; 25(6): 647-50. Rendle DF. Advances in chemistry applied to forensic science. Chemical Society Reviews 2005;34(12):1021. Reyes JG, Castro AO, Rodriguez AS, Rodas LC. Trends of the drug use in Mexico City (1986-2003). Drug information reporting system. Salud Mental 2005;28(3):51. Ribaux O, Walsh SJ, Margot P. The contribution of forensic science to crime analysis and investigation: Forensic intelligence. Forensic Science International 2006;156(23):171. Schuetz H, Verhoff MA. Designer drugs: Effects and clinical toxicological interactions. MTA Dialog 2004;5(2):90. [Microgram Editor’s Notes: A minor review on (unspecified) designer drugs. This article is written in German. Contact: Institut fuer Rechtsmedizin, Universitaetsklinikum Giessen, 35392 Giessen, Germany.] Smith F, Siegel J, Eds. Handbook of Forensic Drug Analysis. Elsevier: New York, NY: 2005. Solomon KR, Anadon A, Carrasquilla G, Cerdeira AL, Marshall J, Sanin LH. Coca and poppy eradication in Colombia: environmental and human health assessment of aerially applied glyphosate. Rev Environ Contam Toxicol, Jan 2007; 190: 43-125. Zhao CZ, Liu ZM, Zhao D, Liu YH, Liang JH, Tang YL, Liu ZY, Zheng JW. Drug abuse in China. Current Status Of Drug Dependence / Abuse Studies: Cellular And Molecular Mechanisms Of Drugs Of Abuse And Neurotoxicity (Series: Annals Of The New York Academy Of Sciences) 2004;(1025):439. 156

Scientific Working Group for Forensic Analysis of Illicit Drugs: Amphetamine, Methamphetamine, and Dimethylamphetamine (see also Substituted Amphetamines, Phenethylamines, and Methylenedioxyamphetamines): Apollonio LG, Pianca DJ, Whittall IR, Maher WA, Kyd JM. A demonstration of the use of ultra-performance liquid chromatography-mass spectrometry [UPLC/MS] in the determination of amphetamine-type substances and ketamine for forensic and toxicological analysis. Journal of Chromatography B-Analytical Technologies In The Biomedical And Life Sciences 2006;836(1-2):111. Chafer-Pericas C, Campins-Falco P, Herraez-Hernandez R. Application of solidphase microextraction combined with derivatization to the enantiomeric determination of amphetamines. Journal Of Pharmaceutical And Biomedical Analysis 2006;40(5):1209. ChaferPericas C, CampinsFalco P, HerraezHernandez R. Application of solid-phase microextraction combined with derivatization to the determination of amphetamines by liquid chromatography. Analytical Biochemistry 2004;333(2):328. Chia KJ, Huang SD. Simultaneous derivatization and extraction of amphetaminelike drugs in urine with headspace solid-phase microextraction followed by gas chromatography-mass spectrometry. Analytica Chimica Acta 2005;539(1-2):49. Deventer K, Van Eenoo P, Delbeke FT. Screening for amphetamine and amphetamine-type drugs in doping analysis by liquid chromatography/mass spectrometry. Rapid Communications In Mass Spectrometry 2006;20(5):877. Escamilla B, Bertsch A. N,N-Dimethylamphetamine in Sacramento. Journal of the Clandestine Laboratory Investigating Chemists Association 2004;14(4):19. [Microgram Editor’s Notes: Presents the analysis of samples of dimethylamphetamine and also mixed samples of methamphetamine and dimethylamphetamine. Note that JCLICA is a law enforcement restricted journal. Contact: Sacramento County, Office of the District Attorney, Laboratory of Forensic Services, 4800 Broadway, Suite 200, Sacramento, CA 95820.] Far HRM, Torabi F, Danielsson B, Khayyami M. ELISA on a microchip with a photodiode for detection of amphetamine in plasma and urine. Journal of Analytical Toxicology 2005;29(8):790. Frison G, Tedeschi L, Favretto D, Reheman A, Ferrara SD. Gas chromatography/mass spectrometry determination of amphetamine-related drugs and ephedrines in plasma, urine and hair samples after derivatization with 2,2,2trichloroethyl chloroformate. Rapid Communications In Mass Spectrometry 2005;19(7):919.



Fuh MR, Wu TY, Lin TY. Determination of amphetamine and methamphetamine in urine by solid phase extraction and ion-pair liquid chromatography-electrospraytandem mass spectrometry. Talanta 2006;68(3):987. Gosav S, Praisler M, Dorohoi DO, Popa G. Automated identification of novel amphetamines using a pure neural network and neural networks coupled with principal component analysis. Journal Of Molecular Structure 2005;744(Sp. Iss. SI):821. Gulaboski R, Cordeiro MN, Milhazes N, Garrido J, Borges F, Jorge M, Pereira CM, Bogeski I, Morales AH, Naumoski B, Silva AF. Evaluation of the lipophilic properties of opioids, amphetamine-like drugs, and metabolites through electrochemical studies at the interface between two immiscible solutions. Anal Biochem, Feb 2007; 361(2): 236-43. Hanna GM. NMR regulatory analysis: enantiomeric purity determination for (R)-(-)desoxyephedrine and antipode methamphetamine. Pharmazie, Mar 2006; 61(3): 18893. Hida M, Satoh M, Mitsui T. Detection of trace methamphetamine in dimethylamphetamine hydrochloride as stimulant material. Bunseki Kagaku 2004;53(8):847. [Microgram Editor’s Notes: A study to determine whether trace methamphetamine in a dimethylamphetamine sample is an artifact or an actual impurity. This article is written in Japanese. Contact: Criminal Investigation Lab., Aichi Prefectural Police HDQS, Nagoya, Aichi 460 8502, Japan.] Holler JM, Vorce SP, Bosy TZ, Jacobs A. Quantitative and isomeric determination of amphetamine and methamphetamine from urine using a nonprotic elution solvent and R(-)-alpha-methoxy-alpha-trifluoromethylphenylacetic acid chloride derivatization. Journal of Analytical Toxicology 2005;29(7):652. Iio R, Chinaka S, Takayama N, Hayakawa K. Simultaneous chiral analysis of methamphetamine and related compounds by capillary electrophoresis/mass spectrometry using anionic cyclodextrin. Analytical Sciences 2005;21(1):15. [Microgram Editor’s Notes: Focus is on urinalysis. Contact: Forensic Science Laboratory, Ishikawa Prefectural Police Headquarters, Kanazawa 920-8553, Japan.] Jehanli AMT. Detection of methamphetamine class of drugs. (Patent) Chemical Abstracts 2005:45418. Kankaanpaa A, Gunnar T, Ariniemi K, Lillsunde P, Mykkanen S, Seppala T. Singlestep procedure for gas chromatography-mass spectrometry screening and quantitative determination of amphetamine-type stimulants and related drugs in blood, serum, oral fluid and urine samples. Journal of Chromatography B Analytical Technologies in the Biomedical and Life Sciences 2004;810(1):57. Katainen E, Elomaa M, Laakkonen U-M, Sippola E, Niemela P, Suhonen J, Jarvinen K. Quantification of the amphetamine content in seized street samples by Raman 158

spectroscopy. Journal of Forensic Sciences 2007;52(1):88. [Microgram Editor’s Notes: Presents the title study. The results were favorably compared against LC. Contact: Department of Pharmaceutics, University of Kuopio, P.O Box 1627, FIN-70211 Kuopio, Finland.] Kato N, Fujita S, Kubo H, Homma H. Fluorescence analysis for phydroxymethamphetamine in urine by HPLC with post-column reaction. Journal Of Liquid Chromatography , Related Technologies 2005;28(19):3099. Kawase K, Ogawa Y, Watanabe Y. Component pattern analysis of chemicals using multispectral THz-imaging system. Proceedings of SPIE - The International Society for Optical Engineering. 2004;5354:63. [Microgram Editor’s Notes: A minor review of the title topic. Includes discussion of the application of the technique for the detection of methamphetamine and MDMA concealed in envelopes. Contact: RIKEN, 2-1 Hirosawa, Wako, Japan 351-0198.] Kim JY, Suh SI, In MK, Chung BC. Gas chromatography-high-resolution mass spectrometric method for determination of metamphetamine and its major metabolite amphetamine in human hair. Journal of Analytical Toxicology 2005;29(5):370. Kimura H, Matsumoto K, Mukaida M. Rapid and simple quantitation of methamphetamine by using a homogeneous time-resolved fluoroimmunoassay based on fluorescence resonance energy transfer from europium to Cy5. Journal of Analytical Toxicology 2005;29(8):799. Kishi T, Kanamori T, Tsujikawa K, Iwata YT, Inoue H, Ohtsuru O, Hoshina H, Otani C, Kawase K. Differentiation of optical active form and racemic form of amphetamine-type stimulants by terahertz spectroscopy. Chemical Abstracts 2005;1273200. Klette KL, Jamerson MH, MorrisKukoski CL, Kettle AR, Snyder JJ. Rapid simultaneous determination of amphetamine, methamphetamine, 3,4methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, and 3,4methylenedioxyethylamphetamine in urine by fast gas chromatography-mass spectrometry. Journal of Analytical Toxicology 2005;29(7):669. Knops LA, Northrop DM, Person EC. Capillary electrophoretic analysis of phosphorus species in clandestine methamphetamine laboratory samples. Journal of Forensic Sciences 2006;51(1):82. [Microgram Editor’s Notes: Presents a CE technique that can separate a wide variety of anions (18 listed), including various phosphorus species, in illicitly prepared methamphetamine samples. Contact: Washington State Patrol, Marysville Crime Laboratory, 2700 116 Street NE, Suite P, Marysville, WA 98271.] Koper C, Ali Tolppa E, Bozenko Jr. JS, Dufey V, Puetz M, Weyermann C, Zrcek F. Identification of a new amphetamine type stimulant: 3,4-methylenedioxy(2hydroxyethyl)amphetamine (MDHOET). Microgram Journal 2005;3(3-4):166.



[Microgram Editor’s Notes: Presents the title study. Contact: Netherlands Forensic Institute, P. O. Box 24044, 2490 AA The Hague, The Netherlands.] Lee WS, Chan MF, Tam WM, Hung MY. The application of capillary electrophoresis for enantiomeric separation of N,N-dimethylamphetamine and its related analogs: intelligence study on N,N-dimethylamphetamine samples in crystalline and tablet forms. Forensic Sci Int, Jan 2007; 165(1): 71-7. Lin DL, Liu HC, Yin RM, Chen DT, Soong SJ, Liu RH. Effectiveness of multiple internal standards: Deuterated analogues of methylenedioxymethamphetamine, methylenedioxyamphetamine, methamphetamine, and amphetamine. Journal of Analytical Toxicology 2004;28(8):650. [Microgram Editor’s Notes: Focus is toxicological. Contact: Fooyin Univ, Dept Med Technol, 151 Ching Hsueh Rd, Kaohsiung 831, Hsien, Taiwan.] Liu J. Test kit for detecting rapidly methamphetamine and its manufacture. (Patent) Chemical Abstracts 2005:150146s. Martins L, Yegles M, Chung HS, Wennig R. Simultaneous enantioselective determination of amphetamine and congeners in hair specimens by negative chemical ionization gas chromatography-mass spectrometry. Journal of Chromatography B-Analytical Technologies In The Biomedical And Life Sciences 2005;825(1):57. Meng P, Fang N, Wang M, Liu H, Chen DD. Analysis of amphetamine, methamphetamine and methylenedioxy-methamphetamine by micellar capillary electrophoresis using cation-selective exhaustive injection. Electrophoresis, Aug 2006; 27(16): 3210-7. [Microgram Editor’s Notes: CSEI is used as an on-line concentration method; in this case, sensitivity was increased 1000-fold versus standard capillary MEKC. Contact: Department of Chemistry, University of British Colombia, 2036 Nain Mall, Vancouver V6T 1Z1, Canada.] Mitrevski B, Zdravkovski Z. Rapid and simple method for direct determination of several amphetamines in seized tablets by GC-FID. Forensic Science International 2005;152(2-3):199. Moore KA. Amphetamine/sympathomimetic amines. Principles of Forensic Toxicology (2nd Edition) 2003:245. Nguyen DT, Bui TH. Analysis of amphetamines in narcotic samples. Tap Chi Duoc Hoc 2005;45(2):20. Nieddu M, Boatto G, Carta A, Sanna A, Pisano M. Simultaneous determination of ten amphetamine designer drugs in human whole blood by capillary electrophoresis with diode array detection. Biomedical Chromatography 2005;19(10):737. Paul BD, Jemionek J, Lesser D, Jacobs A, Searles DA. Enantiomeric separation and quantitation of (+/-)-amphetainine, (+/-)-methamphetamine, (+/-)-MDA, (+/-)MDMA, and (+/-)-MDEA in urine specimens by GC-EI-MS after derivatization with 160

(R)-(-)- or (S)-(+)-alpha-Methoxy-alpha-(Trifluoromethy)phenylacetyl (MTPA). Journal of Analytical Toxicology 2004;28(6):449.


Rudaz S, Geiser L, Souverain S, Prat J, Veuthey JL. Rapid stereoselective separations of amphetamine derivatives with highly sulfated gamma-cyclodextrin. Electrophoresis 2005;26(20):3910. Sachs SB, Woo F. A detailed mechanistic fragmentation analysis of methamphetamine and select regioisomers by GC/MS. Journal of Forensic Sciences 2007;52(2):308. [Microgram Editor’s Notes: Presents the title study. Includes methamphetamine and 7 related compounds. Contact: San Francisco Police Department Crime Laboratory, 850 Bryant St., San Francisco, CA 94103.] Sato M, Hida M, Nagase H. Analysis of pyrolysis products of methamphetamine. Journal Of Analytical Toxicology 2004;28(8):638. Sorokin VI, Orlova OS, Semenova LA, Simonov EA, Savchuk SA. Sample preparation and the detection of alpha-aminopropiophenone and amphetamine in nanarcotic drugs using IR spectroscopy. Journal of Analytical Chemistry 2004;59(11): 1050. Sun JH, Shen JL, Liang LS, Xu XY, Liu HB, Zhang CL. Experimental investigation on terahertz spectra of amphetamine type stimulants. Chinese Physics Letters 2005;22(12):3176. Teshima N, Fukui N, Sakai T. Reagents regeneration flow injection analysis (RRFIA) for spectrophotometric determination of methamphetamine coupled with solvent extraction. Talanta 2005;68(2):253. Tomaszewski W, Gun’ko VM, Leboda R, Skubiszewska-Zieba J. Interaction of amphetamine and its N-alkyl-substituted derivatives with micro- and mesoporous adsorbents in polar liquids. Journal of Colloid and Interface Science 2004;282(2):261. [Microgram Editor’s Notes: The title technique is used to concentrate amphetamines from “dilute aqueous solutions” (may be biological fluids-not clear in abstract). Contact: Internal Security Agency, Department of Criminalistics,, 1-go Sierpnia 30 A, Warsaw 02-134, Pol.] Verstraete AG, Heyden FV. Comparison of the sensitivity and specificity of six immunoassays for the detection of amphetamines in urine. Journal of Analytical Toxicology 2005;29(5):359. Villamor JL, Bermejo AM, Fernandez P, Tabernero MJ. GC-MS determination of amphetamines in human urine. Analytical Letters 2005;38(5):781. Wang S-M, Chye S-M, Liu RH, Lewis RJ, Canfield DV, Roberts J. Mass spectrometric data of commonly abused amphetamines and their derivatives - Cross contributions of ion intensity between the analytes and their isotopically labeled analogs. Forensic Science Reviews 2005;17(2):67.



Wang SM, Chye SM, Liu RH, Lewis RJ, Canfield DV. Mass spectrometric data characteristics of commonly abused amphetamines with sequential derivatization at two active sites. Forensic Sci Int, Sep 2006; 161(2-3): 97-118. Wang SM. Enantiomeric determination of amphetamines: Exploring a novel onestep solid-phase microextraction-based approach. Journal of Chromatography BAnalytical Technologies in the Biomedical and Life Sciences 2005;825(1):79. Wei F, Fan Y, Zhang M, Feng YQ. Poly(Methacrylic acid-ethylene glycol dimethacrylate) monolith in-tube solid-phase microextraction applied to simultaneous analysis of some amphetamine derivatives in urine by capillary zone electrophoresis. Electrophoresis 2005;26(16):3141. Wen T, Zhao X, Luo G, Wang Y, Wang J, Zhu J, Yu Z. Comparison of the performance of microemulsion electrokinetic chromatography and 1-butanol modified micellar electrokinetic chromatography on the separations of amphetamine and its ephedra alkaloid impurities. Fenxi Huaxue 2006;34(11):1529. [Microgram Editor’s Notes: Nine different compounds (not specified in the abstract) were analyzed within 10 minutes. This article is written in Chinese. Contact: Department of Chemistry, Tsinghua University, Beijing 100084, Peop. Rep. China.] Woodworth A, Saunders AN, Koenig JW, Moyer TP, Turk J, Dietzen DJ. Differentiation of amphetamine/methamphetamine and other crossimmunoreactive sympathomimetic amines in urine samples by serial dilution testing. Clinical Chemistry 2006;52(4):743. Wu TY, Fuh MR. Determination of amphetamine, methamphetamine, 3,4methylenedioxyamphetamine, 3,4-methylenedioxyethylamphetamine, and 3,4methylenedioxymethamphetamine in urine by online solid-phase extraction and ion-pairing liquid chromatography with detection by electrospray tandem mass spectrometry. Rapid Communications in Mass Spectrometry 2005;19(6):775. Wyman JF, Cody JT. Determination of I-methamphetamine: A case history. Journal of Analytical Toxicology 2005;29(7):759. Xie S, Aspromonte J, Balla A, Sershen H, Javitt DC, Cooper TB. Sensitive and simple gas chromatographic-mass spectrometric determination for amphetamine in microdialysate and ultrafiltrate samples. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2004;805(1):27. [Microgram Editor’s Notes: Uses NCI mode for detection of the pentafluorobenzoyl derivatives (biological focus). Contact: Inst Psychiat Res, Analyt Psychopharmacol Lab, 140 Old Orangeburg Rd, Orangeburg, NY 10962.] Yi C, Tao Y, Wang B, Chen X. Electrochemiluminescent determination of methamphetamine based on tris (2,2'-bipyridine)ruthenium(II) ion association in organically modified silicate films. Analytica Chimica Acta 2005;541(1-2):75. Zheng YF, Yamout KA, Berger DE, Hu MW, Liu H-T. Assays for amphetamine and methamphetamine using stereospecific reagents. (Patent) Chem. Abstr. 2005:300636. 162

Zhou JJ, Zeng ZR. Novel fiber coated with beta-cyclodextrin derivatives used for headspace solid-phase microextraction of ephedrine and methamphetamine in human urine. Analytica Chimica Acta 2006;556(2):400.

Para-Substituted Amphetamines: Barbiturates:

Abbaspour A, Mirzajani R. Simultaneous determination of phenytoin, barbital, and caffeine in pharmaceuticals by absorption (zero-order) UV spectra and first order derivative spectra-multivariate calibration methods. Journal of Pharmaceutical and Biomedical Analysis 2005;38(3):420. Ghanem A. True and false reversal of the elution order of barbiturates on a bonded cellulose-based chiral stationary phase. Journal of Chromatography A 2006;1132(12):329. [Microgram Editor’s Notes: Presents the title study on “a set of racemic Nalkylated barbiturates” (not specified in the abstract). Contact: King Faisal Specialist Hosp & Res Ctr, Dept Biol & Med Res, Biomed Chem Unit, MBC-03-95, POB 3354, Riyadh 11211, Saudi Arabia.] Grove AA, Rohwer ER, Laurens JB, Vorster BC. The analysis of illicit methaqualone containing preparations by gas chromatography-mass spectrometry for forensic purposes. Journal of Forensic Sciences 2006;51(2):376. Hori Y, Fujisawa M, Shimada K, Hirose Y, Yoshioka T. Method for screening and quantitative determination of serum levels of salicylic acid, acetaminophen, theophylline, phenobarbital, bromvalerylurea, pentobarbital, and amobarbital using liquid chromatography/electrospray mass spectrometry. Biological & Pharmaceutical Bulletin 2006;29(1):7. Iqbal R, Rizvi SAA, Akbay C, Shamsi SA. Chiral separations in microemulsion electrokinetic chromatography: Use of micelle polymers and microemulsion polymers. Journal of Chromatography A 2004;1043(2):291. [Microgram Editor’s Notes: Presents the title analysis on a series of barbiturates (drugs and matrices not specified in the abstract). Contact: Georgia State Univ, Ctr Biotechnol & Drug Design, Dept Chem, Atlanta, GA 30303.] Komiyama Y, Hori Y, Namera A, Kuroki Y. Barbiturates. Japanese Journal of Toxicology 2004;17(1):79. [Microgram Editor’s Notes: A minor review on two methods for analysis of barbiturates, focus is toxicological. This article is written in Japanese. Contact: Dep. Clin. Exam. Med., Kansai Med. Univ., Japan.] Ni YN, Wang YR, Kokot S. Differential pulse stripping voltammetric determination of paracetamol and phenobarbital in pharmaceuticals assisted by chemometrics. Analytical Letters 2004, 37(15):3219.




Cavazzini A, Dondi F, Marmai S, Minghini E, Massi A, Villani C, Rompietti R, Gasparrini F. Adsorption equilibria of benzodiazepines on a hybrid polymeric chiral stationary phase. Analytical Chemistry 2005;77(10):3113. Cabrera CG, de Waisbaum RG, Nudelman NS. Kinetic and mechanistic studies on the hydrolysis and photodegradation of diazepam and alprazolam. Journal of Physical Organic Chemistry 2005;18(2):156. DeOliveira MH, Queiroz MEC, Carvalho D, Silva SM, Lancas FM. Determination of diazepam in human plasma by solid-phase microextraction and capillary gas chromatography-mass spectrometry. Chromatographia 2005;62(3-4):215. El-Didamony AM. Indirect spectrophotometric determination of diltiazem hydrochloride in pure form and pharmaceutical formulations. Central European Journal of Chemistry 2005;3(3):520. Ghosh P, Reddy MM, Rao BS, Sarin RK. Determination of diazepam in cream biscuits by liquid chromatography. JAOAC International 2004;87(3):569. [Microgram Editor’s Notes: Presents the title analysis, for detection of criminal adulteration. Contact: Directorate of Forensic Science, Central Forensic Science Laboratory, Ministry of Home Affairs, Hyderabad 500 013, India.] Gunnar T, Ariniemi K, Lillsunde P. Determination of 14 benzodiazepines and hydroxy metabolites, zaleplon and zolpidem as tert-butyldimethylsilyl derivatives compared with other common silylating reagents in whole blood by gas chromatography-mass spectrometry. Journal of Chromatography B Analytical Technologies in the Biomedical and Life Sciences 2005;818(2):175. Hanysova L, Grafnetterova T, Dubovska M, Klimes J. Development of the analytical method for LC-MS detection of unknown degradation product of alprazolam. Chemical Papers-Chemicke Zvesti 2005;59(2):99. Hegstad S, Oiestad EL, Johansen U, Christophersen AS. Determination of benzodiazepines in human urine using solid-phase extraction and high-performance liquid chromatography-electrospray ionization tandern mass spectrometry. Journal of Analytical Toxicology 2006;30(1):31. Hou JG, Rizvi SAA, Zheng J, Shamsi SA. Application of polymeric surfactants in micellar electrokinetic chromatography-electrospray ionization mass spectrometry of benzodiazepines and benzoxazocine chiral drugs. Electrophoresis 2006;27(56):1263. Kapnissi CP, Warner IM. Separation of benzodiazepines using capillary electrochromatography. Journal of Chromatographic Science 2004;42(5):238. [Microgram Editor’s Notes: Abstract suggests a biological focus. Contact: Louisiana State Univ, Dept Chem, Baton Rouge, LA 70803.]


Khasanov U, Rasulev U, Usmanov D, Iskhakova S, Nabiev U. Application of surface ionization methods for highly sensitive and selective analysis of benzodiazepine derivatives. Journal of Pharmaceutical and Biomedical Analysis 2005;37(5 Sp. Iss. SI):1125. Klette KL, Wiegand RF, Horn CK, Stout PR, Magluilo J. Urine benzodiazepine screening using Roche Online(R) KIMS immunoassay with beta-glucuronidase hydrolysis and confirmation by gas chromatography-mass spectrometry. Journal of Analytical Toxicology 2005;29(3):193. Kratzsch C, Tenberken O, Peters FT, Weber AA, Kraemer T, Maurer HH. Screening, library-assisted identification and validated quantification of 23 benzodiazepines, flumazenil, zaleplone, zolpidem, and zopiclone in plasma by liquid chromatography/mass spectrometry with atmospheric pressure chemical ionization. Journal of Mass Spectrometry 2004;39(8):856. [Microgram Editor’s Notes: The focus is toxicological. Contact: Univ Saarland, Inst Expt & Clin Pharmacol & Toxicol, Dept Expt & Clin Toxicol, D-64421 Homburg, Germany.] Laloup M, Fernandez MDR, De Boeck G, Wood M, Maes V, Samyn N. Validation of a liquid chromatography-tandem mass spectrometry method for the simultaneous determination of 26 benzodiazepines and metabolites, zolpidem and zopiclone, in blood, urine, and hair. Journal Of Analytical Toxicology 2005;29(7):616. Lestari AD, Prasetyo AT, Palupi T, Umayah E, Yuwono M, Indrayanto G. HPLC determination of Piracetam in tablets, Validation of the method. Journal Of Liquid Chromatography, Related Technologies 2005;28(9):1407. Mali BD, Rathod DS, Garad MV. Thin-layer chromatographic determination of diazepam, phenobarbitone, and saccharin in toddy samples. Journal of Planar Chromatography - Modern TLC 2005;18(104):330. Mikami E, Goto T, Tsutomu OA, Oka H, Kanamori H. Simultaneous analysis of seven benzodiazepines in dietary supplements as adulterants using high performance liquid chromatography and its application to an identification system for diazepam. Journal Of Health Science 2005;51(3):278. Nevado JJB, Cabanillas CG, Llerena MJV, Robledo VR. Enantiomeric determination, validation and robustness studies of racemic citalopram in pharmaceutical formulations by capillary electrophoresis. Journal of Chromatography A 2005;1072(2):249. Prado MSA, Steppe M, Tavares MFM, KedorHackmann ERM, Santoro MIRM. Comparison of capillary electrophoresis and reversed-phase liquid chromatography methodologies for determination of diazepam in pharmaceutical tablets. Journal of Pharmaceutical and Biomedical Analysis 2005;37(2):273. Quaglia MG, Donati E, Fanali S, Bossu E, Montinaro A, Buiarelli F. Analysis of diltiazem and its related substances by HPLC and HPLC/MS. Journal of Pharmaceutical and Biomedical Analysis 2005;37(4):695. 165


Rao RN, Parimala P, Khalid S, Alvi SN. Detection of the adulteration of traditional alcoholic beverages by the separation and determination of alprazolam, chloral hydrate, and diazepam using reversed phase high performance liquid chromatography. Analytical Sciences 2004;20(2):383. [Microgram Editor’s Notes: Presents the title study, 200 seized samples were analyzed. Contact: HPLC Group, Division of Analytical Chemistry, Indian Institute of Chemical Technology, Hyderabad, 500 007 India.] Smink BE, Brandsma JE, Dijkhuizen A, Lusthof KJ, de Gier JJ, Egberts ACG, Uges DRA. Quantitative analysis of 33 benzodiazepines, metabolites and benzodiazepinelike substances in whole blood by liquid chromatography-(tandem) mass spectrometry. Journal Of Chromatography B-Analytical Technologies In The Biomedical And Life Sciences 2004;811(1):13. Svinarov DA, Kotzev C, Kassabova LV. Determination of alprazolam by liquid chromatography-tandem mass spectrometry. Clinica Chimica Acta 2005;355(Suppl. S):S421. Valavani P, AttaPolitou J, Panderi I. Development and validation of a liquid chromatographic/electrospray ionization mass spectrometric method for the quantitation of prazepam and its main metabolites in human plasma. Journal of Mass Spectrometry 2005;40(4):516. Villain M, Concheiro M, Cirimele V, Kintz P. Screening method for benzodiazepines and hypnotics in hair at pg/mg level by liquid chromatography-mass spectrometry/mass spectrometry. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2005;825(1):72. Zhu HL, Luo JW. A fast and sensitive liquid chromatographic-tandem mass spectrometric method for assay of lorazepam and application to pharmacokinetic analysis. Journal of Pharmaceutical and Biomedical Analysis 2005;39(1-2):268.

Dimethoxyphenethylamines: Chlordiazepoxide: Clenbuterol:

Chen Y, Wang W, Duan JP, Chen HQ, Chen GN. Separation and determination of clenbuterol, cimaterol and salbutamol by capillary electrophoresis with amperometric detection. Electroanalysis 2005;17(8):706. Melwanki MB, Hsu WH, Huang SD. Determination of clenbuterol in urine using headspace solid phase microextraction or liquid-liquid-liquid microextraction. Analytica Chimica Acta 2005;552(1-2):67.


Na N, Hu YP, Jin OY, Baeyens WRG, Delanghe JR, Taes YEC, Xie MX, Chen HY, Yang YP. On the use of dispersed nanoparticles modified with single layer betacyclodextrin as chiral selecor to enhance enantioseparation of clenbuterol with capillary electrophoresis. Talanta 2006;69(4):866. Stefan-van-Staden RI, Lai B. Enantioselective, potentiometric carbon paste electrodes based on C-60 derivatives as chiral selectors for the enantioanalysis of S-clenbuterol. Analytical Letters 2006;39(7):1311. [Microgram Editor’s Notes: Presents the title study, using three different electrodes, for analysis of both raw material and serum samples. Contact: Univ Pretoria, Dept Chem, ZA-0002 Pretoria, South Africa.] Thevis M, Schebalkin T, Thomas A, Schanzer W. Quantification of clenbuterol in human plasma and urine by liquid chromatography-tandem mass spectrometry. Chromatographia 2005;62(7-8):435. Xu CL, Peng CF, Hao K, Jin ZG, Wang WK. Determination of clenbuterol residual by chemiluminescent enzyme immunoassay. Chinese Journal of Analytical Chemistry 2005;33(5):699. Yuen AHY, Yacoub MH, Smolenski RT. Determination of clenbuterol concentration in human blood using liquid chromatography with electrospray/ion-trap tandem mass spectrometry. Rapid Communications in Mass Spectrometry 2005;19(23):3603.


Baker BR, Lai RY, Wood MS, Doctor EH, Heeger AJ, Plaxco KW. An electronic, aptamer-based small-molecule sensor for the rapid, label-free detection of cocaine in adulterated samples and biological fluids. J Am Chem Soc, Mar 2006; 128(10): 31389. Bermejo AM, Lopez P, Alvarez I, Tabernero MJ, Fernandez P. Solid-phase microextraction for the determination of cocaine and cocaethylene inhuman hair by gas chromatography-mass spectrometry. Forensic Science International 2006;156(1):2. Bieri S, Brachet A, Veuthey JL, Christen P. Cocaine distribution in wild Erythroxylum species. J Ethnopharmacol, Feb 2006; 103(3): 439-47. Bieri S, Ilias Y, Bicchi C, Veuthey JL, Christen P. Focused microwave-assisted extraction combined with solid-phase microextraction and gas chromatographymass spectrometry for the selective analysis of cocaine from coca leaves. Journal of Chromatography A 2006;1112(1-2):127. Block R. Cocaine base to soup. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(3):21. [Microgram Editor’s Notes: Reports on the reanalysis of partially decomposed samples of cocaine base that had been stored in metal paint cans for 6 years. JCLICA is a law enforcement restricted journal. Contact: Wisconsin State Crime Laboratory, 4626 University Ave., Madison, WI 53705-2156.]



Cardona PS, Chaturvedi AK, Soper JW, Canfield DV. Simultaneous analyses of cocaine, cocaethylene, and their possible metabolic and pyrolytic products. Forensic Science International 2006;157(1):46. Casale JF, Toske SG, Colley VL. Alkaloid content of the seeds from Erythroxylum Coca var. Coca. Journal of Forensic Sciences 2005;50(6):1402. Cognard E, Bouchonnet S, Staub C. Validation of a gas chromatography - Ion trap tandem mass spectrometry for simultaneous analyse of cocaine and its metabolites in saliva. Journal of Pharmaceutical and Biomedical Analysis 2006;41(3):925. Cognard E, Rudaz S, Bouchonnet S, Staub C. Analysis of cocaine and three of its metabolites in hair by gas chromatography-mass spectrometry using ion-trap detection for CI/MS/MS. Journal of Chromatography B - Analytical Technologies in the Biomedical and Life Sciences 2005;826(1-2):17. Dixon SJ, Brereton RG, Carter JF, Sleeman R. Determination of cocaine contamination on banknotes using tandem mass spectrometry and pattern recognition. Analytica Chimica Acta 2006;559(1):54. Fang H, Zeng Z, Liu L, Pang D. On-line back-extraction field-amplified sample injection method for directly analyzing cocaine and thebaine in the extractants by solvent microextraction. Anal Chem, Feb 2006; 78(4): 1257-63. T Gostic T, Klemenc S. Evidence on unusual way of cocaine smuggling: cocainepolymethyl methacrylate (PMMA) solid solution--study of clandestine laboratory samples. Forensic Sci Int, Jul 2007; 169(2-3): 210-9. Huaifang ZZ, Liu L, Pang D. On-Line Back-Extraction Field-Amplified Sample Injection Method for Directly Analyzing Cocaine and Thebaine in the Extractions by Solvent Microextraction. Analytical Chemistry 2006;78(4):1257. Isenschmid DS. Cocaine. Principles of Forensic Toxicology (2nd Edition) 2003:207. Kirby DA. Preparation and analysis of cocaine hydrochloride in a silicone matrix. Journal of the Clandestine Laboratory Investigating Chemists Association 2004;14(4):14. [Microgram Editor’s Notes: Presents the analysis of cocaine that is mixed in silicone and formed into consumer products for smuggling. Includes pertinent commentary from a cooperating individual. Note that JCLICA is a law enforcement restricted journal. Contact: DEA Southwest Laboratory, 2815 Scott Street, Vista, CA 92081.] Littleford RE, Matousek P, Towrie M, Parker AW, Dent G, Lacey RJ, Smith WE. Raman spectroscopy of street samples of cocaine obtained using Kerr gated fluorescence rejection. Analyst 2004;129(6):505. [Microgram Editor’s Notes: Presents the title study. Contact: Univ Strathclyde, Dept Pure & Appl Chem, 295 Cathedral St., Glasgow G1 1XL, Lanark, Scotland.]


Liu JW, Lu Y. Fast colorimetric sensing of adenosine and cocaine based on a general sensor design involving aptamers and nanoparticles. Angewandte ChemieInternational Edition 2006;45(1):90. Paul BD, Lalani S, Bosy T, Jacobs AJ, Huestis MA. Concentration profiles of cocaine, pyrolytic methyl ecgonidine and thirteen metabolites in human blood and urine: determination by gas chromatography-mass spectrometry. Biomedical Chromatography 2005;19(9):677. Ragoucy-Sengler C, Kintz P. Detection of smoked cocaine marker (Anhydroecgonine methylester) in nails. Journal of Analytical Toxicology 2005;29(7):765. Staples EJ, Viswanathan S. Detection of cocaine in a cargo container using a fast SAW/GC vapor analyzer. (Proceedings) Chemical Abstracts 2006:462179q. Staples, Edward J. Viswanathan, Shekar. Detection of contraband and drugs of abuse using an ultrafast SAW/GC vapor analyzer. AIChE Annual Meeting, Conference Proceedings, Cincinnati, OH, United States, Oct. 30-Nov. 4, 2005. [Microgram Editor’s Notes: Presents the title technique. Contact: Electronic Sensor Technology, Newbury Park, CA 91320.] Zuccato E, Chiabrando C, Castiglioni S, Calamari D, Bagnati R, Schiarea S, Fanelli R. Cocaine in surface waters: A new evidence-based tool to monitor community drug abuse. Environmental Health 2005;4(14):(No Page Numbers).

Ergot Alkaloids (see also LSD):

Aranda M, Morlock G. Simultaneous Determination of Caffeine, Ergotamine, and Metamizol in Solid Pharmaceutical Formulation by HPTLC-UV-FLD with Mass Confirmation by Online HPTLC-ESI-MS. J Chromatogr Sci, May 2007; 45(5): 251-5. Burk G, Hobel W, Richt A. Ergot alkaloids in cereal products: results from the Bavarian Health and Food Safety Authority. Mol Nutr Food Res, Apr 2006; 50(4-5): 437-42. Lehner AF, Craig M, Fannin N, Bush L, Tobin T. Fragmentation patterns of selected ergot alkaloids by electrospray ionization tandem quadrupole mass spectrometry. Journal of Mass Spectrometry 2004;39(11):1275. [Microgram Editor’s Notes: Compounds included ergovaline, ergotamine, ergocornine, ergocryptine, ergocrystine, ergonovine, lysergic acid, and lysergol. Contact: Univ Kentucky, Dept Vet Sci, Maxwell H Gluck Equine Res Ctr, Lexington, KY 40546.] Lehner AF, Craig M, Fannin N, Bush L, Tobin T. Electrospray [+] tandem quadrupole mass spectrometry in the elucidation of ergot alkaloids chromatographed by HPLC: Screening of grass or forage samples for novel toxic compounds. Journal of Mass Spectrometry 2005;40(11):1484.



Marti EP, Icardo MC, Zamora LL, Fos GMA, Calatayud JM. Theoretical prediction of the chemiluminescence behaviour of the ergot alkaloids - Direct flow injection chemiluminescence determination of ergotamine tartrate. Analytica Chimica Acta 2004;527(2):177. Mohamed R, Gremaud E, Richoz-Payot J, Tabet JC, Guy PA. Quantitative determination of five ergot alkaloids in rye flour by liquid chromatography electrospray ionisation tandem mass spectrometry. Journal of Chromatography A 2006;1114(1):62. [Microgram Editor’s Notes: The target alkaloids were ergocristine, ergotamine, ergonovine, ergocornine, and ergokryptine; 15 samples of rye flour were analyzed. Contact: Nestec Ltd, Nestle Res Ctr, Dept Qual & Safety Assurance, Vers Chez Les Blanc, POB 44, CH-1000 Lausanne 26, Switzerland.] Mohamed R, Gremaud E, Tabet J-C, Guy PA. Mass spectral characterization of ergot alkaloids by electrospray ionization, hydrogen/deuterium exchange, and multiple stage mass spectrometry: Usefulness of precursor ion scan experiments. Rapid Communications in Mass Spectrometry 2006;20:2787-99. [Microgram Editor’s Notes: Presents the title study; compounds include: Ergonovine, methysergide hydrogen maleinate, ergocristine, ergotamine, ergocornine, and alpha-ergokryptine. Contact: Department of Quality and Safety Assurance, Nestle Research Center, Nestec Ltd., P.O. Box 44, Vers-chez-les-Blanc, 1000 Lausanne 26, Switzerland. See also: Mohamed R, Gremaud E, Richoz-Payot J, Tabet JC, Guy PA. Quantitative determination of five ergot alkaloids in rye flour by liquid chromatography-electrospray ionisation tandem mass spectrometry. Journal of Chromatography A 2006;1114(1):62. ] Moldvai I, TemesvariMajor E, Ineze M, Domyei G, Szentirmay E, Szantay C. Synthetic route to ergot alkaloids. Helvetica Chimica Acta 2005;88(6):1344. Schiff PL. Ergot and its alkaloids. American Journal of Pharmaceutical Education 2006;70(5):1. [Microgram Editor’s Notes: A historical overview and review. Contact: Department of Pharmaceutical Sciences, School of Pharmacy, University of Pittsburgh, Pittsburgh, PA 15261.] Uhlig S, Vikoren T, Ivanova L, Handeland K. Ergot alkaloids in Norwegian wild grasses: a mass spectrometric approach. Rapid Commun Mass Spectrom, Jan 2007; 21(10): 1651-60.


Boddiger D. Fentanyl-laced street drugs "kill hundreds". Lancet, Aug 2006; 368(9535): 569-70. Drug Enforcement Administration (DEA), U.S. Department of Justice. Control of a chemical precursor used in the illicit manufacture of fentanyl as a List I chemical. Interim rule with request for comments. Fed Regist, Apr 2007; 72(77): 20039-47.


Gupta PK, Manral L, Ganesan K, Dubey DK. Use of single-drop microextraction for determination of fentanyl in water samples. Anal Bioanal Chem, Jun 2007; 388(3): 579-83. Huynh NH, Tyrefors N, Ekman L, Johansson M. Determination of fentanyl in human plasma and fentanyl and norfentanyl in human urine using LC-MS/MS. Journal of Pharmaceutical and Biomedical Analysis 2005;37(5, Sp. Iss. SI):1095. Maroge W, Bordelon JA, Katz JM, Zhivago VR. Large fentanyl and MDA laboratory in Los Angeles, California. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(2):12. [Microgram Editor’s Notes: A brief overview of the subject laboratory. Note that JCLICA is a law enforcement restricted journal. Contact: DEA Southwest Laboratory, 2815 Scott St., Vista, CA 92081.] Martin TL, Woodall KL, McLellan BA. Fentanyl-related deaths in Ontario, Canada: toxicological findings and circumstances of death in 112 cases (2002-2004). J Anal Toxicol, Oct 2006; 30(8): 603-10. Pihlainen K, Grigoras K, Franssila S, Ketola R, Kotiaho T, Kostiainen R. Analysis of amphetamines and fentanyls by atmospheric pressure desorption/ionization on silicon mass spectrometry and matrix-assisted laser desorption/ionization mass spectrometry and its application to forensic analysis of drug seizures. Journal of Mass Spectrometry 2005;40(4):539. Skulska A, Kala M, Parczewski A. Fentanyl and its analogues in the forensic laboratory. Medical and analytical problems. Z Zagadnien Nauk Sadowych 2004;59:127. Van Nimmen NF, Veulemans HA. Validated GC-MS analysis for the determination of residual fentanyl in applied Durogesic reservoir and Durogesic D-Trans matrix transdermal fentanyl patches. J Chromatogr B Analyt Technol Biomed Life Sci, Feb 2007; 846(1-2): 264-72.

Flos Daturae:

Gao Y, Tian YL, Wang EK. Simultaneous determination of two active ingredients in Flos daturae by capillary electrophoresis with electrochemiluminescence detection. Analytica Chimica Acta 2005;545(2):137. Hou SG, Gu XX, Wang SY, Li HX. [Determination of scopolamine and atropine in Flos Daturae by RP-HPLC]. Zhongguo Zhong Yao Za Zhi, Jul 2006; 31(13): 1065-7. Mroczek T, Glowniak K, Kowalska J. Solid-liquid extraction and cation-exchange solid-phase extraction using a mixed-mode polymeric sorbent of Datura and related alkaloids. Journal of Chromatography A 2006;1107(1-2):9.

Fluoxetine (Prozac):

Afkhami A, Madrakian T, Khalafi L. Spectrophotometric determination of fluoxetine by batch and flow injection methods. Chem Pharm Bull (Tokyo), Dec 2006; 54(12): 1642-6.



Kovacevic I, Miljkovic B, Jovanovic D, Prostran M. Comparison of liquid chromatography with fluorescence detection to liquid chromatography-mass spectrometry for the determination of fluoxetine and norfluoxetine in human plasma. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2006;830(2):372. Yu L, Mei-Li F, Jie-Guo X. Enantiomeric separation of fluoxetine derivatives on polysaccharide-based chiral columns. Arch Pharm (Weinheim), Aug 2006; 339(8): 461-5. Zhou J, Ren QL, Wu PD. Chromatographic separation of fluoxetine hydrochloride enantiomers by cellulose chiral stationary phase. Journal of Liquid Chromatography & Related Technologies 2005;28(20):3229.


Agg KM, Craddock AF, Bos R, Francis PS, Lewis SW, Barnett NW. A rapid test for heroin (3,6-diacetylmorphine) based on two chemiluminescence reactions. J Forensic Sci, Sep 2006; 51(5): 1080-4. Anastos N, Lewis SW, Barnett NW, Pearson JR, Kirkbride KP. The rapid analysis of heroin drug seizures using micellar electrokinetic chromatography with short-end injection. Journal of Forensic Sciences 2005;50(1):37. [Microgram Editor’s Notes: Presents the title study. Good separation of heroin and various adulterants and diluents was obtained. Contact: School of Biological and Chemical Sciences, Deakin University, Geelong, Victoria 3217, Australia.] Balchin E, Malcolme-Lawes DJ, Rowe MD, Smith JAS, Bearpark MJ, Steed JW, Wu W, Horsewill AJ, Stephenson D. The unusual solid state structure of heroin hydrochloride monohydrate and its selective detection using NQR spectroscopy. New Journal of Chemistry 2004;28(11):1309. [Microgram Editor’s Notes: The title technique was successfully demonstrated with standards and illicit samples. Contact: King’s College London, The Strand, London, UK WC2R 2LS.] Beckerleg S, Telfer M, Sadiq A. A rapid assessment of heroin use in Mombasa, Kenya. Substance Use & Misuse 2006;41:1029. [Microgram Editor’s Notes: Presents the title survey, done in March, 2004. 496 Heroin users were interviewed. Contact: London School of Hygiene & Tropical Medicine, London, UK.] Garrido JMPJ, Delerue-Matos C, Borges F, Macedo TRA, Oliveira-Brett AM. Voltammetric oxidation of drugs of abuse III. Heroin and metabolites. Electroanalysis 2004;16(18):1497. Klous MG, Bronner GA, Nuijen B, van Ree JA, Beijnen JH. Pharmaceutical heroin for inhalation: Thermal analysis and recovery experiments after volatilisation. Journal of Pharmaceutical and Biomedical Analysis 2005;39(5):944.


Klous MG, Lee WC, Hillebrand MJX, van den Brink W, van Ree JM, Beijnen JH. Analysis of diacetylmorphine, caffeine, and degradation products after volatilization of pharmaceutical heroin for inhalation. Journal of Analytical Toxicology 2006;30(1):6. Macchia M, Bertini S, Mori C, Orlando C, Papi C, Placanica G. Efficient application of monolithic silica column to determination of illicit heroin street sample by HPLC. Farmaco 2004;59(3):237. [Microgram Editor’s Notes: Presents the title analysis (complete in 7 minutes). Contact: Department of Pharmaceutical Sciences, University of Pisa, 56126 Pisa, Italy.] Ren J, Gao J-z, Suo N, Zhao G-h, Yang W, Lue D-y, Sun K-j, Li C-y. Determination of heroin based on analyte pulse perturbation to an oscillating chemical reaction. Chemical Research in Chinese Universities 2004;20(5):534. [Microgram Editor’s Notes: For trace level detection of heroin. The application(s) for the technique were not reported in the abstract. Contact: Institute of Chemistry, Northwest Normal University, Lanzhou, Peop. Rep. China 730070.] Sun Y-F, Wang L-C, Huang X-J, Wu Z-C, Liu J-H. Fast detection of heroin by chemiluminescence with luminol – H2O2. Guangpu Shiyanshi 2004;21(4):663. Zhuang YF, Zhang DM, Ju HX. Sensitive determination of heroin based on electrogenerated chemiluminescence of tris(2():2'-bipyridyl)ruthenium(II) immobilized in zeolite Y modified carbon paste electrode. Analyst 2005;130(4):534.

gamma-Hydroxybutyric Acid (GHB), gamma-butyrolactone (GBL) and 1,4-butanediol (BD):

Bell SC, Oldfield LS, Shakleya DM, Petersen JL, Mercer JW. Chemical composition and structure of the microcrystals formed between silver(I) and gammahydroxybutyric acid and gamma-hydroxyvaleric acid. J Forensic Sci, Jul 2006; 51(4): 808-11. Bishop SC, Lerch M, McCord BR. Micellar electrokinetic chromatographic screening method for common sexual assault drugs administered in beverages. Forensic Science International 2004;141 (1):7. [Microgram Editor’s Notes: The title analysis was applied for detection of GHB, GBL, and eight benzodiazepines (unspecified in abstract) in spiked beverages. Contact: 136 Clippinger Laboratories, Department of Chemistry and Biochemistry, Ohio University, Athens, OH 45701.] DeFrancesco JV, Witkowski MR, Ciolino LA. GHB free acid: I. Solution formation studies and spectroscopic characterization by 1HNMR and FT-IR. J Forensic Sci, Mar 2006; 51(2): 321-9. [Microgram Editor’s Notes: Presents the title study. The technique is especially suited for analysis of forensic samples containing the free acid, its corresponding salt, and GBL. Contact: U.S. Drug Enforcement Administration, North Central Laboratory, Chicago, IL 60606.] Del Signore AG, McGregor M, Cho BP. 1H NMR analysis of GHB and GBL: Further findings on the interconversion and a preliminary report on the analysis of GHB in



serum and urine. Journal of Forensic Sciences 2005;50(1):81. [Microgram Editor’s Notes: Presents the title study. Spiked samples are included. Focus is toxicological, but the results are pertinent for spiked beverages. Contact: Department of Biomedical and Pharmaceutical Sciences, College of Pharmacy, University of Rhode Island, Kingston, RI 02881.] Elliott S, Burgess V. The presence of gamma-hydroxybutyric acid (GHB) and gamma-butyrolactone (GBL) in alcoholic and non-alcoholic beverages. Forensic Science International 2005;151(2-3):289. Gottardo R, Bortolotti F, Trettene M, DePaoli G, Tagliaro F. Rapid and direct analysis of gamma-hydroxybutyric acid in urine by capillary electrophoresiselectrospray ionization ion-trap mass spectrometry. Journal of Chromatography A 2004;1051(1-2):207. Grootveld M, Algeo D, Silwood CJL, Blackburn JC, Clark AD. Determination of the illicit drug gamma-hydroxybutyrate (GHB) in human saliva and beverages by 1HNMR analysis. BioFactors 2006;27(1-4):121. [Microgram Editor’s Notes: Presents the title study. Contact: Department of Applied Science, London South Bank University, London, UK SE1 0AA.] Grossman SI, Campbell JG, Loane CJ. Apparatus for detection of drugs in a beverage. (Patent (for detection of GHB and ketamine)) Chem. Abstr. 2005:998813. Hennessy SA, Moane SM, McDermott SD. The reactivity of gamma-hydroxybutyric acid (GHB) and gamma-butyrolactone (GBL) in alcoholic solutions. Journal of Forensic Sciences2004;49(6):1220. [Microgram Editor’s Notes: Presents a study of the formation of esters of GHB, with an emphasis on the formation of the ethyl ester in alcoholic beverages. Contact: Forensic Science Laboratory, Garda H.Q., Phoenix Park, Dublin 8, Ireland.] Marinetti LJ, Isenschmid DS, Hepler BR, Kanluen S. Analysis of GHB and 4-methylGHB in postmortem matrices after long-term storage. Journal of Analytical Toxicology 2005;29(1):41. Matsuda K, Asakawa N, Iwanaga M, Gohda A, Fukushima S, Ishii Y, Yamada H. Conversion of gamma-hydroxybutyric acid to a fluorescent derivative: A method for screening. Forensic Toxicology 2006;24(1):41. [Microgram Editor’s Notes: GHB is converted to a fluorescent derivative using 3-bromomethyl-6,7-dimethoxy-1-methyl1,2-dihydroquinoxaline-2-one. The focus is toxicological, but analysis of powdered and tableted forms of GHB is specifically mentioned in the abstract. Contact: Graduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan.] Mercer JW, Oldfield LS, Hoffman KN, Shakleya DM, Bell SC. Comparative analysis of gamma-hydroxybutyrate and gamma-hydroxyvalerate using GC/MS and HPLC. Journal of Forensic Sciences 2007;52(2):383. [Microgram Editor’s Notes: GHB and GHV were derivatized with BSTFA with trimethylchlorosilane prior to GC/MS analyses. UV/Vis detection at 254 nm was used for the HPLC analyses. Contact: C. 174

Eugene Bennett Department of Chemistry, West Virginia University, 217 Clark Hall, Morgantown, WV 26056.] Mercer J, Shakleya D, Bell S. Applications of ion mobility spectrometry (IMS) to the analysis of gamma-hydroxybutyrate and gamma-hydroxyvalerate in toxicological matrices. J Anal Toxicol, Oct 2006; 30(8): 539-44. Meyers JE, Almirall JR. Analysis of gamma-hydroxybutyric acid (GHB) in spiked water and beverage samples using solid phase microextraction (SPME) on fiber derivatization/gas chromatography-mass spectrometry (GC/MS). Journal of Forensic Sciences 2005;50(1):31. [Microgram Editor’s Notes: Presents the title study. Contact: International Forensic Research Institute, Department of Chemistry, Florida International University, Miami, FL 33199.] Morris-Kukowski CL. gamma-Hydroxybutyrate: Bridging the clinical-analytical gap. Toxicological Review 2004;23(1):33. PerezPrior MT, Manso JA, GarciaSantos MD, Calle E, Casado J. Reactivity of lactones and GHB formation. Journal of Organic Chemistry 2005;70(2):420. Petek MJ, Vrdoljak AL. [Qualitative and quantitative gamma-hydroxybutyrate analysis]. Arh Hig Rada Toksikol, Dec 2006; 57(4): 397-404. Richard D, Ling B, Authier N, Faict TW, Eschalier A, Coudore F. GC/MS profiling of gamma-hydroxybutyrate and precursors in various animal tissues using automatic solid-phase extraction. Preliminary investigations of its potential interest in postmortem interval determination. Analytical Chemistry 2005;77(5):1354. Sabucedo AJ, Furton KG. Extractionless GC/MS analysis of gamma hydroxybutyrate and gamma butyrolactone with trifluoroacetic anhydride and heptafluoro-1-butanol from aqueous samples. Journal of Separation Science 2004;27(9):703. [Microgram Editor’s Notes: Presents a novel technique for the derivatization and analysis of the title compounds directly from dilute aqueous solutions (i.e., beverages). Contact: Department of Chemistry and Biochemistry, Advanced Mass Spectrometry Facility and International Forensic Research Institute, Florida International University, Miami, FL 33199.] Saudan C, Augsburger M, Kintz P, Saugy M, Mangin P. Detection of exogenous GHB in blood by gas chromatography-combustion-isotope ratio mass spectrometry: Implications in postmortem toxicology. Journal of Analytical Toxicology 2005;29(8):777. Vanhee P, Neels H, DeDoncker M, Vrydags N, Schatteman K, Uyttenbroeck K, Hamers N, Himpe D, Lambert W. Analysis of gamma-hydroxybutyric acid, DLlactic acid, glycolic acid, ethylene glycol and other glycols in body fluids by a direct injection gas chromatography-mass spectrometry assay for wide. Clinical Chemistry and Laboratory Medicine 2004;42(11):1341.



Witkowski MR, Ciolino LA, Defrancesco JV. GHB free acid: II. Isolation and spectroscopic characterization for forensic analysis. J Forensic Sci, Mar 2006; 51(2): 330-9. Zhang SY, Huang ZP. [A color test for rapid screening of gamma-hydroxybutyric acid (GHB) and gamma-butyrolactone (GBL) in drink and urine]. Fa Yi Xue Za Zhi, Dec 2006; 22(6): 424-7.


Adamowicz P, Zuba D, Kala M. Ketamine: A new substance on the Polish drug market. Z Zagadnien Nauk Sadowych 2004;56:26. [Microgram Editor’s Notes: Presents a case analyzed by the laboratory, along with some background concerning the title subject. Contact: Institute of Forensic Research, Krakow, Pol.] da Silva IJ, dos Santos MAG, de Veredas V, Santana CC. Experimental determination of chromatographic separation parameters of ketamine enantiomers on MCTA. Separation And Purification Technology 2005;43(2):103. Huang MK, Liu C, Li JH, Huang SD. Quantitative detection of ketamine, norketamine, and dehydronorketamine in urine using chemical derivatization followed by gas chromatography-mass spectrometry. Journal of Chromatography BAnalytical Technologies in the Biomedical and Life Sciences 2005;820(2):165. Jen HP, Tsai YC, Su HL, Hsieh YZ. On-line preconcentration and determination of ketamine and norketamine by micellar electrokinetic chromatography Complementary method to gas chromatography/mass spectrometry. Journal of Chromatography A 2006;1111(2):159. Jia J, Wang Y, Chen Z, Zhao Y, An J. Determination of ketamine by TLCS. Shanxi Yike Daxue Xuebao 2005;36(1):69. Lin HR, Lua AC. Simultaneous determination of amphetamines and ketamines in urine by gas chromatography/mass spectrometry.Rapid Communications in Mass Spectrometry 2006;20(11):1724. Lua AC, Lin HR. A rapid and sensitive ESI-MS screening procedure for ketamine and norketamine in urine samples. Journal of Analytical Toxicology 2004;28(8):680. Miksa IR, Cummings MR, Poppenga RH. Determination of acepromazine, ketamine medetomidine, and xylazine in serum: Multi-residue screening by liquid chromatography-mass spectrometry. Journal of Analytical Toxicology 2005;29(6):544. Morris JA. Modified cobalt thiocyanate presumptive color test for ketamine hydrochloride. J Forensic Sci, Jan 2007; 52(1): 84-7. Tanaka E, Honda K, Yasuhara H. Ketamine: Its pharmacology and toxicology. Japanese Journal of Forensic Toxicology 2005;23(3):187.


Theurillat R, Knobloch M, Levionnois O, Larenza P, Mevissen M, Thormann W. Characterization of the stereoselective biotransformation of ketamine to norketamine via determination of their enantiomers in equine plasma by capillary electrophoresis. Electrophoresis 2005;26(20):3942. Wang Y, Liu L, Jia J, Liao L, Wang Y. Determination of ketamine by use of TLC and GC-MS. Zhongguo Yiyuan Yaoxue Zazhi 2005;25(6):497. [Microgram Editor’s Notes: Included analysis of morphine and heroin. Focus appears to be toxicological (not clear in abstract). This article is written in Chinese. Contact: School of Forensic Medicine, Shanxi Medical University, Taiyuan, Shanxi Province 030001, Peop. Rep. China.]


Al-Hebshi NN, Skaug N. Khat (Catha edulis) - An updated review. Addiction Biology 2005;10:299.


Johansen SS, Jensen JL. Liquid chromatography-tandem mass spectrometry determination of LSD, ISO-LSD, and the main metabolite 2-oxo-3-hydroxy-LSD in forensic samples and application in a forensic case. Journal of Chromatography BAnalytical Technologies in the Biomedical and Life Sciences 2005;825(1):21. Pietsch J, Schulz K, Korner B, Trauer H, Dressler J, Gey M. Alternative method for forensic determination of lysergic acid diethylamide and related compounds in body fluids by liquid-liquid extraction and HPLC with fluorescence detection. Chromatographia 2004;60(1-2):89. Suzuki S. Lysergic acid diethylamide (LSD). Drugs and Poisons in Humans 2005:225. (Edited by Suzuki and Watanabe; Springer GmbH; Berlin.). Zheng C-s, Zheng H, Liu K-l, He Y, Hou Z-p. Analysis of lysergide tablets by gas chromatography - mass spectrometry. Zhipu Xuebao 2004;25(Suppl.):161.

Marijuana and Related Cannabinoids:

Below E, Rosenstock S, Lignitz E. Hemp products in the German food market place. THC content and forensic meaning. Blutalkohol 2005;42(6):442. Caligiani A, Palla G, Bernardelli B. GC-MS analysis of hashish samples: A case of adulteration with colophony. Journal of Forensic Sciences 2006;51(5):1096. [Microgram Editor’s Notes: Presents the title study on a sample seized in Italy (colophony is the acidic flux used for soldering). Contact: Dipartimento di Chimica Organica e Industriale, Universita degli Studi di Parma, Parco Area delle Scienze 17A, 43100-Parma, Italy.] Carpentier C, Griffiths P, King LA. An overview of cannabis potency in Europe. Report EMCDDA Insights 2004:1. [Microgram Editor’s Notes: Presents the title study, and discusses the results versus the comparable data for the United States



and Australia/New Zealand. Contact: 27 Ivar Gardens, Basingstoke, Hampshire, RG24 8YD, UK.] Choi YH, Hazekamp A, Peltenburg-Looman AMG, Frederich M, Erkelens C, Lefeber AWM, Verpoorte R. NMR assignments of the major Cannabinoids and cannabiflavonoids isolated from flowers of Cannabis sativa. Phytochemical Analysis 2004;15(6):345. Concheiro M, deCastro A, Quintela O, Cruz A, LopezRivadulla M. Development and validation of a method for the quantitation of Delta(9)-tetrahydrocannabinol in oral fluid by liquid chromatography electrospray-mass-spectrometry. Journal of Chromatography B - Analytical Technologies in the Biomedical and Life Sciences 2004;810(2):319. Dussy FE, Hamberg C, Luginbuhl M, Schwerzmann T, Briellmann TA. Isolation of Delta(9)-THCA-A from hemp and analytical aspects concerning the determination of Delta(9)-THC in cannabis products. Forensic Science International 2005;149(1):3. ElSohly MA, Slade D. Chemical constituents of marijuana: The complex mixture of natural cannabinoids. Life Sciences 2005;78:539. Hanson AJ. Specificity of the Duquenois-Levine and cobalt thiocyanate tests substituting methylene chloride or butyl chloride for chloroform. Microgram Journal 2005;3(3-4):183. [Microgram Editor’s Notes: Performs the named tests using methylene chloride or butyl chloride as substitutes for chloroform. Contact: Wisconsin State Crime Laboratory Madison, 4626 University Avenue, Madison, WI 53705.] Hazekamp A, Choi YH, Verpoorte R. Quantitative analysis of cannabinoids from Cannabis sativa using H1 NMR. Chemical and Pharmaceutical Bulletin 2004;52(6):718. [Microgram Editor’s Notes: Allows analysis of pure cannabinoids or cannabinoid mixtures from plant material in less than 5 minutes, without prepurification. Contact: Leiden Univ, Div Pharmacognosy, Inst Biol, Einsteinweg 55, NL 2300 RA Leiden, Netherlands.] Hazekamp A, Simons R, Peltenburg-Looman A, Sengers M, van Zweden R, Verpoorte R. Preparative isolation of cannabinoids from Cannabis sativa by centrifugal partition chromatography. Journal of Liquid Chromatography & Related Technologies 2004;27(15):2421. [Microgram Editor’s Notes: Seven major cannabinoids were isolated in large scale and better than 90 percent purity. Contact: Leiden Univ, Inst Biol, Div Pharmacognosy, Einsteinweg 55, NL-2300 RA Leiden, Netherlands.] Hazekamp A, Peltenburg A, Verpoorte R, Giroud C. Chromatographic and spectroscopic data of cannabinoids from Cannabis sativa L. Journal of Liquid Chromatography & Related Technologies 2005;28(15):2361.


Hewavitharana AK, Golding G, Tempany G, King G, Holling N. Quantitative GGMS analysis of Delta(9)-tetrahydrocannabinol in fiber hemp varieties. Journal of Analytical Toxicology 2005;29(4):258. Honorio KM, daSilva ABF. A study on the influence of molecular properties in the psychoactivity of cannabinoid compounds. Journal of Molecular Modeling 2005;11(3):200. Huestis MA. Marijuana. Principles of Forensic Toxicology (2nd Edition) 2003:229. Huq S, Dixon A, Kelly K, Kallury KMR. Novel solid-phase extraction protocol for 11-nor-9-carboxy-Delta(9)-tetrahydrocannabinol from urine samples employing a polymeric mixed-mode cation-exchange resin, Strata-X-C, suitable for gas chromatography-mass spectrometry or liquid chromatography-mass spectrometry analysis. Journal of Chromatography A 2005;1073(1-2):355. Ilias Y, Rudaz S, Mathieu P, Christen P, Veuthey JL. Extraction and analysis of different Cannabis samples by headspace solid-phase microextraction combined with gas chromatography-mass spectrometry. Journal of Separation Science 2005;28(17):2293. Jamerson MH, Welton RM, MorrisKokski CL, Klette KL. Rapid quantification of urinary 11-nor-Delta(9)-tetrahydrocannabinol-9-carboxylic acid using fast gas chromatography-mass spectrometry. Journal of Analytical Toxicology 2005;29(7):664. Jehanli AMT, Hand CW. Delta-9-tetrahydrocannabinol detection method. (Patent) Chemical Abstracts 2005:45419. Kim JY, Suh SI, In MK, Paeng KJ, Chung BC. Simultaneous determination of cannabidiol, cannabinol, and Delta(9)-tetrahydrocannabinol in human hair by gas chromatography-mass spectrometry. Archives of Pharmacal Research 2005;28(9):1086. Lachenmeier DW. Analysis and toxicological evaluation of cannabinoids in hemp food products - A review. Electronic Journal of Environmental, Agricultural and Food Chemistry 2005;4(1):812. Laloup M, Fernandez MDR, Wood M, DeBoeck G, Henquet U, Maes V, Samyn N. Quantitative analysis of Delta(9)-tetrahydrocannabinol in preserved oral fluid by liquid chromatography-tandem mass spectrometry. Journal of Chromatography A 2005;1082(1):15. Le Vu S, Aquatias S, Bonnet N, Debrus M, Fournier G, Beauverie P. [Chemical content of street cannabis]. Presse Med, May 2006; 35(5 Pt 1): 755-8. Lewis R., Ward S, Johnson R, Burns D, Thorburn D. Distribution of the principal cannabinoids within bars of compressed cannabis resin. Analytica Chimica Acta 2005;538(1-2):399. 179


Lowe ER, Banks CE, Compton RG. Indirect detection of substituted phenols and cannabis based on the electrochemical adaptation of the Gibbs reaction. Analytical and Bioanalytical Chemistry 2005;383(3):523. Moore C, Rana S, Coulter C, Feyerherm F, Prest H. Application of two-dimensional gas chromatography with electron capture chemical ionization mass Spectrometry to the detection of 11-nor-Delta(9)-tetrahydrocannabinol-9-carboxylic acid (THCCOOH) in hair. Journal of Analytical Toxicology 2006;30(3):171. Nadulski T, Sporkert F, Schnelle M, Stadelmann AM, Roser P, Schefter T, Pragst F. Simultaneous and sensitive analysis of THC, 11-OH-THC, THC-COOH, CBD, and CBN by GC-MS in plasma after oral application of small doses of THC and cannabis extract. Journal Of Analytical Toxicology 2005;29(8):782. Pellegrini M, Marchei E, Pacifici R, Pichini S. A rapid and simple procedure for the determination of cannabinoids in hemp food products by gas chromatography-mass spectrometry. Journal of Pharmaceutical and Biomedical Analysis 2005;36(5):939. Pijlman FTA, Rigter SM, Hoek J, Goldschmidt HMJ, Niesink RJM. Strong increase in total delta-THC in cannabis preparations sold in Dutch coffee shops. Addiction Biology 2005;10(2):171. Raharjo TJ, Verpoorte R. Methods for the analysis of cannabinoids in biological materials: A review. Phytochemistry Analysis 2004;15:79. [Microgram Editor’s Notes: Focus is biological, but covers a wide variety of techniques. Contact: Division of Pharmacognosy, Leiden University, Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.] Ross SA, ElSohly MA, Sultana GNN, Mehmedic Z, Houssain CF, Chandra S. Flavonoid glycosides and cannabinoids from the pollen of Cannabis sativa L. Phytochemical Analysis 2005;16:45. Stolker AAM, van Schoonhoven J, deVries AJ, Bobeldjik-Pastorova I, Vaes WHJ, vandenBerg R. Determination of cannabinoids in cannabis products using liquid chrmoatography-ion trap mass spectrometry. Journal of Chrmoatography A 2004;1058(1-2):143. [Microgram Editor’s Notes: The presented method analyzes for CBD, CBD-COOH, CBN, THC, and THC-COOH. Contact: TNO, Nutr & Food Res, Dept Analyt Sci, POB 360, NL-3700 AJ Zeist, Netherlands.] Yotoriyama M, Ishiharajima E, Kato Y, Nagato A, Sekita S, Watanabe K, Yamamoto I. Identification and determination of cannabinoids in both commercially available and cannabis oils stored long term. Journal of Health Science 2005;51(4):483.


Mescaline/Peyote: Methadone:

Etter ML, George S, Graybiel K, Eichhorst J, Lehotay DC. Determination of free and protein-bound methadone and its major metabolite EDDP: Enantiomeric separation and quantitation by LC/MS/MS. Clinical Biochemistry 2005;38(12):1095. Kelly T, Doble P, Dawson M. Chiral analysis of methadone and its major metabolites (EDDP and EMDP) by liquid chromatography-mass spectrometry. Journal of Chromatography B Analytical Technologies in the Biomedical and Life Sciences 2005;814(2):315. RodriguezRosasa ME, Medrano JG, Epstein DH, Moolchan ET, Preston KL, Wainer IW. Determination of total and free concentrations of the enantiomers of methadone and its metabolite (2-ethylidene-1,5-dimethyl-3,3-diphenyl-pyrrolidine) in human plasma by enantioselective liquid chromatography with mass spectrometric detection. Journal of Chromatography A 2005;1073(1-2):237.

Methylenedioxyamphetamines and Related Compounds:

Aalberg L, DeRuiter J, Sippola E, Clark CR. Gas chromatographic optimization study on the side chain and ring regioisomers of methylenedioxymethamphetamine. Journal of Chromatographic Science 2004;42(6):293. [Microgram Editor’s Notes: Includes the analysis of 10 isomeric compounds (not specified in the abstract). Contact: Department of Pharmaceutical Sciences, School of Pharmacy, Auburn University, Auburn, AL 36849.] Adamowicz P, Chudzikiewicz E, Lechowicz W. Illicit Ecstasy tablets in southern Poland: A two-year review. Z Zagadnien Nauk Sadowych 2004;56:100. [Microgram Editor’s Notes: Presents analytical results for 199 tablet seizures submitted over a two year period (time frame not specified in the abstract). Contact: Institute of Forensic Research, Cracow, Poland.] Awad T, Clark CR, DeRuiter J. Chromatographic and mass spectral studies on methoxymethcathinones related to 3,4-methylenedioxymethamphetamine. Journal of Chromatographic Science 2006;44(3):155. Awad T, DeRuiter J, Clark CR. GC-MS analysis of acylated derivatives of the side chain and ring regioisomers of methylenedioxymethamphetamine. Journal of Chromatographic Science 2005;43(6):296. Bernschneider-Reif S, Oxler F, Freudenmann RW. The origin of MDMA (ecstasy)separating the facts from the myth. Pharmazie, Nov 2006; 61(11): 966-72. Casteele SRV, Bouche MPL, Van Bocxlaer JF. LC-MS/MS in the elucidation of an isomer of the recreational drug methylenedioxy ethylamphetamine: Methylenedioxy dimethylamphetamine. Journal of Separation Science 2005;28(14):1729.



Concheiro M, de Castro A, Quintela O, Lopez-Rivadulla M, Cruz A. Determination of MDMA, MDA, MDEA and MBDB in oral fluid using high performance liquid chromatography with native fluorescence detection. Forensic Science International 2005;150(2-3):221. daCosta JL, Chasin AAD. Determination of MDMA, MDEA and MDA in urine by high performance liquid chromatography with fluorescence detection. Journal of Chromatography B - Analytical Technologies in the Biomedical and Life Sciences 2004;811(1):41. Huang YS, Tsai CC, Liu JT, Lin CH. Comparison of the use of aqueous and nonaqueous buffers in association with cyclodextrin for the chiral separation of 3,4methylenedioxymethamphetamine and related compounds. Electrophoresis 2005;26(20):3904. Jiang H-p, Ren C-h. Study on DFT of the structure and property of MDMA molecule. Xihua Daxue Xuebao, Ziran Kexueban 2006;25(5):69 6A. [Microgram Editor’s Notes: A theoretical study of the structure and properties of MDMA by the “d. functional theory” (“d.” was not defined in the abstract). This article is written in Chinese. Contact: Department of Criminal Technology, College of Sichuan Police Officer, Luzhou Sichuan 646000, Peop. Rep. China.] Kalasinsky KS, Hugel J, Kish SJ. Use of MDA (the Love Drug) and methamphetamine in Toronto by unsuspecting users of ecstasy. Journal of Forensic Sciences 2004;49(5):1106. [Microgram Editor’s Notes: An overview of the use of alleged MDMA tablets containing mixed and/or alternative drugs, focus is biological/toxicological. Contact: stephen_kish .] Kochana J, Zakrzewska A, Parczewski A, Wilamowski J. TLC screening method for identification of active components of Ecstasy tablets. Influence of diluents and adulterants. Journal of Liquid Chromatography & Related Technologies 2005;28(18):2875. Koelliker S, Oehme M. Structure elucidation of nanogram quantities of unknown designer drugs based on phenylalkylamine derivates by ion trap multiple mass spectrometry. Analytical and Bioanalytical Chemistry 2004;378(5):1294. [Microgram Editor’s Notes: Presents the use of HPLC multiple mass spectrometry on 55 phenylalkylamines (focus is on compounds in European ecstasy tablets). Contact: Organic Analytical Chemistry, University of Basel, 4057 Basel, Switz.] Lapachinske SF, Yonamine M, Moreau RLdM. Validation of a gas chromatographic method for the determination of 3,4-methylenedioxymethamphetamine (MDMA) in ecstasy tablets. Revista Brasileira de Ciencias Farmaceuticas 2004;40(1):75. [Microgram Editor’s Notes: Uses nitrogen/phosphorus detection. This article is written in Portugese. Contact: Laboratorio de Analises Toxicologicas, Departamento de Analises Clinicas e Toxicologicas, Faculdade de Ciencias Farmaceuticas, Universidade de Sao Paulo, Brazil.]


Leuthold LA, Mandscheff J-F, Fathi M, Giroud C, Augsburger M, Varesio E, Hopfgartner G. Desorption electrospray ionization mass spectrometry: Direct toxicological screening and analysis of illicit Ecstasy tablets. Rapid Communications in Mass Spectrometry 2006;20(6):103. Leuthold LA, Mandscheff JF, Fathi M, Giroud C, Augsburger M, Varesio E, Hopfgartner G. Direct ambient analysis of pharmaceutical and ecstasy tablets. Chimia 2006;60(4):190. Liu J-T. GC-MS and pentafluoropropionic anhydride derivatization methods for the differentiation of 3,4-methylenedioxymethamphetamine (MDMA) from their regioisomeric 1-(3,4-methylenedioxyphenyl)-2-ethylamines (MDPEAs). Huaxue 2005;63(1):95. Maresova V, Hampl J, Chundela Z, Zrcek F, Polasek M, Chadt J. The identification of a chlorinated MDMA. Journal of Analytical Toxicology 2005;29(5):353. Mc Fadden K, Gillespie J, Carney B, O'Driscoll D. Development and application of a high-performance liquid chromatography method using monolithic columns for the analysis of ecstasy tablets. Journal of Chromatography A 2006;1120(1-2):54. Muller IB, Windberg CN. Validation of an HPLC method for quantitation of MDMA in tablets. Journal of Chromatographic Science 2005;43(8):434. Newton HR. Indanylamphetamine identified. Journal of the Clandestine Laboratory Investigating Chemists Association 2004;14(3):12. [Microgram Editor’s Notes: Presents analytical data for 1-(5indanyl) -2-aminopropane (commonly mis-named as indanylamphetamine), a recently encountered designer drug that is an analog of MDA. Note that this Journal (JCLICA) is law enforcement restricted. Contact: Indiana State Police, Indianapolis Laboratory (no further addressing information was provided).] Peters FT, Samyn N, Lamers CTJ, Riedel WJ, Kraemer T, De Boeck G, Maurer HH. Drug testing in blood: Validated negative-ion chemical ionization gas chromatographic-mass spectrometric assay for enantioselective measurement of the designer drugs MDEA, MDMA, and MDA and its application to samples from a controlled study with MDMA. Clinical Chemistry 2005;51(10):1811. Pihlainen K, Aalberg L, Tepponen M, Clark CR, Kostiainen R. The identification of 3,4-MDMA from its mass equivalent isomers and isobaric substances using fast LCESI-MS-MS. Journal of Chromatographic Science 2005;43(2):92. Scheidweiler KB, Huestis MA. A validated gas chromatographic-electron impact ionization mass spectrometric method for methylenedioxymethamphetamine (MDMA), methamphetamine and metabolites in oral fluid. Journal Of Chromatography B-Analytical Technologies In The Biomedical And Life Sciences 2006;835(1-2):90.



Skrinska VA. Measurement of 3,4-MDMA and related amines in diagnostic and forensic laboratories. Clinical Laboratory Science 2005;18(2):119. Su AK, Liu JT, Lin CH. Rapid drug-screening and quantitation of 3,4methylenedioxymethamphetamine in urine by MALDI-TOF mass spectrometry. Analytica Chimica Acta 2005;546(2):193. Su AK, Liu JT, Lin CH. Rapid drug-screening of clandestine tablets by MALDI-TOF mass spectrometry. Talanta 2005;67(4):718. Tanner-Smith EE. Pharmacological content of tablets sold as ecstasy: results from an online testing service. Drug Alcohol Depend, Jul 2006; 83(3): 247-54. Teng S-f, Wu S-c, Tsay W-l, Liu C-r. The composition of MDMA tablets seized in Taiwan. Huaxue 2005;63(3):463. Tsai CH, Fang C, Liu JT, Lin CH. Stacking and low temperature technique in nonaqueous capillary electrophoresis for the analysis of 3,4methylenedioxymethamphetamine. Electrophoresis 2004;25(10 11):1601. [Microgram Editor’s Notes: Presents the novel title technique, includes analysis of an illicit sample. Contact: Natl Taiwan Normal Univ, Dept Chem, 88 Sec 4, Tingchow Rd, Taipei, Taiwan.] Vande Casteele SR. LC-MS/MS in the elucidation of an isomer of the recreational drug methylenedioxyethylamphetamine: Methylenedioxydimethylamphetamine. Journal of Separation Science 2005;28:1729. Wu G, Cai X, Xiang B. Forensic identification of ecstasy (MDMA) by pattern recognition. Zhongguo Yaoke Daxue Xuebao 2005;36(2):150. Zgonjanin DM, Loncar ES, Tasic MM. Analysis of forensic samples of “Ecstasy” tablets seized in Novi Sad during the 2004 year. Acta Periodica Technologica 2005;36:247.


Gilbert KM, Skawinski WJ, Misra M, Paris KA, Naik NH, Buono RA, Deutsch HM, Venanzi CA. Conformational analysis of methylphenidate: Comparison of molecular orbital and molecular mechanics methods. Journal of Computer-Aided Molecular Design 2004;18(11):719.

Morphine, Codeine, and Related Opium Alkaloids:

Capella-Peiro ME, Bose D, Rubert MF, Esteve-Romero J. Optimization of a capillary zone electrophoresis method by using a central composite factorial design for the determination of codeine and paracetamol in pharmaceuticals. J Chromatogr B Analyt Technol Biomed Life Sci, Jul 2006; 839(1-2): 95-101. [Microgram Editor’s Notes: Presents the title study; analyses could be done in less than 3 minutes. Contact: Univ Jaume I, Area Quim Analit, Castellon de La Plana 12080, Spain.]


Cristoni S, Cantu M, Bernardi LR, Gerthoux P, Mocarelli P, Brambilla M, Gonella E, Guidugli F. Surface-activated chemical ionization ion trap mass spectrometry in the analysis of drugs in dilute urine samples. Part II: analysis of morphine and other street drugs. Journal Of Mass Spectrometry 2005;40(12):1609. Du LM, Li L, Wu H. [Spectrophotometric determination of codeine through chargetransfer reaction]. Guang Pu Xue Yu Guang Pu Fen Xi, Feb 2007; 27(2): 364-6. Ebejer KA, Brereton RG, Carter JF, Ollerton SL, Sleeman R. Rapid comparison of diacetylmorphine on banknotes by tandem mass spectrometry. Rapid Communications in Mass Spectrometry 2005;19(15):2137. Garrido JMPJ, Delerue-Matos C, Borges F, Macedo TRA, Oliveira-Brett, AM. Voltammetric oxidation of drugs of abuse - I. Morphine and metabolites. Electroanalysis 2004;16(17):1419. Garrido JMPJ, Delerue-Matos C, Borges F, Macedo TRA, Oliveira-Brett AM. Voltammetric oxidation of drugs of abuse - II. Codeine and metabolites. Electroanalysis 2004;16(17):1427. Gomez MR. Development and validation of a capillary electrophoresis method for the determination of codeine, diphenhydramine, ephedrine, and noscapine in pharmaceuticals. Il Farmaco 2005;60(1):85. Gunn JA, Shelley C, Lewis SW, Toop T, Archer M. The determination of morphine in the larvae of Calliphora stygia using flow injection analysis and HPLC with chemiluminescence detection. J Anal Toxicol, Oct 2006; 30(8): 519-23. Hida M, Mitsui T, Tsuge S, Ohtani H. Rapid and sensitive determination of morphine in street opium samples by thermal desorption gas chromatography using a microfurnacepyrolyzer. Journal of Separation Science 2004;27(12):1030. [Microgram Editor’s Notes: Presents the title analysis. Contact: Criminal Investigation Lab., Aichi Prefectural Police HDQS, Nagoya, Aichi 460 8502, Japan.] Joly N, El Aneed A, Martin P, Cecchelli R, Banoub J. Structural determination of the novel fragmentation routes of morphine opiate receptor antagonists using electrospray ionization quadrupole time-of-flight tandem mass spectrometry. Rapid Communications in Mass Spectrometry 2005;19(21):3119. Kuila DK, Lahiri SC. Interactions of morphine and codeine with benzoic acid and substituted benzoic acids. Journal of the Indian Chemical Society 2004;81(11):928. [Microgram Editor’s Notes: Investigates the complexes formed by the title compounds. The focus of this study is not clear from the abstract. Contact: Central Forensic Science Laboratory, Kolkata 700 014, India.] Lewis RJ, Johnson RD, Hattrup RA. Simultaneous analysis of thebaine, 6-MAM and six abused opiates in postmortem fluids and tissues using Zymark(R) automated solid-phase extraction and gas chromatography-mass spectrometry. Journal of



Chromatography B - Analytical Technologies in the Biomedical and Life Sciences 2005;822(1-2):137. Liu HC, Ho HO, Liu RH, Yeh GC, Lin DL. Urinary excretion of morphine and codeine following the administration of single and multiple doses of opium preparations prescribed in Taiwan as brown mixture. J Anal Toxicol, May 2006; 30(4): 225-31. Lyubavina IA, Zinchenko AA, Lapenkov MI, Nikolaeva TL. An express morphine assay in aqueous samples by immunochromatography using monoclonal antibodies labeled with colloidal gold. Russian Journal of Bioorganic Chemistry 2005;31(1):99. Meatherall R. GC-MS quantitation of codeine, morphine, 6-acetylmorphine, hydrocodone, hydromorphone, oxycodone, and oxymorphone in blood. Journal of Analytical Toxicology 2005;29(5):301. Morales ME, Ruiz MA, Oliva I, Oliva M, Gallardo V. Chemical characterization with XPS of the surface of polymer microparticles loaded with morphine. Int J Pharm, Mar 2007; 333(1-2): 162-6. Murphy CM, Huestis MA. LC-ESI-MS/MS analysis for the quantification of morphine, codeine, morphine-3-beta-D-glucuronide, morphine-6-beta-Dglucuronide, and codeine-6-beta-D-glucuronide in human urine. Journal of Mass Spectrometry 2005;40(11):1412. Pejic ND, Blagojevic SM, Anic SR, Vukojevic VB, Mijatovic MD, Ciric JS, Markovic ZS, Markovic SD, Kolar-Anic LZ. Kinetic determination of morphine by means of Bray-Liebhafsky oscillatory reaction system using analyte pulse perturbation technique. Anal Chim Acta, Jan 2007; 582(2): 367-74. Poeaknapo C, Fisinger U, Zenk MH, Schmidt J. Evaluation of the mass spectrometric fragmentation of codeine and morphine after C-13-isotope biosynthetic labeling. Phytochemistry 2004;65(10):1413. Smetkova M, Ondra P, Lemr K. HPLC-MS and CE-MS with atomospheric pressure ionization in analysis of morphine and related compounds. Chemicke Listy 2004;98(6):336. [Microgram Editor’s Notes: A review and discussion of the title subject. Abstract is not clear whether the focus is forensic or toxicological (the latter appears more likely). This article is written in Czech. Contact: Department of Analytical Chemistry, Faculty of Science, Palacky University, Olomouc, Czech Rep.] Sproll C. New methods of morphine analysis in food. No intoxication from poppy cake. CLB Chemie in Labor und Biotechnik 2005;56(10):348. Sproll C, Perz RC, Lachenmeier DW. Optimized LC/MS/MS analysis of morphine and codeine in poppy seed and evaluation of their fate during food processing as a basis for risk analysis. J Agric Food Chem, Jul 2006; 54(15): 5292-8.


Wall DB, Finch JW, Cohen SA. Quantitation of codeine by desorption/ionization on silicon time-of-flight mass spectrometry and comparisons with liquid chromatography/mass spectrometry. Rapid Communications in Mass Spectrometry 2004;18:1403. [Microgram Editor’s Notes: Presents the title analysis, including analyses of standards and a liquid pharmaceutical preparation. Contact: Waters Corporation, Milford, MA 01757.] Wei F, Zhang M, Feng YQ. Application of poly(methacrylic acid-ethylene glycol dimethacrylate) monolith microextraction coupled with capillary zone electrophoresis to the determination of opiates in human urine. Electrophoresis 2006;27(10):1939. Xie Z-r. Determination of the morphine in complex background by tandem mass spectrometry. Zhipu Xuebao 2004;25(Suppl.):103. Zayed MA, El-Shahat MF, Abdullah SM. The use of IR, magnetism, reflectance, and mass spectra together with thermal analyses in structure investigation of codeine phosphate complexes of d-block elements. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy 2005;61(8):1955. Zayed MA, Hawash MF, Fahmey MA. Structure investigation of codeine drug using mass spectrometry, thermal analyses and semi-emperical molecular orbital (MO) calculations. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy 2006;64(3):363.

Opiate Alkaloids:

Braye K, Harwood T, Inder R, Beasley R, Robinson G. Poppy seed tea and opiate abuse in New Zealand. Drug Alcohol Rev, Mar 2007; 26(2): 215-9. Campora P, Bermejo AM, Tabernero MJ, Fernandez P. Use of gas chromatography/mass spectrometry with positive chemical ionization for the determination of opiates in human oral fluid. Rapid Communications In Mass Spectrometry 2006;20(8):1288. CapellaPeiro ME, Bose D, GilAgusti M, EsteveRomero J, CardaBroch S. Direct injection determination of benzoylecgonine, heroin, 6-monoacetylmorphine and morphine in serum by MLC. Journal of Chromatography A 2005;1073(1-2):277. Edinboro LE, Backer RC, Poklis A. Direct analysis of opiates in urine by liquid chromatography-tandem mass spectrometry. Journal of Analytical Toxicology 2005;29(7):704. Garrido JMPJ, Delerue-Matos C, Borges F, Macedo TRA, Oliveira-Brett AM. Electrochemical analysis of opiates - An overview. Analytical Letters 2004;37(5):831. [Microgram Editor’s Notes: An overview and review of the title topic, with an emphasis on morphine, codeine, and heroin. Contact: Univ Coimbra, Fac Ciencias & Tecnol, Dept Quim, P-3004535 Coimbra, Portugal.]



Kerrigan S, Goldberger BA. Opioids. Principles of Forensic Toxicology (2nd Edition) 2003:187. Kim JY, In MK, Paeng KJ, Chung BC. Simultaneous determination of nalbuphine and opiates in human hair by gas chromatography-mass spectrometry. Chromatographia 2004;59(3-4):219. Li J, Ye L. Determination of opioids. Zhongguo Yaowu Yilaixing Zazhi 2004;13(3):235. [Microgram Editor’s Notes: A minor overview, including discussions of the use of TLC, immunoassay, and GC/MS, for the title study. This article is written in Chinese. Contact: Teacher’s College, Beijing Union University, Beijing 100011, Peop. Rep. China.] Li SH, He CY, Liu HW, Li K, Liu F. Ionic liquid-based aqueous two-phase system, a sample pretreatment procedure prior to high-performance liquid chromatography of opium alkaloids. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2005;826(1-2):58. Pellegrini M, Casa A, Marchei E, Pacifici R, Mayne R, Barbero V, GarciaAlgar O, Pichini S. Development and validation of a gas chromatography-mass spectrometry assay for opiates and cocaine in human teeth. Journal of Pharmaceutical and Biomedical Analysis 2006;40(3):662. Pothier J, Galand N. Automated multiple development thin-layer chromatography for separation of opiate alkaloids and derivatives. Journal of Chromatography A 2005;1080(2):186. Qi XH, Mi JQ, Zhang XX, Chang WB. Preparation and application of an immunoaffinity column for direct extraction of morphine and its analogs from opium. Chinese Chemical Letters 2004;15(11):1323. [Microgram Editor’s Notes: The presented method uses an IAC for isolation and CE for analysis. The four alkaloids that are selectively isolated are morphine, codeine, dionin, and thebaine. Contact: The Key Lab of Bioorganic Chemistry and Molecular Engineering, Peking University, Beijing, Peop. Rep. China 100871.] Sukhats’ka IY, Golovei OP, Tkach VI. Ionometric determination of the total content of opium alkaloids in crime-investigation samples. Visnik Kharkivs’kogo Natsional’nogo Universitetu im. V.N. Karazina 2005;648:339. Yoshimatsu K, Kiuchi F, Shimomura K, Makino Y. A rapid and reliable solid-phase extraction method for high-performance liquid chromatographic analysis of opium alkaloids from Papaver plants. Chemical and Pharmaceutical Bulletin 2005;53(11):1446.

Opium (and Opium Poppies):

Chitty JA, Allen RS, Larkin PJ. Opium Poppy (Papaver somniferum). Methods Mol Biol, Jan 2006; 344: 383-91.


Krist S, Stuebiger G, Unterweger H, Bandion F, Buchbauer G. Analysis of volatile compounds and triglycerides of seed oils extracted from different poppy varieties (Papaver somniferum L.). Journal of Agricultural and Food Chemistry 2005;53(21):8310. Lenehan CE, Barnett NW, Lewis SW, Essery KM. Preliminary evaluation of dual acidic potassium permanganate and tris(2,2 '-bipyridyl)ruthenium(II) chemiluminescence detection for the HPLC determination of Papaver somniferum alkaloids. Australian Journal of Chemistry 2004;57(10):1001. Lovkova M, Buzuk GN, Sokolova SM. [Regulatory role of elements in the formation and accumulation of alkaloids in Papaver somniferum L. seedlings]. Prikl Biokhim Mikrobiol, Jul 2006; 42(4): 475-9. Lu F, Hong J-y, He R, Li L-s. Study of Papaver somniferum cultivars identification by TD-RAPD technique. Fayixue Zazhi 2006;22(5):367. [Microgram Editor’s Notes: Presents the title study. The results allow for origin determination. This article is written in Chinese. Contact: Yunnan Criminal Science and Technology Institute, Kunming 650021, Peop. Rep. China.] Salehi P, Sonboli A, Zavareh AF, Sefidkon F, Dayeni M, Cheraghi B. Narcotic alkaloids of four papaver species from Iran. Z Naturforsch [C], Jan 2007; 62(1-2): 16-8 Schulz H, Branska M, Quilitzsch R, Schutze W. Determination of alkaloids in capsules, milk and ethanolic extracts of poppy (Papaver somniferum L.) by ATR-FTIR and FT-Raman spectroscopy. Analyst 2004;129(10):917. [Microgram Editor’s Notes: Enables analysis without special preparation, and the ATR technique requires very little sample. Fluorescence effects in the Raman analysis were negligible. Contact: Fed Ctr Breeding Res Cultivated Plants BAZ, Inst Plant Anal, Neuer Weg 22-23, D-06484 Quedlinburg, Germany.] Weid M, Ziegler J, Kutchan TM. The roles of latex and the vascular bundle in morphine biosynthesis in the opium poppy, Papaver somniferum. Proceedings of the National Academy of Sciences of the United States of America 2004;101(38):13957. Wickens JR, Sleeman R, Keely BJ. Atmospheric pressure ionisation mass spectrometric fragmentation pathways of noscapine and papaverine revealed by multistage mass spectrometry and in-source deuterium labelling. Rapid Commun Mass Spectrom, Jan 2006; 20(3): 473-80.


Allen KR, Azad R, Field HP, Blake DK. Replacement of immunoassay by LC tandem mass spectrometry for the routine measurement of drugs of abuse in oral fluid. Annals of Clinical Biochemistry 2005;42, Part 4):277.



Alvarez I, Palos F, Bermejo AM, Fernandez P, Tabernero MJ. Simultaneous determination of methadone, heroin, cocaine and their metabolites in urine by GCMS. Analytical Letters 2006;39(7):1393. Apollonio LG, Pianca DJ, Whittall IR, Maher WA, Kyd JM. A demonstration of the use of ultra-performance liquid chromatography-mass spectrometry [UPLC/MS] in the determination of amphetamine-type substances and ketamine for forensic and toxicological analysis. J Chromatogr B Analyt Technol Biomed Life Sci, May 2006; 836(1-2): 111-5. Apollonio LG, Whittall IR, Pianca DJ, Kyd JM, Maher WA. Product ion mass spectra of amphetamine-type substances, designer analogues, and ketamine using ultraperformance liquid chromatography/tandem mass spectrometry. Rapid Commun Mass Spectrom, Jan 2006; 20(15): 2259-64. Bishop SC, McCord BR, Gratz SR, Loeliger JR, Witkowski MR. Simultaneous separation of different types of amphetamine and piperazine designer drugs by capillary electrophoresis with a chiral selector. Journal of Forensic Sciences 2005;50(2):326. Bishop SC. Advanced capillary electrophoretic techniques for the detection of daterape and club drugs for a forensic setting. Diss. Abstr. Int. B 2005;66(1):258. Bonato PS, Jabor VAP, de Gaitani CM. Enantioselective analysis of drugs: Contributions of high-performance liquid chromatography and capillary electrophoresis. Quimica Nova.2005;28(4):683. Burnett A, Fan W, Upadhya P, Cunningham J, Linfield E, Davies G, Edwards H, Munshi T, O’Neil A. Analysis of drugs-of-abuse and explosives using terahertz timedomain and Raman spectroscopy. (Proceedings) Chemical Abstracts 2006:300182. Caldwell GW, Yan ZY. Screening for reactive intermediates and toxicity assessment in drug discovery. Current Opinion in Drug Discovery & Development 2006;9(1):47. Chen Z, Wang Y, Zhao Y, An J, Qi T. Analysis of mixed drugs of abuse by gas chromatography - mass spectrometry. Zhongguo Yaowu Yilaixing Zazhi 2005;14(1):68. Dahlen J, von Eckardstein S. Development of a capillary zone electrophoresis method including a factorial design and simplex optimisation for analysis of amphetamine, amphetamine analogues, cocaine, and heroin. Forensic Science International 2006;157(2-3):93. ElMaali NA. Voltammetric analysis of drugs. Bioelectrochemistry 2004;64(1):99. Fang H-F, Zeng Z-R, Liu L, Pang D-W. A novel method for capillary electrophoresis directly analyzing trace amount analytes in the water-immiscible solution samples. Xuexiao Huaxue Xuebao 2006;27(5):856. [Microgram Editor’s Notes: Abstract specifies cocaine and thebaine. Focus may be toxicological (not clear in abstract). 190

This article is written in Chinese. Contact: College of Chemistry and Molecular Science, Wuhan University, Wuhan, Peop. Rep. China 430072.] Fernandez P, Vazquez C, Morales L, Bermejo AM. Analysis of opiates, cocaine and metabolites in urine by high-performance liquid chromatography with diode array detection (HPLC-DAD). Journal of Applied Toxicology 2005;25(3):200. Gaulier J-M, Fonteau F, Jouanel E, Lachatre G. Rape drugs: Pharmacological and analytical aspects. Annales de Biologie Clinique 2004;62(5):529. Gratz SR, Gamble BM, Flurer RA. Accurate mass measurement using Fourier transform ion cyclotron resonance mass spectrometry for structure elucidation of designer drug analogs of tadalafil, vardenafil and sildenafil in herbal and pharmaceutical matrices. Rapid Commun Mass Spectrom, Jan 2006; 20(15): 2317-27. Gunnar T, Ariniemi K, Lillsunde P. Validated toxicological determination of 30 drugs of abuse as optimized derivatives in oral fluid by long column fast gas chromatography/electron impact mass spectrometry. Journal of Mass Spectrometry 2005;40(6):739. Hays PA. Proton nuclear magnetic resonance spectroscopy (NMR) methods for determining the purity of reference drug standards and illicit forensic drug seizures. Journal of Forensic Sciences 2005;50(6):1342. Karetnikov MD, Meleshko EA, Yakovlev GV. Detection, identification, and localization of organic substances, including explosive and narcotic substances, using pulsed fast neutrons. Chemical Abstracts 2004:894555. Kawase K, Ogawa Y, Watanabe Y. Terahertz spectroscopic imaging and its application to drug detection. IEICE Transactions On Electronics 2004;E87C(7):1186. Kolliker S, Oehme M. High-speed identification of designer drugs by multiple mass spectrometry. Chimia 2005;59(9):708. Laks S, Pelander A, Vuori E, Ali-Toippa E, Sippola E, Ojanpera I. Analysis of street drugs in seized material without primary reference standards. Analytical Chemistry 2004;76(24):7375. [Microgram Editor’s Notes: Uses a combination of LC-Time-ofFlight-MS and LC-Chemiluminescence Nitrogen Detection on 21 samples (different drugs). The results were found to be reasonable, with variances from established methods ranging from 4 to 21 percent, and only one apparent false positive. Contact: Department of Forensic Medicine, University of Helsinki, P.O. Box 40, FIN-00014 Helsinki, Fnland.] Lowe RH, Barnes AJ, Lehrmann E, Freed WJ, Kleinman JE, Hyde TM, Herman MM, Huestis MA. A validated positive chemical ionization GC/MS method for the identification and quantification of amphetamine, opiates, cocaine, and metabolites in human postmortem brain. Journal of Mass Spectrometry 2006;41(2):175.



Lu NT, Taylor BG. Drug screening and confirmation by GC-MS: Comparison of EMIT II and Online KIMS against 10 drugs between US and England laboratories. Forensic Science International 2006;157(2-3):106. Maurer HH, Kraemer T, Springer D, Staack RF. Chemistry, pharmacology, toxicology, and hepatic metabolism of designer drugs of the amphetamine (Ecstasy), piperazine, and pyrrolidinophenone types - A synopsis. Therapeutic Drug Monitoring 2004;26(2):127. Maurer HH. Multi-analyte procedures for screening for and quantification of drugs in blood, plasma, or serum by liquid chromatography-single stage or tandem mass spectrometry (LC-MS or LGMS/MS) relevant to clinical and forensic toxicology. Clinical Biochemistry 2005;38(4):310. Maurer HH. Position of chromatographic techniques in screening for detection of drugs or poisons in clinical and forensic toxicology and/or doping control. Clinical Chemistry And Laboratory Medicine 2004;42(11):1310. Mueller CA, Weinmann W, Dresen S, Schreiber A, Gergov M. Development of a multi-target screening analysis for 301 drugs using a QTrap liquid chromatography/tandem mass spectrometry system and automated library searching. Rapid Communications In Mass Spectrometry 2005;19(10):1332. Nakashima K. High-performance liquid chromatographic analysis of drugs of abuse in biologic samples. Journal Of Health Science 2005;51(3):272. Nerkis S, Oruc HH. Determination of amounts of the active substance and added substances in cannabis, heroin, and ecstasy tablets used in Bursa and in the Bursa region. Bagimlilik Dergisi 2006;7(1):11. [Microgram Editor’s Notes: 21 Cannabis, 55 heroin, and 65 Ecstasy tablet exhibits were characterized by GC/MS and FTIR. This article is written in Turkish. Contact: Bursa Leg. Med. Soc., Turk.] Nordgren HK, Holmgren P, Liljeberg P, Eriksson N, Beck O. Application of direct urine LC-MS-MS analysis for screening of novel substances in drug abusers. Journal Of Analytical Toxicology 2005;29(4):234. Ogawa Y, Kawase K, Yamashita M, Inoue H. Non-destructive inspection techniques for illicit drugs using tetrahertz imaging. Trends in Optics and Photonics 2004;96/A:CMG3/1-CMG3/3. Ogawa Y, Shibuya T, Otani C, Kawase K. Inspection of illicit drugs in envelopes using terahertz imaging. Hikari Araiansu 2006;17(2):12. Rodriguez-Cruz SE. Rapid analysis of controlled substances using desorption electrospray ionization mass spectrometry. Rapid Commun Mass Spectrom, Jan 2006; 20(1): 53-60. Rook EJ, Hillebrand MJX, Rosing H, van Ree JM, Beijnen JH. The quantitative analysis of heroin, methadone and their metabolites and the simultaneous detection 192

of cocaine, acetylcodeine and their metabolites in human plasma by highperformance liquid chromatography coupled with tandem mass spectrometry. Journal Of Chromatography B-Analytical Technologies in the biomedical and life sciences 2005;824(1-2):213. Shen J, Sun J, Li N, Liang L, Xu X, Liu H, Zhang C. Investigation on THz fingerprint spectrum of illicit drugs. (Proceedings) Chemical Abstracts 2006;144:186167e. Stanley SMR, Foo HC. Screening for basic drugs in equine urine using directinjection differential-gradient LC-LC coupled to hybrid tandem MS/MS. Journal Of Chromatography B-Analytical Technologies In The Biomedical And Life Sciences 2006;836(1-2):1. StranoRossi S, Molaioni F, Botre F. Application of solid-phase microextraction to antidoping analysis: Determination of stimulants, narcotics, and other classes of substances excreted free in urine. Journal of Analytical Toxicology 2005;29(4):217. Strano-Rossi S, Molaioni F, Rossi F, Botre F. Rapid screening of drugs of abuse and their metabolites by gas chromatography/mass spectrometry: application to urinalysis. Rapid Communications in Mass Spectrometry 2005;19(11):1529. Stringham RW, Ye YK. Chiral separation of amines by high-performance liquid chromatography using polysaccharide stationary phases and acidic additives. Journal of Chromatography A 2006;1101(1-2):86. Verma RS, Dalela AK, Tripathi RM, Middha D. Designer drugs. Journal of Forensic Medicine and Toxicology 2005;22(1):8. Wen T, Zhao X, Luo GA, Wang J, Wang YM, Li P, Zhu J, Yu ZS. Simultaneous determination of heroin, amphetamine, and their basic impurities and adulterants using microemulsion electrokinetic chromatography. Chinese Chemical Letters 2005;16(11):1499. Wood M, Laloup M, Fernandez MDR, Jenkins KM, Young MS, Ramaekers JG, De Boeck G, Samyn N. Quantitative analysis of multiple illicit drugs in preserved oral fluid by solid-phase extraction and liquid chromatography-tandem mass spectrometry. Forensic Science International 2005;150(2-3):227. Wu ZP. Analysis of drugs of abuse by AccuTOF (TM) dual ESI LC/TOF mass spectrometry. Lc Gc North America 2006;Suppl. S:19. Wylie FM, Torrance H, Anderson RA, Oliver JS. Drugs in oral fluid - Part I. Validation of an analytical procedure for licit and illicit drugs in oral fluid. Forensic Science International 2005;150(2-3):191. Yang WY, Barnes AJ, Ripple MG, Fowler DR, Cone EJ, Moolchan ET, Chung HS, Huestis MA. Simultaneous quantification of methamphetamine, cocaine, codeine, and metabolites in skin by positive chemical ionization gas chromatography-mass



spectrometry. Journal of Chromatography B-Analytical Technologies In The Biomedical And Life Sciences 2006;833(2):210. Yazdi AS, Eshaghi Z. Surfactant enhanced liquid-phase microextraction of basic drugs of abuse in hair combined with high performance liquid chromatography. Journal of Chromatography A 2005;1094(1-2):1.


Farina A, Gostoli G, Bossu E, Montinaro A, Lestingi C, Lecce R. LC-MS determination of MPTP at sub-ppm level in pethidine hydrochloride. Journal of Pharmaceutical and Biomedical Analysis 2005;37(5, Sp. Iss. SI):1089.

Phenethylamines (including mixtures of Amphetamines, Methylenedioxy-amphetamines, and Related Compounds): Bishop SC, McCord BR, Gratz SR, Loeliger JR, Witkowski MR. Simultaneous separation of different types of amphetamine and piperazine designer drugs by capillary electrophoresis with a chiral selector. Journal of Forensic Sciences 2005;50(2):326.

Blachut D, Danikiewicz W, Olejnik M, Czarnocki Z. Electron ionization mass spectrometry as a tool for the investigation of the ortho effect in fragmentation of some Schiff bases derived from amphetamine analogs. Journal of Mass Spectrometry 2004;39(8):966. [Microgram Editor’s Notes: Presents and discusses the fragmentation patterns of Schiff bases derived from 2-, 3-, and 4-methoxyamphetamine. Contact: Faculty of Chemistry, Warsaw University, Warsaw 02 093, Pol.] Boatto G, Nieddu M, Carta A, Pau A, Palomba M, Asproni B, Cerri R. Determination of amphetamine-derived designer drugs in human urine by SPE extraction and capillary electrophoresis with mass spectrometry detection. Journal of Chromatography B Analytical Technologies in the Biomedical and Life Sciences 2005;814(1):93. Carmo H, Brulport M, Hermes M, Oesch F, de Boer D, Remiao F, Carvalho F, Schon MR, Krebsfaenger N, Doehmer J, Bastos ML, Hengstler JG. CYP2D6 increases toxicity of the designer drug 4-methylthioamphetamine (4-MTA). Toxicology, Jan 2007; 229(3): 236-44. Ewald AH, Fritschi G, Bork WR, Maurer HH. Designer drugs 2,5-dimethoxy-4bromo-amphetamine (DOB) and 2,5-dimethoxy-4-bromo-methamphetamine (MDOB): studies on their metabolism and toxicological detection in rat urine using gas chromatographic/mass spectrometric techniques. Journal of Mass Spectrometry 2006;41(4):487. Ewald AH, Fritschi G, Maurer HH. Designer drug 2,4,5-trimethoxyamphetamine (TMA-2): studies on its metabolism and toxicological detection in rat urine using gas chromatographic/mass spectrometric techniques. J Mass Spectrom, Sep 2006; 41(9): 1140-8.


Gong XY, Hauser PC. Enantiomeric separation of 1-phenylethylamine and 1cyclohexylethylamine in capillary electrophoresis with contactless conductivity detection. Journal of Chromatography A 2005;1094(1-2):196. Habrdova V, Peters FT, Theobald DS, Maurer HH. Screening for and validated quantification of phenethylamine-type designer drugs and mescaline in human blood plasma by gas chromatography/mass spectrometry. Journal of Mass Spectrometry 2005;40(6):785. Hyun MH, Tan G, Cho YJ. Liquid chromatographic enantioseparation of aryl alphaamino ketones; cathinone. Biomedical Chromatography 2005;19(3):208. Kanamori T, Tsujikawa K, Ohmae Y, Iwata YT, Inoue H, Kishi T, Nakahama T, Inouye Y. A study of the metabolism of methamphetamine and 4-bromo-2,5dimethoxyphenethylamine (2C-B) in isolated rat hepatocytes. Forensic Science International 2005;148(2-3):131. King JW, Molnar SP. A study of ring-substituent influence on pharmacological activity in a series of phenethylamine-type psychedelics. International Journal Of Quantum Chemistry 2004;100(6):1114. Rosner P, Quednow B, Girreser U, Junge T. Isomeric fluoro-methoxyphenylalkylamines: A new series of controlled-substance analogues (designer drugs). Forensic Science International 2005;148(2-3):143. [Microgram Editor’s Notes: Provides an overview of and comprehensive spectral data for a series of fluoroamphetamines, fluoromethoxyamphetamines, and a few similar compounds. Contact: Landeskriminalamt Schleswig-Holstein, Sachgebiet Toxikologie/Betaubungsmittel, Muhlenweg 166, D-24116 Kiel, Germany.] Theobald DS, Fehn S, Maurer HH. New designer drug, 2,5-dimethoxy-4-propylthiobeta-phenethylamine (2C-T-7): studies on its metabolism and toxicological detection in rat urine using gas chromatography mass spectrometry. Journal of Mass Spectrometry 2005;40(1):105. Theobald DS, Fritschi G, Maurer HH. Studies on the toxicological detection of the designer drug 4-bromo-2,5-dimethoxy-beta-phenethylamine (2C-B) in rat urine using gas chromatography-mass spectrometry. J Chromatogr B Analyt Technol Biomed Life Sci, Feb 2007; 846(1-2): 374-7. Theobald DS, Maurer HH. Studies on the metabolism and toxicological detection of the designer drug 2,5-dimethoxy-4-methyl-beta- phenethylamine (2C-D) in rat urine using gas chromatographic/mass spectrometric techniques. J Mass Spectrom, Nov 2006; 41(11): 1509-19. Theobald DS, Maurer HH. Studies on the metabolism and toxicological detection of the designer drug 4-ethyl-2,5-dimethoxy-beta-phenethylamine (2C-E) in rat urine using gas chromatographic-mass spectrometric techniques. J Chromatogr B Analyt Technol Biomed Life Sci, Oct 2006; 842(2): 76-90.



Theobald DS, Putz M, Schneider E, Maurer HH. New designer drug 4-iodo-2,5dimethoxy-beta-phenethylamine (2C-I): studies on its metabolism and toxicological detection in rat urine using gas chromatographic/mass spectrometric and capillary electrophoretic/mass spectrometric techniques. J Mass Spectrom, Jul 2006; 41(7): 872-86. Theobald DS, Staack RF, Puetz M, Maurer HH. New designer drug 2,5-dimethoxy-4ethylthio-beta-phenethylamine (2C-T-2): studies on its metabolism and toxicological detection in rat urine using gas chromatography/mass spectrometry. Journal Of Mass Spectrometry 2005;40(9):1157. Thigpen A, Deruiter J, Clark CR. GC-MS Studies on the Regioisomeric 2,3- and 3,4Methylenedioxyphenethylamines Related to MDEA, MDMMA, and MBDB. J Chromatogr Sci, May 2007; 45(5): 229-35. Tsai C-C, Liu J-T, Shu Y-R, Chan P-H, Lin C-H. Optimization of the separation and on-line sample concentration of phenethylamine designer drugs with capillary electrophoresis-fluorescence detection. Journal of Chromatography A 2006;1101:319. Verdu-Andres J, Campins-Falco P, Herraez-Hernandez R. Enantioselective analysis of amphetamine-related designer drugs in body fluids using liquid chromatography and solid-phase derivatization. Chromatographia 2004;60(9-10):537.


Couch RAF, Moore G. Detection of 1-benzylpiperazine, a designer recreational drug marketed in New Zealand. Clinical And Experimental Pharmacology And Physiology 2004;31(11):A227. Denis CM, Baryla NE. Determination of piperazine in pharmaceutical drug substances using capillary electrophoresis with indirect UV detection. J Chromatogr A, Mar 2006; 1110(1-2): 268-71. GadzalaKopciuch R. Accurate HPLC determination of piperazine residues in the presence of other secondary and primary amines. Journal of Liquid Chromatography & Related Technologies 2005;28(14):2211. Inoue H, Iwata Y-T, Kanamori T, Miyaguchi H, Tsujikawa K, Kuwayama K, Tsutsumi H, Katagi M, Tsuchihashi H, Kiski T. Analysis of benzylpiperazine-like compounds. Japanese Journal of Forensic Identification 2004;9(2):165. [Microgram Editor’s Notes: Provides comprehensive analytical data for BZP and TFMPP. Contact: National Research Institute of Police Science, 6-3-1 Kashiwanoha, Kashiwa, Chiba 277-0882, Japan.] Lecompte Y, Evrard I, Arditti J. [Metachlorophenylpiperazine (mCPP): a new designer drug]. Therapie, Nov 2006; 61(6): 523-30.


Lovely AE, Wenzel TJ. Chiral NMR discrimination of piperidines and piperazines using (18-crown-6)-2,3,11,12-tetracarboxylic acid. J Org Chem, Nov 2006; 71(24): 9178-82. Tsutsumi H, Katagi M, Miki A, Shima N, Kamata T, Nakajima K, Inoue H, Kishi T, Tsuchihashi H. Isolation, identification and excretion profile of the principal urinary metabolite of the recently banned designer drug 1-(3trifluoromethylphenyl)piperazine (TFMPP) in rats. XENOBIOTICA 2005;35(1):107. Tsutsumi H, Katagi M, Miki A, Shima N, Kamata T, Nakajima K, Inoue H, Kishi T, Tsuchihashi H. Metabolism and the urinary excretion profile of the recently scheduled designer drug N-Benzylpiperazine (BZP) in the rat. J Anal Toxicol, Jan 2006; 30(1): 38-43. Tsutsumi H, Katagi M, Miki A, Shima N, Kamata T, Nishikawa M, Nakajima K, Tsuchihashi H. Development of simultaneous gas chromatography-mass spectrometric and liquid chromatography-electrospray ionization mass spectrometric determination method for the new designer drugs, Nbenzylpiperazine (BZP), 1-(3-trifluoromethylphenyl)piperazine (TFMPP) and their main metabolites in urine. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2005;819(2):315. Wu ZJ, Li GY, Fang DM, Qi HY, Ren WJ, Zhang GL. Electrospray tandem mass spectrometry of epipolythiodioxopiperazines. J Mass Spectrom, Jun 2007; 42(6): 74960. Wu N, Yehl PM, Gauthier D, Dovletoglou A. Retention and thermodynamic studies of piperazine diastereomers in reversed-phase liquid chromatography. Chromatographia 2004;59(3-4):189.


Conemans JMH, Van Der Burgt AAM, Van Rooij JML, Pijnenburg CC. The simultaneous determination of illicit drugs with HPLC-DAD. Bull TIAFT 2004;34(1):11. [Microgram Editor’s Notes: The presented method is applied to drug powders, various dosage forms, and various biological matrices, in a clinical setting. Contact: Ziekenhuisapotheek Noordoost-Brabant, Hervensebaan 2, 5232 JL’sHertogenbosch, The Netherlands.] Day JS, Edwards HGM, Dobrowski SA, Voice AM. The detection of drugs of abuse in fingerprints using Raman spectroscopy II: Cyanoacrylate-fumed fingerprints. Spectrochimica Acta 2004;60:1725. [Microgram Editor’s Notes: Includes analyses of codeine, cocaine, amphetamine, barbital, nitrazepam, and five common adulterants. Contact: Chemical and Forensic Sciences, University of Bradford, Bradford, West Yorkshire, BD7 1DP, UK.]



He H, Sun C, Wang XR, PhamHuy C, ChikhiChorfi N, Galons H, Thevenin M, Claude JR, Warnet JM. Solid-phase extraction of methadone enantiomers and benzodiazepines in biological fluids by two polymeric cartridges for liquid chromatographic analysis. Journal of Chromatography B Analytical Technologies in the Biomedical and Life Sciences 2005;814(2):385. Magnuson EE, Burnett LJ. Screening system for detection of contraband swallowed narcotics. Applied Magnetic Resonance 2004;25(3-4):567. [Microgram Editor’s Notes: Presents a nonimaging, low-frequency NMR technique to detect pellets of heroin or cocaine. Contact: Quantum Magnetics, Inc., San Diego, CA] Maslanka A, Krzek J. Densitometric high performance thin-layer chromatography identification and quantitative analysis of psychotropic drugs. Journal of AOAC International 2005;88(1):70. Nordgren HK, Holmgren P, Liljeberg P, Eriksson N, Beck O. Application of direct urine LC-MS-MS analysis for screening of novel substances in drug abusers. Journal Of Analytical Toxicology 2005;29(4):234. Ohyama K, Wada M, Ohba Y, Fujishita O, Nakashima K, Kuroda N. Rapid separation of barbiturates and benzodiazepines by capillary electrochromatography with 3-(1,8-naththalimido)propyl-modified silyl silica gel. Biomedical Chromatography 2004;18(6):396. [Microgram Editor’s Notes: Barbiturates: Barbital, phenobarbital, secobarbital, thiopental, benzodiazepines: Nitrazepam, diazepam, triazolam. Contact: Nagasaki Univ, Course Pharmaceut Sci, Grad Sch Biomed Sci, 112 Bunkyo Machi, Nagasaki 8528521, Japan.] Strano-Rossi S, Molaioni F, Botre F. Application of solid-phase microextraction to antidoping analysis: Determination of stimulants, narcotics, and other classes of substances excreted free in urine. Journal of Analytical Toxicology 2005;29(4):217. Zhang C S, Liu K l, Zheng H, He Y, Wang Z h, Wang J. Investigation of rolling pills by GC/MS. Wuhan Huagong Xueyuan Xuebao 2004;26(1):9. [Microgram Editor’s Notes: Abstract (and title) are unclear appears to be an analysis of a case of tablets containing methamphetamine, ephedrine, caffeine, and ketamine. This article is written in Chinese. Contact: Institute of Forensic Science of Public Security Ministry of China, Beijing 100038, Peop. Rep. China.]


Poklis A. Propoxyphene: Still popular after five decades of use. Clinical and Forensic Toxicology News 2004:5. [Microgram Editor’s Notes: An overview of the title compound. Contact: Dept. of Chemistry and Forensic Science, Virginia Commonwealth University, Richmond, VA] Schifano F, Deluca P, Baldacchino A. Online availability of dextropropoxyphene over time, 2003-2005. Cyberpsychol Behav, Aug 2006; 9(4): 404-9.


Psilocybin Mushrooms, Psilocybin, and Psilocin:

Anastos N, Barnett NW, Lewis SW, Gathergood N, Scammells PJ, Sims DN. Determination of psilocin and psilocybin using flow injection analysis with acidic potassium permanganate and tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence detection, respectively. Talanta 2005;67(2):354. Anastos N, Barnett NW, Pfeffer FM, Lewis SW. Investigation into the temporal stability of aqueous standard solutions of psilocin and psilocybin using high performance liquid chromatography. Sci Justice, Apr 2006; 46(2): 91-6. Anastos N, Lewis SW, Barnett NW, Sims DN. The determination of psilocin and psilocybin in hallucinogenic mushrooms by HPLC utilizing a dual reagent acidic potassium permanganate and tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence detection system. J Forensic Sci, Jan 2006; 51(1): 45-51. Jensen N, Gartz J, Laatsch H. Aeruginascin, a trimethylammonium analogue of psilocybin from the hallucinogenic mushroom Inocybe aeruginascens. Planta Med, Jun 2006; 72(7): 665-6. Kamata T, Nishikawa M, Katagi M, Tsuchihashi H. Liquid chromatography - mass spectrometric and liquid chromatography - tandem mass spectrometric determination of hallucinogenic indoles psilocin and psilocybin in “Magic Mushroom” samples. Journal of Forensic Sciences 2005;50(2):336. Rodriguez-Cruz SE. Analysis and characterization of psilocybin and psilocin using liquid chromatography - electrospray ionization mass spectrometry (LC-ESI-MS) with collision induced dissociation (CID) and source induced dissociation (SID). Microgram Journal 2005;3(3-4):175. [Microgram Editor’s Notes: Presents the title study. Contact: U.S. Department of Justice, Drug Enforcement Administration, Southwest Laboratory, 2815 Scott Street, Vista, CA 92081.] Saito K, Toyo'oka T, Kato M, Fukushima T, Shirota O, Goda Y. Determination of psilocybin in hallucinogenic mushrooms by reversed-phase liquid chromatography with fluorescence detection. Talanta 2005;66(3):562. Yamaguchi M, Saito T, Horiguchi Y, Ogawa K, Tsuchiya Y, Hishinuma K, Chikuma T, Makino Y, Hojo H. Preparation of monoclonal antibodies reactive to a hallucinogenic drug, psilocin. Journal of Health Sciences 2004;50(6):600. [Microgram Editor’s Notes: Focus is on detection and identification of “magic mushrooms”. Contact: Department of Hygienic Chemistry, Showa Pharmaceutical University, Tokyo, Japan 194-8543.]

Psychotria Viridis: Salvia Divinorum: Bertea CM, Luciano P, Bossi S, Leoni F, Baiocchi C, Medana C, Azzolin CMM, Temporale G, Lombardozzi MA, Maffei ME. PCR and PCR-RFLP of the 5S-rRNA-



NTS region and salvinorin A analyses for the rapid and unequivocal determination of Salvia divinorum. Phytochemistry 2006;67:371. Bucheler R, Gleiter CH, Schwoerer R, Gaertner I. Use of nonprohibited hallucinogenic plants: Increasing relevance for public health? A case report and literature review on the consumption of Salvia divinorum. Pharmacopsychiatry 2005;38(1):1. Harding WW, Schmidt M, Tidgewell K, Kannan P, Holden KG, Gilmour B, Navarro H, Rothman RB, Prisinzano TE. Synthetic studies of neoclerodane diterpenes from Salvia divinorum: semisynthesis of salvinicins A and B and other chemical transformations of salvinorin A. J Nat Prod, Jan 2006; 69(1): 107-12. Harding WW, Schmidt M, Tidgewell K, Kannan P, Holden KG, Dersch CM, Rothman RB, Prisinzano TE. Synthetic studies of neoclerodane diterpenes from Salvia divinorum: selective modification of the furan ring. Bioorg Med Chem Lett, Jun 2006; 16(12): 3170-4. Lee DYW, Karnati WR, He MS, LiuChen LY, Kondaveti L, Ma ZZ, Wang YL, Chen Y, Beguin C, Carlezon WA, Cohen B. Synthesis and in vitro pharmacological studies of new C(2) modified salvinorin A analogues. Bioorganic & Medicinal Chemistry Letters 2005;15(16):3744. Lee DY, He M, Liu-Chen LY, Wang Y, Li JG, Xu W, Ma Z, Carlezon Jr WA, Cohen B. Synthesis and in vitro pharmacological studies of new C(4)-modified salvinorin A analogues. Bioorg Med Chem Lett, Nov 2006; 16(21): 5498-502. Lee DYW, Ma ZZ, LiuChen LY, Wang YL, Chen Y, Carlezon WA, Cohen B. New neoclerodane diterpenoids isolated from the leaves of Salvia divinorum and their binding affinities for human kappa opioid receptors. Bioorganic & Medicinal Chemistry 2005;13(19):5635. Lingham AR, Hugel HM, Rook TJ. Studies towards the synthesis of Salvinorin A. Australian Journal of Chemistry 2006;59:340. [Microgram Editor’s Notes: Presents the title study. Contact: RMIT University, School of Applied Sciences, Melbourne VIC 3001, Australia.] Medana C, Massolino C, Pazzi M, Baiocchi C. Determination of salvinorins and divinatorins in Salvia divinorum leaves by liquid chromatography/multistage mass spectrometry. Rapid Commun Mass Spectrom, Jan 2006; 20(2): 131-6. Munro TA, Goetchius GW, Roth BL, Vortherms TA, Rizzacasa MA. Autooxidation of salvinorin A under basic conditions. Journal of Organic Chemistry 2005;70(24):10057. Munro TA, Rizzacasa MA, Roth BL, Toth BA, Yan F. Studies towards the pharmacophore of salvinorin A, a potent kappa opioid receptor agonist. Journal of Medicinal Chemistry 2005;48(2):345.


Pichini S, Abanades S, Farre M, Pellegrini M, Marchei E, Pacifici R, de la Torre R, Zuccaro P. Quantification of the plant-derived hallucinogen Salvinorin A in conventional and non-conventional biological fluids by gas chromatography/mass spectrometry after Salvia divinorum smoking. Rapid Communications in Mass Spectrometry 2005;19(12):1649. Schmidt MS, Prisinzano TE, Tidgewell K, Harding W, Kreek MJ, Murry DJ. Determination of Salvinorin A in body fluids by high performance liquid chromatography - Atmospheric pressure chemical ionization. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2005;818(2):221. Shirota O, Nagamatsu K, Sekita S. Neo-clerodane diterpenes from the hallucinogenic sage Salvia divinorum. J Nat Prod, Dec 2006; 69(12): 1782-6. Siemann H, Specka M, Schifano F, Deluca P, Scherbaum N. [Salvia divinorum-representation of a new drug in the Internet]. Gesundheitswesen, May 2006; 68(5): 323-7. Tidgewell K, Harding WW, Lozama A, Cobb H, Shah K, Kannan P, Dersch CM, Parrish D, Deschamps JR, Rothman RB, Prisinzano TE. Synthesis of salvinorin A analogues as opioid receptor probes. J Nat Prod, Jun 2006; 69(6): 914-8. Vortherms TA, Roth BL. Salvinorin A: From Natural Product to Human Therapeutics. Mol. Interv. Oct 2006; 6: 257 - 265. Wolowich WR, Perkins AM, Cienki JJ. Analysis of the psychoactive terpenoid Salvinorin A content in five Salvia divinorum herbal products. Pharmacotherapy 2006;26(9):1268. [Microgram Editor’s Notes: Analyses were conducted using HPLC and TLC/GC/MS. The samples were purchased from Internet and “Head Shops.” The samples were all subpotent with respect to stated Salvinorin A content, and three also contained unreported adulterants. Contact: Nova Southeastern University, 3200 University Drive, Fort Lauderdale, FL 33328.]


Nakamura M, Ono M, Nakajima T, Ito Y, Aketo T, Haginaka J. Uniformly sized molecularly imprinted polymer for atropine and its application to the determination of atropine and scopolamine in pharmaceutical preparations containing scopolia extract. Journal of Pharmaceutical and Biomedical Analysis 2005;37(2):231. Ondra P, Zednikova K, Valka I. Detection and determination of abused hallucinogens in biological material. Neuro Endocrinol Lett, Dec 2006; 27 Suppl 2: 125-9. Tsujikawa K, Mohri H, Kuwayama K, Miyaguchi H, Iwata Y, Gohda A, Fukushima S, Inoue S, Kishi T. Analysis of hallucinogenic constituents in Amanita mushrooms circulated in Japan. Forensic Sci Int, Dec 2006; 164(2-3): 172-8.



Zhang L, Ma L, Gong H, Li L. Determination of scopolamine content in compound Huangqi capsules by HPLC. Zhongcaoyao 2005;36(11):1661. [Microgram Editor’s Notes: Presents the title analysis. This article is written in Chinese. Contact: Department of Pharmaceutical Chemistry, Medical College of Chinese People’s Armed Police Force, Tianjin 300162, Peop. Rep. China.]


Amundsen LK, Kokkonen JT, Rovio S, Siren H. Analysis of anabolic steroids by partial filling micellar electrokinetic capillary chromatography and electrospray mass spectrometry. Journal of Chromatography A 2004;1040(1):123. [Microgram Editor’s Notes: Presents the title analysis on six steroids (androstenedione, metandienone, fluoxymesterone, methyltestosterone, 17-epimetandienone, and testosterone). Contact: VTT Processes, FIN 02044 Espoo, Finland.] Antignac JP, Brosseaud A, GaudinHirret I, Andre F, LeBizec B. Analytical strategies for the direct mass spectrometric analysis of steroid and corticosteroid phase II metabolites. Steroids 2005;70(3):205. Blackledge RD. The identification of 1-dehydromethandrostenolone. Microgram Journal 2005;3(3-4):186. [Microgram Editor’s Notes: A recent steroid seizure was identified by GC/MS as 1-dehydromethandrostenolone, a positional isomer of methyltestosterone. Contact: Naval Criminal Investigative Service, Regional Forensic Laboratory, 3405 Welles St., Ste. 3, San Diego, CA 92136.] Fourcroy J. Designer steroids: Past, present, and future. Current Opinion in Endocrinology & Diabetes 2006;13(3):306. [Microgram Editor’s Notes: A historical overview and minor review of the title subject. Contact: Department of Surgery/Urology, Uniformed Services University Health Sciences, Bethesda, MD] Gaertner P, Bica K, Felzmann W, Forsdahl G, Gmeiner G. Synthesis and analytics of 2,2,3,4,4-d5-19-nor-5alpha-androsterone--an internal standard in doping analysis. Steroids, May 2007; 72(5): 429-36. Gentili A. Determination of non-steroidal anti-inflammatory drugs in environmental samples by chromatographic and electrophoretic techniques. Anal Bioanal Chem, Feb 2007; 387(4): 1185-202. Gomes RL, Birkett JW, Scrimshaw MD, Lester JN. Simultaneous determination of natural and synthetic steroid estrogens and their conjugates in aqueous matrices by liquid chromatography/mass spectrometry. International Journal Of Environmental Analytical Chemistry 2005;85(1):1. Gorog S. Recent advances in the analysis of steroid hormones and related drugs. Analytical Sciences 2004;20(5):767. Guan F, Soma LR, Luo Y, Uboh CE, Peterman S. Collision-induced dissociation pathways of anabolic steroids by electrospray ionization tandem mass spectrometry. Journal of the American Society for Mass Spectrometry 2006;17(4):477. [Microgram


Editor’s Notes: Fragmentation pathways were elucidated for boldenone, methandrostenolone, tetrahydrogestrinone, trenbolone, normethandrolone, and mibolerone. Contact: Department of Clinical Studies, School of Veterinary Medicine, University of Pennsylvania, Kennett Square, PA (zip code not provided).] Hu JY, Zhang HF, Chang H. Improved method for analyzing estrogens in water by liquid chromatography-electrospray mass spectrometry. Journal of Chromatography A 2005;1070(1-2):221. Lommen A, van der Weg G, van Engelen MC, Bor G, Hoogenboom LA, Nielen MW. An untargeted metabolomics approach to contaminant analysis: pinpointing potential unknown compounds. Anal Chim Acta, Feb 2007; 584(1): 43-9. Martello S, Felli M, Chiarotti M. Survey of nutritional supplements for selected illegal anabolic steroids and ephedrine using LC-MS/MS and GC-MS methods, respectively. Food Addit Contam, Mar 2007; 24(3): 258-65. MateusAvois L, Mangin P, Saugy M. Use of ion trap gas chromatography-multiple mass spectrometry for the detection and confirmation of 3'hydroxystanozolol at trace levels in urine for doping control. Journal of Chromatography B Analytical Technologies in the Biomedical and Life Sciences 2005;816(1-2):193. Nielen MW, van Engelen MC, Zuiderent R, Ramaker R. Screening and confirmation criteria for hormone residue analysis using liquid chromatography accurate mass time-of-flight, Fourier transform ion cyclotron resonance and orbitrap mass spectrometry techniques. Anal Chim Acta, Mar 2007; 586(1-2): 122-9. Nielen MWF, Bovee TFH, vanEngelen MC, Rutgers P, Hamers ARM, vanRhijn IHA, Hoogenboom LRAP. Urine testing for designer steroids by liquid chromatography with androgen bioassay detection and electrospray quadrupole time-of-flight mass spectrometry identification. Analytical Chemistry 2006;78(2):424. Noppe H, Verheyden K, Gillis W, Courtheyn D, Vanthemsche P, De Brabander HF. Multi-analyte approach for the determination of ng L(-1) levels of steroid hormones in unidentified aqueous samples. Anal Chim Acta, Mar 2007; 586(1-2): 22-9. Panusa A, Ottaviani M, Picardo M, Camera E, Gagliardi L, Chimenti P, Granese A, Tonelli D. Analysis of corticosteroids by high performance liquid chromatographyelectrospray mass spectrometry. Analyst 2004;129(8):719. Pozo OJ, Van Eenoo P, Deventer K, Delbeke FT. Ionization of anabolic steroids by adduct formation in liquid chromatography electrospray mass spectrometry. J Mass Spectrom, Apr 2007; 42(4): 497-516. Sekera MH, Ahrens BD, Chang YC, Starcevic B, Georgakopoulos C, Catlin DH. Another designer steroid: discovery, synthesis, and detection of madol in urine. Rapid Communications in Mass Spectrometry 2005;19(6):781.



Seo J, Kim HY, Chung BC, Hong JK. Simultaneous determination of anabolic steroids and synthetic hormones in meat by freezing-lipid filtration, solid-phase extraction and gas chromatography-mass spectrometry. Journal of Chromatography A 2005;1067(1-2):303. Thevis M, Bommerich U, Opfermann G, Schaenzer W. Characterization of chemically modified steroids for doping control purposes by electrospray ionization tandem mass spectrometry. Journal of Mass Spectrometry 2005;40(4):494. Thevis M, Geyer H, Mareck U, Schanzer W. Screening for unknown synthetic steroids in human urine by liquid chromatography-tandem mass spectrometry. Journal Of Mass Spectrometry 2005;40(7):955. Thevis M, Schanzer W. Mass spectrometric analysis of androstan-17 beta-ol-3-one and androstadiene-17 beta-ol-3-one isomers. Journal of the American society for mass spectrometry 2005;16(10):1660. Touber ME, van Engelen MC, Georgakopoulus C, van Rhijn JA, Nielen MW. Multidetection of corticosteroids in sports doping and veterinary control using highresolution liquid chromatography/time-of-flight mass spectrometry. Anal Chim Acta, Mar 2007; 586(1-2): 137-46. Van Poucke C, Detavernier C, Van Cauwenberghe R, Van Peteghem C. Determination of anabolic steroids in dietary supplements by liquid chromatography-tandem mass spectrometry. Anal Chim Acta, Mar 2007; 586(1-2): 35-42. Van Thuyne W, Delbeke FT. Validation of a GC-MS screening method for anabolizing agents in solid nutritional supplements. Biomedical Chromatography 2004;18(3):155. [Microgram Editor’s Notes: Presents the title study, including analyses of testosterone, nandralone, stanazolol, metandienone, and various prohormones. Contact: Doping Control Laboratory, Ghent University, B-9820 Merelbeke, Belg.] Verheyden K, Le Bizec B, Courtheyn D, Mortier V, Vandewiele M, Gillis W, Vanthemsche P, De Brabander HF, Noppe H. Mass spectrometric detection of and similarities between 1-androgens. Anal Chim Acta, Mar 2007; 586(1-2): 57-72. Xie ZH, Ouyang XQ, Guo LQ, Lin XC, Chen GN. Determination of methyltestosterone using flow injection with chemiluminescence detection. Luminescence 2005;20(3):231. Yasueda S, Higashiyama M, Shirasaki Y, Inada K, Ohtori A. An HPLC method to evaluate purity of a steroidal drug, loteprednol etabonate. Journal of Pharmaceutical and Biomedical Analysis 2004;36(2):309. Zarzycki PK, Kulhanek KM, Smith R, Clifton VL. Determination of steroids in human plasma using temperature-dependent inclusion chromatography for metabolomic investigations. Journal of Chromatography A 2006;1104(1-2):203. 204

Zuo Y, Zhang K, Lin Y. Microwave-accelerated derivatization for the simultaneous gas chromatographic-mass spectrometric analysis of natural and synthetic estrogenic steroids. J Chromatogr A, May 2007; 1148(2): 211-8.

(Designer) Tryptamines (see also Psilocybin):

Brandt SD, Mansell D, Freeman S, Fleet IA, Alder JF. Analytical characterisation of the routes by thermolytic decarboxylation from tryptophan to tryptamine using ketone catalysts, resulting in tetrahydro-beta-carboline formation. J Pharm Biomed Anal, Jun 2006; 41(3): 872-82. Buchanan MS, Carroll AR, Pass D, Quinn RJ. NMR spectral assignments of a new chlorotryptamine alkaloid and its analogues from Acacia confusa. Magn Reson Chem, Apr 2007; 45(4): 359-61. Clare BW. A novel quantum theoretic QSAR for hallucinogenic tryptamines: a major factor is the orientation of pi orbital nodes. Journal Of Molecular StructureTheochem 2004;712(1-3):143. Huhn C, Putz M, Martin N, Dahlenburg R, Pyell U. Determination of tryptamine derivatives in illicit synthetic drugs by capillary electrophoresis and ultraviolet laser-induced fluorescence detection. Electrophoresis 2005;26(12):2391. Ishida T, Kudo K, Kiyoshima A, Inoue H, Tsuji A, Ikeda N. Sensitive determination of alpha-methyltryptamine (AMT) and 5-methoxy-N,N-diisopropyltryptamine (5MeO-DIPT) in whole blood and urine using gas chromatography-mass spectrometry. Journal of Chromatography B - Analytical Technologies in the Biomedical and Life Sciences 2005;823(1):47. Kamata T, Katagi M, Kamata HT, Miki A, Shima N, Zaitsu K, Nishikawa M, Tanaka E, Honda K, Tsuchihashi H. Metabolism of the psychotomimetic tryptamine derivative 5-methoxy-n,n-diisopropyltryptamine in humans: identification and quantification of its urinary metabolites. Drug Metab. Dispos., Feb 2006; 34: 281-287. Kato N, Kojima T, Yoshiyagawa S, Ohta H, Toriba A, Nishimura H, Hayakawa K. Rapid and sensitive determination of tryptophan, serotonin and psychoactive tryptamines by thin-layer chromatography/fluorescence detection. J Chromatogr A, Mar 2007; 1145(1-2): 229-33. Kikura-Hanajiri R, Hayashi M, Saisho K, Goda Y. Simultaneous determination of nineteen hallucinogenic tryptamines/beta-carbolines and phenethylamines using gas chromatography - mass spectrometry and liquid chromatography - electrospray ionisation - mass spectrometry. Journal of Chromatography B - Analytical Technologies in the Biomedical and Life Sciences 2005;825(1):29. Koepke J, Ma XY, Fritzsch U, Michel H, Stockigt J. Crystallization and preliminary X-ray analysis of strictosidine synthase and its complex with the substrate



tryptamine. Acta Crystallographica Section D - Biological Crystallography 2005;61, Part 6):690. Nguyen TV, Korter TM, Pratt DW. Tryptamine in the gas phase. A high resolution laser study of the structural and dynamic properties of its ground and electronically excited states. Molecular Physics 2005;103(11-12):1603. Rodriguez-Cruz SE. Analysis and characterization of designer tryptamines using electrospray ionization mass spectrometry (ESI-MS). Microgram Journal 2005;3(34):107. [Microgram Editor’s Notes: Presents the title study on 12 “designer” tryptamines. Contact: U.S. Department of Justice, Drug Enforcement Administration, Southwest Laboratory, 2815 Scott Street, Vista, CA 92081.] Rothchild R. Proton and carbon-13 NMR studies of some tryptamines, precursors, and derivatives: Ab initio calculations for optimized structures. Spectroscopy Letters 2005;38(4-5):521. Vorce SP, Sklerov JH. A general screening and confirmation approach to the analysis of designer tryptamines and phenethylamines in blood and urine using GC-EI-MS and HPLCelectrospray-MS. Journal of Analytical Toxicology 2004;28(6):407. [Microgram Editor’s Notes: Presents the analysis of the pentafluoropropionic derivatives of the title drugs, focus is on biological matrices. Contact: Office of the Armed Forces Medical Examiner, Division of Forensic Toxicology, Armed Forces Institute of Pathology, Rockville, MD 20850.] Wilson JM, McGeorge F, Smolinske S, Meatherall R. A “Foxy” intoxication. Forensic Science International 2005;148(1):31. [Microgram Editor’s Notes: Focus is toxicological, but includes mass spectra for the title compound (N,N-diisopropyl-5methoxytryptamine, also known as “Foxy-Methoxy”) and N,N-diisopropyl-5hydroxytryptamine. Note that there are some nomenclature problems in this article, and the structure and term 5-ethoxy-diisopropyltryptamine are incorrectly used in several instances. Contact: Laboratory Medicine, St. Boniface General Hospital, 409 Tache Avenue, Winnipeg Manitoba, Canada R2H 2A6.] Wu YC, Chang FR, Chen CY. Tryptamine-derived amides and alkaloids from the seeds of Annona atemoya. Journal of Natural Products 2005;68(3):406.


Bharathi CH, Prabahar KJ, Prasad CS, Kumar MS, Magesh S, Handa VK, Dandala R, and A Naidu A. Impurity profile study of zaleplon. J Pharm Biomed Anal, May 2007; 44(1): 101-9. Zhang BB, Zhang ZJ, Tian Y, Xu FG, Chen Y. High-performance liquid chromatography-atmospheric pressure chemical ionisation-mass spectrometry determination of zaleplon in human plasma. Journal of Pharmaceutical and Biomedical Analysis 2006;40(3):707.



Kelani KM. Selective potentiometric determination of zolpidem hemitartrate in tablets and biological fluids by using polymeric membrane electrodes. Journal of the AOAC International 2004;87(6):1309. [Microgram Editor’s Notes: Presents the title study, using four different polymeric membrane sensors. Contact: Cairo University, Faculty of Pharmacy, Department of Analytical Chemistry, Kasr el Aini St., PO Box 11562, Cairo, Egypt.] Laviana L, Mangas C, Fernandez-Mari F, Bayod M, Blanco D. Determination and inprocess control of Zolpidem synthesis by high-performance liquid chromatography. Journal of Pharmaceutical and Biomediacal Analysis 2004;36(4):925. [Microgram Editor’s Notes: Includes HPLC analysis of the drug and its synthetic intermediates. Contact: Univ Oviedo, Dept Phys & Analyt Chem, Julian Claveria, Oviedo, Spain.] Radi AE, Bekhiet G, Wahdan T. Electrochemical study of Zolpidem at glassy carbon electrode and its determination in a tablet dosage form by differential pulse voltametry. Chemical & Pharmaceutical Bulletin 2004;52(9):1063. [Microgram Editor’s Notes: Presents the title study. Contact: Mansoura Univ, Fac Sci Dumyat, Dept Chem, Dumyat 34517, Egypt.]

Zopiclone: Miscellaneous:

Abanades S, Peiro AM, Farre M. Club drugs: old medicines as new party drugs. Medicina Clinica 2004;123(8):305. Abbasi K, Bhanger MI, Khuhawar MY. Capillary gas chromatographic determination of phenylpropanolamine in pharmaceutical preparation. Journal of Pharmaceutical and Biomedical Analysis 2006;41(3):998. Aderjon R, Herbold M. Forensic analysis and therapeutic monitoring of psychotropic drugs. Pharmacopsychiatry 2005;38(1):42 Barthelson RA, Sundareshan P, Galbraith DW, Woosley RL. Development of a comprehensive detection method for medicinal and toxic plant species. American Journal of Botany 2006;93(4):566. Bossong MG, Van Dijk JP, Niesink RJM. Methylone and mCPP, two new drugs of abuse? Addiction Biology 2005;10:321. Breton D, Buret D, Clair P, Lafosse A. Chiral separation of atropine by highperformance liquid chromatography. Journal Of Chromatography A 2005;1088(12):104. Camilleri AM. Underground pill testing, down under. Forensic Science International 2005;151(1):53.



Hummel D, Loffler D, Fink G, Ternes TA. Simultaneous determination of psychoactive drugs and their metabolites in aqueous matrices by liquid chromatography mass Spectrometry. Environ Sci Technol, Dec 2006; 40(23): 7321-8. Kim SC, Chung H, Lee SK, Park YH, Yoo YC, Yun Y-P. Simultaneous analysis of d-3methoxy-17-methylmorphinan and l-3-methoxy-17-methylmorphinan by high pressure liquid chromatography equipped with PDA. Forensic Science International 2006;161(2-3):185. [Microgram Editor’s Notes: The title compounds are better known as dextromethorphan and levomethorphan. The technique used a chiral column. 32 confiscated samples were analyzed. Contact: National Institute of Scientific Investigation, Chungbuk National University, 331-1 SinWol 7-dong, Yang-Chun Gu, Seoul 158-707, S. Korea.] Kuila DK, Muhkopadhyay B, Lahiri SC. Identification and estimation of methaqualone in toffee samples using gas chromatography - mass spectrometry, Fourier transform infrared spectrometry, and high-performance thin-layer chromatography. Forensic Science Communications 2006;8(4):(No Page Numbers). [Microgram Editor’s Notes: Presents the analysis of some Indian brand toffee samples suspected to contain adulterants/hypnotic drugs and alcohol. Note that FSC is an on-line journal. Contact: Central Forensic Science Laboratory, Kolkata, India.] Lachenmeier DW, Emmert J, Kuballa T, Sartor G. Thujone-Cause of absinthism? Forensic Science International 2006;158(1):1. Lurie IS, Cox KA. Rapid chiral separation of dextro- and levo-methorphan using capillary electrophoresis with dynamically coated capillaries. Microgram Journal 2005;3(3-4):138. [Microgram Editor’s Notes: Presents the title study. Contact: U.S. Department of Justice, Drug Enforcement Administration, Special Testing and Research Laboratory, 22624 Dulles Summit Court, Dulles, VA 20166.] Miller B, McKibben T. Povidone-iodine. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(2):18. [Microgram Editor’s Notes: An overview of methods for identification of the title formulation. Note that JCLICA is a law enforcement restricted journal. Contact: Colorado Bureau of Investigation, Forensic Laboratory, Pueblo, CO (zip code not provided).] Neuvonen K, Neuvonen H, Fulop F. Effect of 4-substitution on psychotomimetic activity of 2,5-dimethoxy amphetamines as studied by means of different substituent parameter scales. Bioorganic & Medicinal Chemistry Letters 2006;16(13):3495. [Microgram Editor’s Notes: Presents the title study, using various Hammett substituent scales. Contact: Univ Turku, Dept Chem, FIN-20014 Turku, Finland.] Onal A, Kepekci SE, Cetin SM, Erturk S. Spectrophotometric determination of certain antidepressants in pharmaceutical preparations. J AOAC Int, Jul 2006; 89(4): 966-71.


Ondra P, Zednikova K, Valka I. Detection and determination of abused hallucinogens in biological material. Neuro Endocrinol Lett, Dec 2006; 27 Suppl 2: 125-9. Rosner P, Quednow B, Girreser U, Junge T. Isomeric Fluoro-methoxyphenylalkylamines: a new series of controlled-substance analogues (designer drugs). Forensic Science International 2005;148(2-3):143. Sauer C, Peters FT, Staack RF, Fritschi G, Maurer HH. New designer drug N-(1phenylcyclohexyl)-3-ethoxypropanamine (PCEPA): Studies on its metabolism and toxicological detection in rat urine using gas chromatographic/mass spectrometric techniques. J Mass Spectrom, Aug 2006; 41(8): 1014-29. Seto Y. Alkyl nitrites. Drugs and Poisons in Humans 2005:153. Simonov EA, Salomatin VE. Preliminary analysis of substances of unknown origin and complex medicinal formulations. Mikroelementy y Meditsine 2005;6(3):35. [Microgram Editor’s Notes: Abstract is unclear as to what technique is used. “Narcotic materials and psychotropic substances” are mentioned. This article is written in Russian. Contact: Tsentr Sudebno-Med. Kriminal Eksp., Minist. Oborony Ross. Fed., Russia.] Srinivasu MK, Rao BM, Sridhar G, Kumar PR, Chandrasekhar KB, Islam A. A validated chiral LC method for the determination of Zolmitriptan and its potential impurities. Journal of Pharmaceutical and Biomedical Analysis 2005;37(3):453. Szkutova M, Balikova M. [Screening and identification of stimulant and psychedelic drugs as acetyl-derivatives by GC-MS]. Soud Lek, Oct 2006; 51(4): 55-66. Talaty N, Takats Z, Cooks RG. Rapid in situ detection of alkaloids in plant tissue under ambient conditions using desorption electrospray ionization. Analyst 2005;130(12):1624. van Amsterdam JGC, Best W, Opperhuizen A, de Wolff FA. Evaluation of a procedure to assess the adverse effects of illicit drugs. Regulatory Toxicology and Pharmacology 2004;39(1):1. [Microgram Editor’s Notes: Presents a theoretical approach to the title issue, focusing on new synthetic illicit drugs. Contact: Pathology and Genetics, Laboratory for Toxicology, National Institute for Public Health and the Environment (RIVM), Bilthoven, Neth.] Westphal F, Junge T, Rosne Pr, Fritschi G, Klein B, Girreser U. Mass spectral and NMR spectral data of two new designer drugs with an alpha-aminophenone structure: 4'-methyl-alpha-pyrrolidinohexanophenone and 4'-methyl-alphapyrrolidinobutyrophenone. Forensic Sci Int, Jun 2007; 169(1): 32-42. Yuan X, Forman BM. Detection of designer steroids. Nuclear Receptor Signaling 2005;3:(No Page Numbers Listed). [Microgram Editor’s Notes: Presents an analytical strategy that detects use of unknown designer steroids “without prior knowledge of their existence”. Focus is toxicological (testing of athletes). Contact: Gene Regulation 209


and Drug Discovery Department, Gonda Diabetes Research Center, The Beckman Research Institute, The City of Hope National Medical Center, Duarte, CA 91010.] Synthesis and/or Cultivation of Abused Substances, their Precursors, and Essential Chemicals Issue: Forensic chemists must maintain familiarity with existing and new clandestine syntheses of abused substances, their precursors, and essential chemicals, and with the cultivation of abused natural products, in order to assist enforcement activities, to ensure safety and effectiveness during enforcement operations, and to provide expert testimony in legal proceedings. Solution: Illicit drug seizures, clandestine laboratory operations, and illicit grow operations are continuously monitored to maintain a comprehensive overview of the field. In cases where new drugs are synthesized, or new methodologies are utilized, case reports are generated for the forensic and enforcement communities. References:

Production of Abused Substances and/or their Precursors and Essential Chemicals:

Ahmadi A, Mahmoudi A. Synthesis and biological properties of 2-hydroxy-1-(1phenyltetralyl)piperidine and some of its intermediates as derivatives of phencyclidine. Arzneimittel - Forschung - Drug Research 2005;55(9):528. Alberico D, Rudolph A, Lautens M. Synthesis of tricyclic heterocycles via a tandem aryl alkylation/heck coupling sequence. J Org Chem, Feb 2007; 72(3): 775-81. Berkheij M, vanderSluis L, Sewing C, denBoer DJ, Terpstra JW, Hiemstra H, Bakker WII, vandenHoogenband A, vanMaarseveen JH. Synthesis of 2-substituted piperazines via direct alpha-lithiation. Tetrahedron Letters 2005;461(4):2369. Black SN, Collier EA, Davey RJ, Roberts RJ. Structure, solubility, screening, and synthesis of molecular salts. J Pharm Sci, May 2007; 96(5): 1053-68. Brandt SD, Freeman S, Fleet IA, McGagh, Alder JF. Analytical chemistry of synthetic routes to psychoactive tryptamines - Part I. Characterisation of the Speeter and Anthony route to 5-methoxy-N,N-diisopropyltryptamine using ESI-MS-MS and ESITOF-MS. Analyst 2004;129(11):1047. [Microgram Editor’s Notes: Presents the title study. Contact: UMIST, Dept Instrumental & Analyt Sci, Manchester M60 1QD, Lancs, England.] Brandt SD, Freeman S, Fleet IA, McGagh P, Alder JF. Analytical chemistry of synthetic routes to psychoactive tryptamines - Part II. Characterisation of the Speeter


and Anthony synthetic route to N,N-dialkylated tryptamines using GC-EI-ITMS, ESI-TQ-MS-MS and NMR. Analyst 2005;130(3):330. Brandt SD, Freeman S, McGagh P, Abdul-Halim N, Alder JF. An analytical perspective on favoured synthetic routes to the psychoactive tryptamines. Journal of Pharmaceutical and Biomedical Analysis 2004;36(4):675. [Microgram Editor’s Notes: Appears to be a review of the topic, focusing on the probable impurities and marker compounds resulting from common illicit syntheses. Contact: Department of Instrumentation and Analytical Science, UMIST, Institute of Science and Technology, P.O. Box 88, Manchester M60 1QD, U.K.] Brandt SD, Freeman S, Fleet IA, Alder JF. Analytical chemistry of synthetic routes to psychoactive tryptamines - Part III. Characterisation of the Speeter and Anthony route to N,N-dialkylated tryptamines using CI-IT-MS-MS. Analyst 2005;130(9):1258. Cami-Kobeci G, Slatford PA, Whittlesey MK, Williams JMJ. N-alkylation of phenethylamine and tryptamine. Bioorganic & Medicinal Chemistry Letters 2005;15(3):535. De SK, Gibbs RA. Scandium(III) triflate as an efficient and reusable catalyst for synthesis of 1,5-benzodiazepine derivatives. Tetrahedron Letters 2005;46(11):1811. DiPari SC, Bordelon JA, Skinner HF. Desloratadine: The reaction byproduct of the reduction of cold tablets containing loratadine with hydriodic acid - red phosphorus. Journal of the Clandestine Laboratory Investigating Chemists Association 2005;15(1):4. Doi K, Miyazawa M, Fujii H, Kojima T. [Analysis of the chemical drugs among structural isomer]. Yakugaku Zasshi, Sep 2006; 126(9): 815-23. Donohoe TJ, Thomas RE. Partial reduction of pyrroles: application to natural product synthesis. Chem Rec, Jan 2007; 7(3): 180-90. Dubash NP, Mangu NK, Satyam A. Synthesis of 7-alkoxy/hydroxy-alphamethyltryptamines. Synthetic Communications 2004;34(10):1791. Gawronski J. Asymmetric syntheses and transformations--tools for chirality multiplication in drug synthesis. Acta Pol Pharm, Sep 2006; 63(5): 333-51. Hansen DB, Joullie MM. The development of novel ninhydrin analogues. Chemical Society Reviews 2005;34(5):408. Heegel RA, Knops LA, Northrop DM, Person EC. Abbreviated reaction times in the red phosphorus iodine manufacturing method. Journal of the Clandestine Laboratory Investigating Chemists Association 2004;14(3):11. [Microgram Editor’s Notes: Presents the title study, details withheld in accordance with Microgram policy. Note that this Journal (JCLICA) is law enforcement restricted. Contact: Washington State Patrol, Marysville Crime Laboratory, 2700 116th Street NE, Suite P, Marysville, WA 98271.] 211


Heegel RA, Northrop DM. “One-Pot” methamphetamine manufacture via the lithium-ammonia method with multi-ingredient, liquid, and/or soft-gel pseudoephedrine preparations. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(1):25. Heureux N, Wouters J, Norberg B, Marko IE. Short, asymmetric synthesis of epimorphine ACNO analogues. Org Biomol Chem, Nov 2006; 4(21): 3898-900. Ivanovic MD, Micovic IV, Vuckovic S, Prostran M, Todorovic Z, Ivanovic ER, Kiricojevic VD, Djordjevic JB, Dosen-Micovic LJ. The synthesis and pharmacological evaluation of ()-2,3-seco-fentanyl analogues. Journal Of The Serbian Chemical Society 2004;69(11):955. Karpiesiuk W, Lehner AF, Hughes CG, Tobin T. Preparation and chromatographic characterization of tetrahydrogestrinone, a new “designer” anabolic steroid. Chromatographia 2004;60(5-6):359. [Microgram Editor’s Notes: The synthesis of THG from gestrinone is reported. Contact: Univ Kentucky, Dept Vet Sci, Maxwell H Gluck Equine Res Ctr, Lexington, KY 40546.] Khedkar V, Tillack A, Michalik M, Beller M. Efficient one-pot synthesis of tryptamines and tryptamine homologues by amination of chloroalkynes. Tetrahedron Letters 2004;45(15):3123. [Microgram Editor’s Notes: Presents the title study. Contact: M Beller, Univ Rostock, Leibniz Inst Organ Katalyse, Buchbinderstr 5-6, D-18005 Rostock, Germany.] Knops LA, Northrop DM, Person EC. Capillary electrophoretic analysis of phosphorus species in clandestine methamphetamine laboratory samples. Journal Of Forensic Sciences 2006;51(1):82. Liu KG, Robichaud AJ. A general and convenient synthesis of N-aryl piperazines. Tetrahedron Letters 2005;46(46):7921. Love DW. [Withheld] being utilized as a source of hydrogen peroxide for iodine recovery. Journal of the Clandestine Laboratory Investigating Chemists Association 2004;14(3):9. [Microgram Editor’s Notes: Describes the use of a commercial product as a source of hydrogen peroxide. The name of the product is withheld in accordance with Microgram policy. Note that this Journal (JCLICA) is law enforcement restricted. Contact: DEA Southwest Laboratory, 2815 Scott Street, Vista, CA 92081.] Love DW, Orlando PM. Examining the specificity of anhydrous ammonia analytical techniques. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(1):14. Milhazes N, Borges F, Calheiros R, Marques MPM. Identification of synthetic precursors of amphetamine amphetamine-like drugs using Raman spectroscopy and ab initio calculations: beta-Methyl-beta-nitrostyrene derivatives. Analyst 2004;129(11):1106. [Microgram Editor’s Notes: The study includes the nitrostyrene 212

precursors for MDMA, MDA, PMA, and 4-MTA. Contact: Univ Coimbra, Fac Ciencias & Tecnol, Unidade I&D Quim Fis Mol, Ap 3126, P-3001401 Coimbra, Portugal.] Moldvai I, Temesvari-Major E, Incze M, Szentirmay K, Gacs-Baitz E, Szantay C. Enantioefficient synthesis of alpha-ergocryptine: First direct synthesis of (+)-lysergic acid. Journal of Organic Chemistry 2004;69(18):5993. [Microgram Editor’s Notes: Presents the title synthesis. Contact: Hungarian Acad Sci, Inst Biomol Chem, Chem Res Ctr, POB 17, H-1525 Budapest, Hungary.] Moore T, Adhikari R, Gunatillake P. Chemosynthesis of bioresorbable poly(Gammabutyrolactone) by ring-opening polymerisation: a review. Biomaterials 2005;26(18):3771.

Person EC, Meyer JA, Vyvyan JR. Structural determination of the principal byproduct of the lithium-ammonia reduction method of methamphetamine manufacture. Journal of Forensic Sciences 2005;50(1):87. [Microgram Editor’s Notes: Identifies the title byproduct (1-(1',4'-cyclohexadienyl)-2-methylaminopropane) via comprehensive spectral and chromatographic methodologies. Contact: Washington State Patrol, Marysville Crime Laboratory, 2700 116th Street NE, Suite P, Marysville, WA 98271.] Poortman-Van Der Meer A. The synthesis of MDMA with NaBH4 as the reducing agent; the “Cold Method.” Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(3):10. [Microgram Editor’s Notes: Details withheld in accordance with Microgram policy. JCLICA is a law enforcement restricted journal. Contact: Netherlands Forensic Institute, Postbus 24044 The Hague, The Netherlands.] Rodriguez WR, Allred RA. Synthesis of trans-4-methylaminorex from norephedrine and potassium cyanate. Microgram Journal 2005;3(3-4):154. [Microgram Editor’s Notes: Presents the title study. Contact: U.S. Department of Justice, Drug Enforcement Administration, Southeast Laboratory, 5205 NW 84th Avenue, Miami, FL 33166.] Schieferecke J, Worley D. Analysis of red phosphorus using a pyrolysis gas chromatograph/mass spectrometer. Journal of Analytical and Applied Pyrolysis 2004;71(1):47. [Microgram Editor’s Notes: For analysis of red P found in clandestine methamphetamine sites. Contact: Kansas Bureau of Investigation Headquarters Laboratory, Topeka, KS 66612.] Swist M, Wilamowski J, Zuba D, Kochana J, Parczewski A. Determination of synthesis route of 1-(3,4-methylenedioxyphenyl)-2-propanone (MDP-2-P) based on impurity profiles of MDMA. Forensic Science International 2005;149(2-3):181.



Tadeusiak EJ. Synthesis of phosphonic analogues of carnitine and gamma-aminobeta-hydroxybutyric acid. Bioorganic Chemistry 2004;32(6):473. Tewari A, Hein M, Zapf A, Beller M. An easy three step synthesis of perfluoroalkylated amphetamines. Tetrahedron Letters 2004;45(41):7703. Trost BM, Tang WP, Toste FD. Divergent enantioselective synthesis of (-)galanthamine and (-)-morphine. Journal of the American Chemical Society 2005;127(42):14785. Uchida K, Yokoshima S, Kan T, Fukuyama T. Total synthesis of (+/-)-morphine. Organic Letters 2006;8(23):5311. [Microgram Editor’s Notes: Presents the title synthesis. Contact: Graduate School of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.] Waumans D, Hermans B, Bruneel N, Tytgat J. A neolignan-type impurity arising from peracid oxidation reaction of anethole in the surreptitious synthesis of 4methoxyamphetamine (PMA). Forensic Science International 2004;143(2-3):133. [Microgram Editor’s Notes: A forensic marker for peracid oxidation of anethole (a precursor for illicit synthesis of PMA) is identified and discussed. Contact: Laboratory of Toxicology, Eduard van Evenstraat 4, 3000 Leuven, Belgium.] Xu YZ, Chen C. Synthesis of deuterium labeled standards of 5-methoxy-N,Ndimethyltryptamine (5-MeO-DMT). Journal of Labelled Compounds & Radiopharmaceuticals 2006;49(10):897. [Microgram Editor’s Notes: Presents the synthesis of the trideuteromethoxy analogue. Contact: Natl Dong Hwa Univ, Dept Chem, Hualien 974, Taiwan.] Xu YZ, Chen CP. Synthesis of deuterium labeled phenethylamine derivatives. Journal of Labelled Compounds & Radiopharmaceuticals 2006;49(13):1187. [Microgram Editor’s Notes: For use as internal standards in GC/MS. Compounds included 2C-B, 2C-C, 2C-I, 2C-T-2, and 2C-T-7. Contact: Natl Dong Hwa Univ, Dept Chem, Soufeng 974, Hualien, Taiwan.] Yadav JS, Reddy BVS, Praveenkumar S, Nagaiah K. Indium(III) bromide: A novel and efficient reagent for the rapid synthesis of 1,5-benzodiazepines under solventfree conditions. Synthesis Stuttgart 2005;(3):480. Zhang QB, Rich JO, Cotterill IC, Pantaleone DP, Michels PC. 14-Hydroxylation of opiates: Catalytic direct autooxidation of codeinone to 14-hydroxycodeinone. Journal of the American Chemical Society 2005;127(20):7286. Zhong BH, Liu H, Wu B, Wang YP. Synthesis and crystal structure of Ncyclopropylmethyl-7alpha-[(R)-1-hydroxyl-1-methyl-3-(2-thienyl)propyl])-6,14endoethano-6,7,8,9-tetrahydrodemethylthebaine. Chinese Journal Of Organic Chemistry 2005;25(2):210. Zvilichovsky G, Gbar-Haj-Yahia I. Birch reduction of (-)-ephedrine formation of a new, versatile intermediate for organic synthesis. Journal of Organic Chemistry 214

2004;69(16):5490. [Microgram Editor’s Notes: The Li/NH3 reduction of (-)-ephedrine gave S-1-(1,4-cyclohexadien-1-yl)-methyl-2-propanamine. Contact: Hebrew Univ Jerusalem, Dept Organ Chem, IL-91904 Jerusalem, Israel.] Clandestine Laboratories - Appraisals and Safety Issue: Forensic chemists must maintain familiarity with clandestine laboratory procedures, setups, and techniques in order to assist enforcement activities, to ensure safety and effectiveness during enforcement operations, and in order to provide expert testimony in court proceedings. Solution: Clandestine laboratory operations are continuously reviewed to provide a comprehensive overview of the field. In cases where new methodologies are noted, or unusual safety concerns are salient, reports are generated for the forensic and enforcement communities. References:

Clandestine Laboratory Appraisals and Safety:

Caldicott DGE, Pigou PE, Beattie R, Edwards JW. Clandestine drug laboratories in Australia and the potential for harm. Australian And New Zealand Journal Of Public Health 2005;29(2):155. Friese G. The methamphetamine crisis. What EMS providers need to know to stay safe and treat patients. Emerg Med Serv, Mar 2006; 35(3): 55-64. Hammon TL, Griffin S. Support for selection of a methamphetamine cleanup standard in Colorado. Regul Toxicol Pharmacol, Jun 2007; 48(1): 102-14. Santos AP, Wilson AK, Hornung CA, Polk HC, Rodriguez JL, Franklin GA. Methamphetamine laboratory explosions: A new and emerging burn injury. Journal of Burn Care, Rehabilitation 2005;26(3):228.

Safety Issues - Case Reports:

Sudakin DL. Occupational exposure to aluminium phosphide and phosphine gas? A suspected case report and review of the literature. Human & Experimental Toxicology 2005;24(1):27.


Hadlington S. The twilight world of the clandestine chemist. Chemistry World 2005;2(1):7. Lewis LD. Method and means of disposing of hazardous wastes connected with criminal activity. (Patent) Chem. Abstr. 2006:57039.



Lewis LD. Method of disposing of hazardous wastes connected with criminal activity. (Patent) Chem. Abstr. 2005:1132386. Oliver TL. Clandestine laboratory (Clan-Lab) home test kit system, protocol, method and apparatus. (Patent) Chemical Abstracts 2006:1342029. Marris E. Police urge speedy action to clean up home drug laboratories. Nature 2005;434(7030):129. Reference Drug Standards and Total Syntheses Issue: Many reference drug standards or structurally related internal standards are either commercially unavailable, or if available are extremely expensive. Solution: Controlled substances and their structural or isotopically labelled analogs are synthesized as needed. Internal standards are also prepared as needed. Case reports are published for new or unusual standards or improved synthetic approaches. References: Aalberg L, Andersson K, Bertler C, Boren H, Cole MD, Dahlen J, Finnon Y, Huizer H, Jalava K, Kaa E, Lock E, Lopes A, Poortman-van der Meer A, Sippola E. Development of a harmonised method for the profiling of amphetamines - I. Synthesis of standards and compilation of analytical data. Forensic Science International 2005;149(2-3):219. Felzmann W, Gmeiner GN, Gartner P. First synthesis of a pentadeuterated 3'hydroxystanozolol - an internal standard in doping analysis. Steroids 2005;70(2):103. Gay ML, Niemann RA, Musser SA. An isotopically labeled internal standard liquid chromatography-tandem mass spectrometry method for determination of ephedrine alkaloids and synephrine in dietary supplements. Journal Of Agricultural And Food Chemistry 2006;54(2):285. Katsifis A, Papazian V, Jackson T, Loc'h C. A rapid and efficient preparation of [123I]radiopharmaceuticals using a small HPLC (Rocket) column. Appl Radiat Isot, Jan 2006; 64(1): 27-31. Polli JE, Hoag SW. Drug authentication. (Patent) Chemical Abstracts 2005:300687. Sharpless KE, Anderson DL, Betz JM, Butler TA, Capar SG, Cheng J, Fraser CA, Gardner G, Gay ML, Howell DW, Ihara T, Khan MA, Lam JW, Long SE, McCooeye M, Mackey EA, Mindak WR, Mitvalsky S, Murphy KE, NguyenPho A, Phinney KW, Porter BJ, Roman M, Sander LC, Satterfield MB, Scriver C, Sturgeon R, Thomas JB, Vocke Jr RD, Wise SA, Wood LJ, Yang L, Yen JH, Ziobro GC. Preparation and characterization of a suite of ephedra-containing standard reference materials. J AOAC Int, Nov 2006; 89(6): 1483-95.


Thevis M, Opfermann G, Krug O, Schanzer W. Electrospray ionization mass spectrometric characterization and quantitation of xanthine derivatives using isotopically labelled analogues: an application for equine doping control analysis. Rapid Communications in Mass Spectrometry 2004;18(14):1553. Thevis M, Opfermann G, Schaenzer W. N-Methyl-Ntrimethylsilyltrifluoroacetamide synthesis and mass spectrometric characterization of deuterated ephedrines. European Journal of Mass Spectrometry 2004;10(5):673. [Microgram Editor’s Notes: Presents the title study. The results are of interest in elucidating the fragmentation mechanism for ephedrine. Contact: Institute of Biochemistry, German Sport University Cologne, Cologne 50933, Germany.] Tidgewell, Harding WW, Schmidt M, Holden KG, Murry DJ, Prisinzano TE. A facile method for preparation of deuterium labeled salvinorin A: Synthesis of [2,2,2-H2(3)]-salvinorin A. Bioorganic & Medicinal Chemistry Letters 2004;14(20):5099. [Microgram Editor’s Notes: For use as an internal standard in LC/MS analyses of biological fluids. Contact: Univ Iowa, Coll Pharm, Div Med & Nat Prod Chem, Iowa City, IA 52242.] Source Determination of Drugs (Impurity Profiling) and Comparative Analyses Issues: Impurity profiling of drugs is important for comparative analysis protocols, geosourcing, and synthetic route determinations. However, although certain drugs have been well characterized with respect to their impurity profiles, most have not been properly investigated. Comparative analysis (i.e., the systematic application of impurity profiling for determination of commonality of origin) is complicated due to both the high complexity of the data and the large numbers of exhibits. Improved analytical and data handling techniques are needed. Solution: High sensitivity analytical techniques (primarily chromatographic) provide detailed profiles of trace-level impurities, ions, trace metals, and stable isotopes. Identification of individual impurities enhance origin identification and comparative analyses and also aid in development of internal standards for improved accuracy and precision of analysis. In-depth analysis via improved instrumental methodologies help identify discriminatory components in impurity profiles. Computer databases, sorting programs, and pattern recognition/neural networks provide enhanced data handling and analysis, enabling and improving comparative analyses. Case reports are generated for the forensic and enforcement communities.





Aalberg L, Andersson K, Bertler C, Cole MD, Finnon Y, Huizer H, Jalava K, Kaa E, Lock E, Lopes A, Poortman-van der Maar A, Sippola E, Dahlen J. Development of a harmonised method for the profiling of amphetamines - II. Stability of impurities in organic solvents. Forensic Science International 2005;149(2-3):231. Andersson K, Jalava K, Lock E, Huizer H, Kaa E, Lopes A, Poortman-van der Meer A, Cole MD, Dahlen J, Sippola E. Development of a harmonised method for the profiling of amphetamines: IV. Optimisation of sample preparation. Forensic Sci Int, Jun 2007; 169(1): 64-76. Blachut D, Wojtasiewicz K, Czarnocki Z. Some pyridine derivatives as “routespecific markers” in 4-methoxyamphetamine (PMA) prepared by the Leuckart method. Forensic Science International 2005;152(2-3):157. Goldmann T, Taroni F, Margot P. Analysis of dyes in illicit pills (amphetamine and derivatives). Journal of Forensic Sciences 2004;49(4):716. [Microgram Editor’s Notes: Analysis for 14 dyes present in European ecstasy tablets is performed using SPE followed by TLC and/or CEC DAD, the results can be used to link cases. Contact: Institut de Medecine Legale, The University of Lausanne, Rue de Bugnon 21, 1005 Lausanne, Switzerland.] Gosav S, Praisler M, Dorohoi DO, Popa G. Automated identification of novel amphetamines using a pure neural network and neural networks coupled with principal component analysis. Journal of Molecular Structure 2005:744 and 821. Gosav S, Praisler M, Van Bocxlaer J, De Leenheer AP, Massart DL. Class identity assignment for amphetamines using neural networks and GC-FTIR data. Spectrochim Acta A Mol Biomol Spectrosc, Aug 2006; 64(5): 1110-7. [Microgram Editor’s Notes: Presents a feasibility study of the title technique, including a variety of stimulant amphetamines, hallucinogenic amphetamines, and non-amphetamines (not specified in the Abstract). Contact: Department of Physics, Faculty of Sciences, University of Galati, Domneasca St. 43, Galati 6200, Rom.] Lock E, Aalberg L, Andersson K, Dahlen J, Cole MD, Finnon Y, Huizer H, Jalava K, Kaa E, Lopes A, Poortman-van der Meer A, Sippola E. Development of a harmonised method for the profiling of amphetamines V: Determination of the variability of the optimised method. Forensic Sci Int, Jun 2007; 169(1): 77-85. Poortman-Van der Meer A, Lock E. Identification of 4-tert-butylamphetamine in clandestine amphetamine samples. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(2):23. [Microgram Editor’s Notes: The title compound results from the presence of 4- tert-butylphenylacetone as an impurity in phenylacetone possibly produced in eastern Europe. Note that JCLICA is a law enforcement restricted journal. Contact: Netherlands Forensic Institute, Postbus 24044, 2490AA The Hague, The Netherlands.]



Bieri S, Brachet A, Veuthey J-L, Christen P. Cocaine distribution in wild Erythroxylum species. Journal of Ethnopharmacology 2006;103:439. Brock A, Bieri S, Christen P, Drager B. Calystegines in wild and cultivated Erythroxylum species. Phytochemistry 2005;66(11):1231. Johnson EL, Zhang DP, Emche SD. Inter- and intra-specific variation among five Erythroxylum taxa assessed by AFLP. Annals Of Botany 2005;95(4):601. Sellers K, Morehead R. Efficient profiling of cocaine adulterants, using GC-MS and HPLC-RI. LCGC North America 2005(Suppl.):91.

Cocaine and Heroin:

Casale JF, Ehleringer JR, Morello DR, Lott MJ. Isotopic fractionation of carbon and nitrogen during the illicit processing of cocaine and heroin in South America. Journal of Forensic Sciences 2005;50(6):1315. Lociciro S, Hayoz P, Esseiva P, Dujourdy L, Besacier F, Margot P. Cocaine profiling for strategic intelligence purposes, a cross-border project between France and Switzerland. Part I. Optimisation and harmonisation of the profiling method. Forensic Sci Int, Apr 2007; 167(2-3): 220-8. Morley SR, Hall CJ, Forrest ARW, Galloway JH. Levamisole as a contaminant of illicit cocaine. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(4):11. [Microgram Editor’s Notes: Focus is on detection in body fluids of cocaine abusers (including six who were deceased) acquired over a 20 week period in the United Kingdom. JCLICA is a law enforcement restricted journal. Contact: Toxicology Section, Department of Clinical Chemistry, Sheffield Teaching Hospital Foundation Trust, Sheffield, S10 2JF, United Kingdom.] Valentino AMM, Fuentecilla K. Levamisole: An analytical profile. Microgram Journal 2005;3(3-4):134. [Microgram Editor’s Notes: Presents the title study. Contact: U.S. Department of Justice, Drug Enforcement Administration, Northeast Laboratory, 99 10th Avenue, Suite 721, New York, NY 10011.]

Dimethylamphetamine: Heroin:

Al-Amri AM, Smith RM, El-Haj BM, Juma’a MH. The GC-MS detection and characterization of reticuline as a marker of opium use [Erratum]. Forensic Science International 2004;142(1):59. [Microgram Editor’s Notes: Provides a correction to the original article, published 2004;140(2-3):175. Contact: Sharjah Police Forensic Science Laboratory, Sharjah, United Arab Emirates.]



Anastos N, Barnett NW, Lewis SW, Pearson JR, Kirkbride KP. Rapid determination of carbohydrates in heroin drug seizures using capillary electrophoresis with shortend injection. Journal Of Forensic Sciences 2005;50(5):1039. Casale J, Casale E, Collins M, Morello D, Cathapermal S, Panicker S. Stable isotope analyses of heroin seized from the merchant vessel Pong Su. Forensic Sciences 2006;51(3):603. [Microgram Editor’s Notes: Contact: U.S. Drug Enforcement Administration, Special Testing and Research Laboratory, 22624 Dulles Summit Court, Dulles, VA 20166.] Collins M, Casale E, Hibbert DB, Panicker S, Robertson J, Vujic S. Chemical profiling of heroin recovered from the North Korean merchant vessel Pong Su. Journal of Forensic Sciences 2006;51(3):597. [Microgram Editor’s Notes: The heroin was classified as “unknown” in origin (that is, having a profile that did not resemble any known heroin types). Contact: Australian Forensic Drug Laboratory, National Measurement Institute, 1 Suakin St., Pymble 2067, Sydney, Australia.] Dufey, Dujourdy L, Besacier F, Chaudron H. A quick and automated method for profiling heroin samples for tactical intelligence purposes. Forensic Sci Int, Jul 2007; 169(2-3): 108-17. El-Haj BM, Al-Amri AM, Ali HS. Heroin profiling: Mannitol hexaacetate as an unusual ingredient of some illicit drug seizures. Forensic Science International 2004;145(1):41. [Microgram Editor’s Notes: The identification and presence of the title impurity is discussed. Contact: Sharjah Police Forensic Science Laboratory, Sharjah, United Arab Emirates.] Esseiva P, Anglada F, Dujourdy L, Taroni F, Margot P, Du Pasquier E, Dawson M, Roux C, Doble P. Chemical profiling and classification of illicit heroin by principal component analysis, calculation of inter sample correlation and artificial neural networks. Talanta 2005;67(2):360. Idoine FA, Carter JF, Sleeman R. Bulk and compound-specific isotopic characterisation of illicit heroin and cling film. Rapid Communications in Mass Spectrometry 2005;19(22):3207. Lurie I, Hays P, Valentino A. Analysis of carbohydrates in seized heroin using capillary electrophoresis. Journal Of Forensic Sciences 2006;51(1):39. Klous MG, Lee W, Hillebrand MJ, van den Brink W, van Ree JM,Beijnen JH. Analysis of diacetylmorphine, caffeine, and degradation products after volatilization of pharmaceutical heroin for inhalation. J Anal Toxicol, Jan 2006; 30(1): 6-13. Schmidt J, Boettcher C, Kuhnt C, Kutchan TM, Zenk MH. Poppy alkaloid profiling by electrospray tandem mass spectrometry and electrospray FT-ICR mass spectrometry after [ring-13C6]-tyramine feeding. Phytochemistry, Jan 2007; 68(2): 189-202.


Odell LR, Skopec J, McCluskey A. A cold synthesis of heroin and implications in heroin signature analysis utility of trifluoroacetic/acetic anhydride in the acetylation of morphine. Forensic Sci Int, Dec 2006; 164(2-3): 221-9. [Microgram Editor’s Notes: Focuses on the impurity profile of heroin produced by this unusual route. Several trifluoroacetyl derivatives were identified, but were also found to be sensitive to typical heroin signature workup and analysis procedures. Contact: Chemistry Building, School of Environmental and Life Sciences, The University of Newcastle, University Drive, Callaghan NSW 2308, Australia.] Terrettaz-Zufferey AL, Ratle F, Ribaux O, Esseiva P, Kanevski M. Pattern detection in forensic case data using graph theory: application to heroin cutting agents. Forensic Sci Int, Apr 2007; 167(2-3): 242-6. Toske SG, Cooper SD, Morello DR, Hays PA, Casale JF, Casale E. Neutral heroin impurities from tetrahydrobenzylisoquinoline alkaloids. Journal of Forensic Sciences 2006;51(2):308. [Microgram Editor’s Notes: Four of the title compounds (laudanosine, reticuline, codamine, and laudanine), all naturally occurring in opium, form 18 detectable neutral impurities under typical heroin processing conditions. These latter impurities were found to useful for sourcing illicit heroin. Contact: U.S. Drug Enforcement Administration, Special Testing and Research Laboratory, 22624 Dulles Summit Court, Dulles, VA 20166.] Zamir A, Cohen Y, Azoury M. DNA profiling from heroin street dose packages. Journal of Forensic Sciences 2007;52(2):389. [Microgram Editor’s Notes: Presents the title study. DNA could be recovered from fingerprints along the “amorphic” burnt edges of the plastic wrap typically used to package street-level doses of heroin in Israel. Contact: Latent Fingerprint Laboratory, Division of Identification and Forensic Science (DIFS), Israel Police, National HQ, Jerusalem 91906, Israel.] Zelkowicz A, Magora A, Ravreby MD, Levy R. Analysis of a simulated heroin distribution chain by HPLC. Journal of Forensic Sciences 2005;50(4):849. Zhang ZY, Yang JH, Ouyang H, Li ZJ, Chai ZF, Zhu J, Zhao JZ, Yu ZS, Wang J. Study of trace impurities in heroin by neutron activation analysis. Journal of Radioanalytical and Nuclear Chemistry 2004;262(1):295. [Microgram Editor’s Notes: 62 heroin samples were analyzed for 15 trace elements by NAA. The authors indicate that the results provide origin information. Contact: Institute of High Energy Physics, Key Laboratory of Nuclear Analytical Techniques, The Chinese Academy of Sciences, Beijing, Peop. Rep. China 100039.] Zhang D, Sun W, Yuan ZP, Ju HX, Shi XJ, Wang CH. Origin differentiation of a heroin sample and its acetylating agent with C-13 isotope ratio mass spectrometry. European Journal Of Mass Spectrometry 2005;11(3):277. Zoppi U, Skopec Z, Skopec J, Jones G, Fink D, Hua Q, Jacobsen G, Tuniz C, Williams A. Forensic applications of C 14 bomb pulse dating. Nuclear Instruments & Methods in Physics Research, Section B: Beam Interactions with Materials and Atoms 2004:223. [Microgram Editor’s Notes: A minor review of the title technique. Includes the application to establishing the time of harvest of heroin and opium, and 221


discusses the potential of the technique for profiling illicit drugs deriving from natural sources. Contact: ANSTO Environment, PMB 1, Menai NSW 2234, Australia.]


Anwar F, Latif S, Ashraf M. Analytical characterization of hemp (Cannabis sativa) seed oil from different agro-ecological zones of Pakistan. Journal of the American oil chemists society 2006;83(4):323. Choi YH, Kim HK, Hazekamp A, Erkelens C, Lefeber AWM, Verpoorte R. Metabolomic differentiation of Cannabis sativa cultivars using 1H NMR spectroscopy and principal component analysis. Journal of Natural Products 2004;67:953. [Microgram Editor’s Notes: Cultivars could be differentiated by measurement of delta-9-tetrahydrocannabinolic acid and cannabidiolic acid. Contact: Division of Pharmacognosy, Section Metabolomics, Institute of Biology, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.] Datwyler SL, Weiblen GD. Genetic variation in hemp and marijuana (Cannabis sativa L.) according to amplified fragment length polymorphisms. Journal of Forensic Sciences 2006;51(2):371. [Microgram Editor’s Notes: The results are useful in linking seizures, for source determination, and for differentiating licit and illicit cultivars of cannabis. Contact: Department of Plant Biology, University of Minnesota, 1445 Gortner Avenue, Saint Paul, MN 55108.] Hewavitharana AK, Golding G, Tempany G, King G, Holling N. Quantitative GGMS analysis of Delta(9)-tetrahydrocannabinol in fiber hemp varieties. Journal of Analytical Toxicology 2005;29(4):258. Hsieh HM, Hou RJ, Chen KF, Tsai LC, Liu SW, Liu KL, Linacre A, Lee JC I. Establishing the rDNA IGS structure of Cannabis sativa. Journal of Forensic Sciences 2004;49(3):477. [Microgram Editor’s Notes: Presents the title study. The authors indicate that the technique can be used to identify and classify samples. Contact: Department of Forensic Science, Central Police University, Kwei San, Taoyuan, Taiwan 33334, Taiwan.] Ilias Y, Rudaz S, Christen P, Veuthey JL. Cannabis profiling: Which analytical strategy to apply? Chimia 2006;60(5):290. Pacifico D, Miselli F, Micheler M, Carboni A, Ranalli P, Mandolino G. Genetics and marker-assisted selection of the chemotype in Cannabis sativa L. Molecular Breeding 2006;17(3):257. Rabarjo TJ, Widjaja I, Roytrakul S, Verpoorte R. Comparative proteomics of Cannabis sativa plant tissues. Journal of Biomolecular Techniques 2004;15(2):97. [Microgram Editor’s Notes: Presents the title study. Contact: verpoort ]


Ross SA, ElSohly MA, Sultana GNN, Mehmedic Z, Hossain CF, Chandra S. Flavonoid glycosides and cannabinoids from the pollen of Cannabis sativa L. Phytochemical Analysis 2005;16(1):45. Sanger M. Plant identification by DNA. Part II. Species identification of marijuana by DNA analysis. Forensic Botany 2004:159. Shibuya EK, Sarkis JE, Negrini-Neto O, Martinelli LA. Carbon and nitrogen stable isotopes as indicative of geographical origin of marijuana samples seized in the city of São Paulo (Brazil). Forensic Sci Int, Mar 2007; 167(1): 8-15. Shibuya EK, Sarkis JES, Neto ON, Moreira MZ, Victoria RL. Sourcing Brazilian marijuana by applying IRMS analysis to seized samples. Forensic Sci Int, Jun 2006; 160(1): 35-43. Toonen M, Ribot S, Thissen J. Yield of illicit indoor cannabis cultivation in the Netherlands. Journal of Forensic Sciences 2006;51(5):1050. [Microgram Editor’s Notes: Presents a formula for determining a total expected yield of mature female flower buds (sinsimella) from indoor grow operations, regardless of maturity at the time of seizure. Contact: Plant Research International, Wageningen-UR, PO Box 16, 6700 AA Wageningen, The Netherlands.]


Armellin S, Brenna E, Frigoli S, Fronza G, Fuganti C, Mussida D. Determination of the synthetic origin of methamphetamine samples by 2H NMR spectroscopy. Analytical Chemistry 2006;78(9):3113. [Microgram Editor’s Notes: Presents the title study. The results suggest that site specific deuterium NMR can assist in classifying methamphetamine as to precursors and synthetic routes. Contact: Dipartimento di Chimica, Materiali, Ingegneria Chimica, Politecnico di Milano, I-20131 Milan, Italy.]

Barker WD, Antia U. A study of the use of Ephedra in the manufacture of methamphetamine. Forensic Sci Int, Mar 2007; 166(2-3): 102-9. Blok A, Cox M, Ward C. 4-Chlorodiphenylmethane, a precursor specific methylamphetamine manufacturing by-product. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(2):14. [Microgram Editor’s Notes: The title product results from use of pseudoephedrine pharmaceuticals containing cetirizine for the production of methamphetamine via the iodine/hypophosphorous acid route. Note that JCLICA is a law enforcement restricted journal. Contact: Flinders Univ. of South Australia, Bedford Park, South Australia, Australia.] Dayrit FM, Dumlao MC. Impurity profiling of methamphetamine hydrochloride drugs seized in the Phillipines. Forensic Science International 2004;144(1):29. [Microgram Editor’s Notes: Presents a cluster analysis study of trace impurities in



seized methamphetamine samples. Contact: Chemistry Department, Ateneo de Manila University, Loyola Heights, Quezon City, Phillipines.] Ishibashi H. Analysis of stable isotope ratio of carbon and nitrogen, as a powerful tool to identify smuggling routes of illegal drugs. Kagaku to Kogyo 2004;57(9):964. [Microgram Editor’s Notes: A review of the title topic, including discussion of application to methamphetamine and MDMA. This article is written in Japanese. Contact: Moji Customs, Japan (no further addressing information was provided).] Iwata YT, Inoue H, Kuwayama K, Kanamori T, Tsujikawa K, Miyaguchi H, Kishi T. Forensic application of chiral separation of amphetamine-type stimulants to impurity analysis of seized methamphetamine by capillary electrophoresis. Forensic Science International 2006;161:92. [Microgram Editor’s Notes: A highly sulfated gamma-cyclodextrin was used as the chiral selector. Contact: National Research Institute of Police Science, 6-3-1 Kashiwanoha, Kashiwa, Chiba 277-0882, Japan.] Kurashima N, Makino Y, Sekita S, Urano Y, Nagano T. Determination of origin of ephedrine used as precursor for illicit methamphetamine by carbon and nitrogen stable isotope ratio analysis. Analytical Chemistry 2004;76(14):4233. [Microgram Editor’s Notes: The title technique could easily differentiate between ephedrine of synthetic versus semi synthetic versus biosynthetic origins, and the differences were found to carry through to the methamphetamine produced from those different origins of ephedrine. Contact: [email protected] .] Kuwayama K, Tsujikawa K, Miyaguchi H, Kanamori T, Iwata Y, Inoue H, Saitoh S, Kishi T. Identification of impurities and the statistical classification of methamphetamine using headspace solid phase microextraction and gas chromatography-mass spectrometry. Forensic Sci Int, Jun 2006; 160(1): 44-52. [Microgram Editor’s Notes: The title techniques can be used for impurity profiling and discrimination. Contact: First Chemistry Section, National Research Institute of Police Science, 6-3-1, Kashiwanoha, Kashiwa-shi, Chiba 277-0882, Japan.] Lee JS, Han EY, Lee SY, Kim EM, Park YH, Lim MA, Chung HS, Park JH. Analysis of the impurities in the methamphetamine synthesized by three different methods from ephedrine and pseudoephedrine. Forensic Sci Int, Sep 2006; 161(2-3): 209-15. Li TL, Giang YS, Hsu JF, Cheng SG, Liu RH, Wang SM. Artifacts in the GC-MS profiling of underivatized methamphetamine hydrochloride. Forensic Sci Int, Oct 2006; 162(1-3): 113-20. Microgram Editor’s Notes: GC/MS analysis of methamphetamine hydrochloride in methanol with old inlet liners at temperatures above 200 °C gave appreciable amounts of N,N-dimethylamphetamine and amphetamine. Contact: Department of Forensic Sciences, Taoyuan, Central Police University, Chinese Taipei, Taichung.] Nguyen XT, Dang VD, Hoang TT. Impurity profiling analysis of illicit methamphetamine by capillary gas chromatography. Part I - Study on and optimum analysis methods. Tap Chi Hoa Hoc 2005;43(6):707. [Microgram Editor’s Notes: Presents the title study. This article is written in Vietnamese. Contact: Criminal Sci. Dept., Bureau of Public Security, Vietnam.] 224

Person EC, Savopolos JA. Elemental identification of lithium in clandestine laboratory casework by atomic emission spectroscopy. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(3):23. [Microgram Editor’s Notes: Presents the title study. JCLICA is a law enforcement restricted journal. Contact: Department of Forensic/Analytical Chemistry, California State University, Fresno, 2555 East San Ramon Ave., SB/70, Fresno, CA 93740-8034.] Qi Y, Evans I, McCluskey A. New impurity profiles of recent Australian imported 'ice': methamphetamine impurity profiling and the identification of (pseudo)ephedrine and Leuckart specific marker compounds. Forensic Sci Int, Jul 2007; 169(2-3): 173-80. Qi Y, Evans ID, McCluskey A. Australian Federal Police seizures of illicit crystalline methamphetamine ('ice') 1998-2002: impurity analysis. Forensic Sci Int, Dec 2006; 164(2-3): 201-10. [Microgram Editor’s Notes: 19 samples seized at Australian POE’s were analyzed by methamphetamine impurity profiling techniques; over 30 characteristic impurities were identified. Contact: Chemistry Building, School of Environmental and Life Sciences, The University of Newcastle, University Drive, Callaghan NSW 2308, Australia.] Sasaki T, Makino Y. Effective injection in pulsed splitless mode for impurity profiling of methamphetamine crystal by GC or GC/MS. Forensic Sci Int, Jun 2006; 160(1): 1-10. Shakleya DM, Tarr SG, Kraner JC, Clay DJ, Callery PS. Potential marker for smoked methamphetamine hydrochloride based on a gas chromatography-mass spectrometry quantification method for trans-phenylpropene. Journal of Analytical Toxicology 2005;29(6):552. Takagi T, Makino Y, Tanaka Y, Okamoto K, Yamashita N, Matsumoto T, Yokota M, Kurokawa K, Yasunaga T. Application of revised version of neural independent component analysis to classification problems of confiscated methamphetamine. Chemical & Pharmaceutical Bulletin 2004,52(12):1427.

4-Methoxyamphetamine and 4-Methoxymethamphetamine: Methylenedioxyamphetamines and MDMA:

Aalberg L, Clark CR, DeRuiter J. Chromatographic and mass spectral studies on isobaric and isomeric substances related to 3,4-methylenedioxymethamphetamine. Journal of Chromatographic Science 2004;42(9):464. [Microgram Editor’s Notes: Reports on the preparation of a number of compounds that are isobaric or isomeric with MDMA, and comments on the similarities and differences in their mass spectra (actual compounds not reported in the abstract). Contact: National Bureau of Investigation Crime Laboratory, Vantaa 01370, Finland.]



Cheng JY, Chan MF, Chan TW, Hung MY. Impurity profiling of ecstasy tablets seized in Hong Kong by gas chromatography-mass spectrometry. Forensic Sci Int, Oct 2006; 162(1-3): 87-94. Cox M, Klass G. Synthesis by-products from the Wacker oxidation of safrole in methanol using rho-benzoquinone and palladium chloride. Forensic Sci Int, Dec 2006; 164(2-3): 138-47. [Microgram Editor’s Notes: Presents the title study, including analyses of samples from a clandestine laboratory seized in Australia that was employing this synthesis route. Contact: Forensic Science, 21 Divett Place, Adelaide 5000 SA, Australia.] Gimeno P, Besacier F, Botex M, Dujordy L, Chaudron-Thozet H. A study of impurities in intermediates and 3,4-methylenedioxymethamphetamine (MDMA) samples produced via reductive amination routes. Forensic Science International 2005;155(2-3):141. Kochana J, Wilamowski J, Parczewski A. SPE-TLC profiling of impurities in 1-(3,4methylenedioxyphenyl)-2-nitropropene, and intermediate in 3,4methylenedioxymeth-amphetamine (MDMA) synthesis. Chromatographia 2004;60(7-8):481. [Microgram Editor’s Notes: Presents the title study. Appears to be closely related to a similarly titled article published in the Journal of Liquid Chromatography & Related Techniques 2004;27(15):2463. Contact: Jagiellonian Univ, Fac Chem, Dept Analyt Chem, Ingardena 3, PL-30060 Krakow, Poland.] Kochana J, Wilamowski J, Parczewski A. TLC profiling of impurities of 1-(3,4methylene-dioxyphenyl)-2-nitropropene, an intermediate in MDMA synthesis. Influence of sample preparation methods and conditions. Journal of Liquid Chromatography & Related Techniques 2004;27(15):2463. [Microgram Editor’s Notes: Presents the title study. Contact: Jagiellonian Univ, Fac Chem, Dept Analyt Chem, Ingardena 3, PL-30060 Krakow, Poland.] Kraj A, Swist M, Strugala A, Parczewski A, Silberring J. Fingerprinting of 3, 4methylenedioxymethamphetamine markers by desorption/ionization on porous silicon. Eur J Mass Spectrom (Chichester, Eng), Jan 2006; 12(4): 253-9. [Microgram Editor’s Notes: Presents the title study on MDMA synthesized by four different routes. Analyses were done using MALDI-ToF mass spectrometry. Contact: Department of Neurobiochemistry, Faculty of Chemistry and Regional Laboratory, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland.] Palhol F, Lamoureux C, Chabrillat M, Naulet N. N 15/N 14 Isotopic ratio and statistical analysis: An efficient way of linking seized Ecstasy tablets. Analytica Chimica Acta 2004;510(1):1. [Microgram Editor’s Notes: Presents the GC/C/IRMS analyses of MDMA from 106 samples. The results can be used for rapid grouping of similar tablets. Contact: Laboratoire des Douanes de Paris, 75141 Paris, France.] Sharma SP, Purkait BC, Lahiri SC. Qualitative and quantitative analysis of seized street drug samples and identification of source. Forensic Science International 2005;152(2-3):235.


Swist M, Wilamowski J, Parczewski A. Basic and neutral route specific impurities in MDMA prepared by different synthesis methods. Forensic Science International 2005;155(2-3):100. Swist M, Wilamowski J, Parczewski A. Determination of synthesis method of Ecstasy based on its basic impurities. Forensic Science International 2005;152(23):175. Swist M, Wilamowski J, Zuba D, Kochana J, Parczewski A. Determination of synthesis route of 1-(3,4-methylenedioxyphenyl)-2-propanone (MDP-2-P) based on impurity profiles of MDMA. Forensic Science International 2005;149(2-3):181. Teng SF, Wu SC, Liu C, Li JH, Chien CS. Characteristics and trends of 3,4methylenedioxymethamphetamine (MDMA) tablets found in Taiwan from 2002 to February 2005. Forensic Sci Int, Sep 2006; 161(2-3): 202-8. [Microgram Editor’s Notes: 181 tablets were analyzed by GC/MS. Photographs of the tablet logos are shown. Contact: National Bureau of Controlled Drugs, Department of Health, 6 Linsen South Road, Taipei 100, Taiwan.] van Deursen MM, Lock ER, Poortman-van der Meere AJ. Organic impurity profiling of 3,4-methylenedioxymethamphetamine (MDMA) tablets seized in The Netherlands. Sci Justice, Jul 2006; 46(3): 135-52. Wu G, Cai X, Xiang B. Identification of synthesis routes of “Ecstasy” by GC-MS coupled soft independent modeling of class analogies. Sepu 2005;23(2):214.

Opium and Opium Alkaoids:

Allen RS, Millgate AG, Chitty JA, Thisleton J, Miller JAC, Fist AJ, Gerlach WL, Larkin PJ. RNAi-mediated replacement of morphine with the nonnarcotic alkaloid reticuline in opium poppy. Nature Biotechnology 2004;22(12):1559 Frick S, Chitty JA, Kramell R, Schmidt J, Allen RS, Larkin PJ, Kutchan TM. Transformation of opium poppy (Papaver somniferumL.) with antisense berberine bridge enzyme gene (Anti-bbe) via somatic embryogenesis results in an altered ratio of alkaloids in latex but not in roots. Transgenic Research 2004;13(6):607. Frick S, Kramell R, Schmidt K, Fist AJ, Kutchan TM. Comparative qualitative and quantitative determination of alkaloids in narcotic and condiment Papaver somniferum cultivars. Journal of Natural Products 2005;68(5):666. Mohana M, Reddy K, Jayshanker G, Suresh V, Sarin RK, Sashidhar RB. Principal opium alkaloids as possible biochemical markers for the source identification of Indian opium. Journal of Separation Science 2005;28(13):1558. Mudiam MR, Kumar SA, Mahadevan S, Ghosh P, Sarin RK, Beedu SR. Quantitative evaluation of 28 mineral elements by inductively coupled plasma/mass spectrometry and its application in source identification of Indian opium. Journal of AOAC International 2005;88(5):1469.



Reddy MM, Krishna JG, Sashidhar RB, Varshney KM, Sarin RK. Evaluation of fatty acids as biochemical markers for source identification of Indian opium. LC-GC Europe 2005;18(10):541. Reddy MMK, Ghosh P, Rasool SN, Sarin RK, Sashidhar RB. Source identification of Indian opium based on chromatographic fingerprinting of amino acids. Journal of Chromatography A 2005;1088(1-2):158. Ziegler J, DiazChavez M, Kramell R, Ammer C, Kutchan TM. Comparative macroarray analysis of morphine containing Papaver somniferum and eight morphine free Papaver species identifies an O-methyltransferase involved in benzylisoquinoline biosynthesis. Planta 2005;222(3):458.

Occluded Solvent Analyses: Multi-Drug and Miscellaneous:

Alabdalla MA. Chemical characterization of counterfeit Captagon tablets seized in Jordan. Forensic Science International 2005;152(2-3):185. Almirall JR, Umpierrez S, Castro W, Gornushkin I, Winefordner J. Forensic elemental analysis of materials by laser induced breakdown spectroscopy (LIBS). Proceedings of SPIE - The International Society for Optical Engineering 2005;5778:657. Bergeron C, Gafner S, Clausen E, Carrier DJ. Comparison of the chemical composition of extracts from Scutellaria lateriflora using accelerated solvent extraction and supercritical fluid extraction versus standard hot water or 70% ethanol extraction. Journal of Agricultural and Food Chemistry 2005;53(8):3076. Carter JF, Grundy PL, Hill JC, Ronan NC, Titterton EL, Sleeman R. Forensic isotope ratio mass spectrometry of packaging tapes. Analyst 2004;129(12):1206. [Microgram Editor’s Notes: Includes some discussion of drug packaging. Contact: Mass Spec Analyt Ltd, Bldg 20F, Golf Course Lane POB 77, Bristol BS99 7AR, Avon, England.] Choi YH, Sertic S, Kim HK, Wilson EG, Michopoulos F, Lefeber AWM, Erkelens C, Kricun SDP, Verpoorte R. Classification of llex species based on metabolomic fingerprinting using nuclear magnetic resonance and multivariate data analysis. Journal of Agricultural and Food Chemistry 2005;53(4):1237. Edwards HGM, Munshi T, Anstis M. Raman spectroscopic characterisations and analytical discrimination between caffeine and demethylated analogues of pharmaceutical relevance. Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy 2005;61(7);1453. Galimov EM, Sevastyanov VS, Kulbachevskaya EV, Golyavin AA. Isotope ratio mass spectrometry: delta C-13 and delta(15) N analysis for tracing the origin of illicit


drugs. Rapid Communications In Mass Spectrometry 2005;19(10):1213. Gambaro V, Arnoldi S, Casagni E, Dell’Acqua L, Fare F, Saligari E, Valoti E. Analytical approach for the identification of impurities, intermediates and precursors of the entactogen synthesis. Bollettino Chimico Farmaceutico 2005;144(1):1. Hu P, Liang QL, Luo GA, Zhao ZZ, Jiang ZH. Multi-component HPLC fingerprinting of radix salviae miltiorrhizae and its LC-MS-MS identification. Chemical & Pharmaceutical Bulletin 2005;53(6):677. Huang M, Russo R, Fookes BG, Sigman ME. Analysis of fiber dyes by liquid chromatography mass spectrometry (LC-MS) with electrospray ionization: Discriminating between dyes with indistinguishable UV-Visible absorption spectra. Journal Of Forensic Sciences 2005;50(3):526. Johnson EL, Zhang D, Emche SD. Inter- and intra-specific variation among five Erythroxylum taxa assessed by AFLP. Annals of botany 2005;95:601. Joshi VC, Khan I. Macroscopic and microscopic authentication of Chinese and North American species of Ephedra. Journal of AOAC International 2005;88(3):707. Kakiuchi N, Nakajima I, Kurita Y, Long CF, Cai SQ, Mikage M. Studies on cultivated Ephedra plants in inner Mongolia autonomous region and Ningxia Hui autonomous region. Biological , Pharmaceutical Bulletin 2006;29(4):746. Kerns EH. Utility of mass spectrometry for pharmaceutical profiling applications. Current Drug Metabolism 2006;7(5):457. Kim HK, Choi YH, Erkelens C, Lefeber AWM, Verpoorte R. Metabolic fingerprinting of Ephedra species using H-1-NMR spectroscopy and principal component analysis. Chemical & Pharmaceutical Bulletin 2005;53(1):105. Kutchan TM. A role for intra- and intercellular translocation in natural product biosynthesis. Current Opinion in Plant Biology 2005;8(3):292. Lee TH, Lin SY. Microspectroscopic FT-IR mapping system as a tool to assess blend homogeneity of drug-excipient mixtures. European Journal of Pharmaceutical Sciences 2004;23(2):117. Leger MN, Ryder AG. Comparison of derivative preprocessing and automated polynomial baseline correction method for classification and quantification of narcotics in solid mixtures. Applied Spectroscopy 2006;60(2):182. Long C, Kakiuchi N, Takahashi A, Komatsu K, Cai S, Mikage M. Phylogenetic analysis of the DNA sequence of the non-coding region of nuclear ribosomal DNA and chloroplast of Ephedra plants in China. Planta Medica 2004;70(11):1080.



Matthijs N, Heyden YV. Enantiomeric impurity determination in capillary electrophoresis using a highly-sulfated cyclodextrins-based method. Biomed Chromatogr, Aug 2006; 20(8): 696-709. Meier AW, Liu RH. Forensic applications of isotope ratio mass spectrometry. Advances in Forensic Applications of Mass Spectrometry 2004:149 (Chapter 4). [Microgram Editor’s Notes: An overview and review. Appears to focus on biological/toxicological forensic applications (not clear in the abstract). This is a CRC Press text. Contact: No contact information was provided in the abstract.] NicDaeid N, Waddell RJH. The analytical and chemometric procedures used to profile illicit drug seizures. Talanta 2005;67(2):280. Novak P, Tepes P, Fistric I, Bratos I, Gabelica V. The application of LC-NMR and LC-MS for the separation and rapid structure elucidation of an unknown impurity in 5-aminosalicylic acid. J Pharm Biomed Anal, Mar 2006; 40(5): 1268-72. Van Gyseghem E, Jimidar M, Sneyers R, De Smet M, Verhoeven E, Vander Heyden Y. Stationary phases in the screening of drug/impurity profiles and in their separation method development: identification of columns with different and similar selectivities. J Pharm Biomed Anal, Jun 2006; 41(3): 751-60. Vassort A, Barrett DA, Shaw PN, Ferguson PD, Szucs R. A generic approach to the impurity profiling of drugs using standardised and independent capillary zone electrophoresis methods coupled to electrospray ionisation mass spectrometry. Electrophoresis 2005;26(9):1712. Visky D, Jimidar I, VanAel W, Vennekens T, Redlich D, DeSmet M. Capillary electrophoresis-mass spectrometry in impurity profiling of pharmaceutical products. Electrophoresis 2005;26(7-8):1541. Visky D, Jimidar I, VanAel W, Vennekens T, Redlich D, DeSmet M. Capillary electrophoresis-mass spectrometry in impurity profiling of pharmaceutical products. Electrophoresis 2005;26(7-8):1541. Vredenbregt MJ, Blok-Tip L, Hoogerbrugge R, Barends DM, de Kaste D. Screening suspected counterfeit Viagra and imitations of Viagra with near-infrared spectroscopy. Journal of Pharmaceutical and Biomedical Analysis 2006;40(4):840. Wang QB, Yang Y, Zhao XM, Zhu B, Nan P, Zhao JY, Wang L, Chen F, Liu ZJ, Zhong Y. Chemical variation in the essential oil of Ephedra sinica from Northeastern China. Food Chemistry 2006;98(1):52. Wiberg K. Quantitative impurity profiling by principal component analysis of highperformance liquid chromatography-diode array detection data. Journal of Chromatography A 2006;1108(1):50.


Widjaja E, Seah RKH. Use of Raman spectroscopy and multivariate classification techniques for the differentiation of fingernails and toenails. Applied Spectroscopy 2006;60(3):343. Witkowski MR. The use of Raman spectroscopy in the detection of counterfeit and adulterated pharmaceutical products. American Pharmaceutical Review 2005;8(1):56. Xue G, Bendick AD, Chen R, Sekulic SS. Automated peak tracking for comprehensive impurity profiling in orthogonal liquid chromatographic separation using mass spectrometric detection. Journal of Chromatography A 2004;1050(2):159. Zomer S, Brereton RG, Wolff JC, Airiau CY, Smallwood C. Component detection weighted index of analogy: Similarity recognition on liquid chromatographic mass spectral data for the characterization of route/process specific impurities in pharmaceutical tablets. Analytical Chemistry 2005;77(6):1607. Analysis of Non-Controlled Diluents, and Precursors




Issue: Most street-level drugs are cut with various adulterants and diluents. Many of these cutting agents are pharmaceutical products or precursors. Others are “carrythrough” compounds present in precursors (especially in cold remedy products). Separation and identification of these extraneous materials can be tedious, especially in exhibits which contain many components. In addition, new or unusual adulterants and/or diluents are occasionally identified in drug exhibits, and standard analytical data are required for these substances. Finally, improved methods of analysis, i.e., faster, more discriminatory, less costly, etc., are needed for all cutting agents. References:


Carducci C, Santagata S, Leuzzi V, Carducci C, Artiola C, Giovanniello T, Batti R, Antonozzi I. Quantitative determination of guanidinoacetate and creatine in dried blood spot by flow injection analysis-electrospray tandem mass spectrometry. Clinica Chimica Acta 2006;364(1-2):180. Zinellu A, Caria MA, Tavera C, Sotgia S, Chessa R, Delana L, Carru C. Plasma creatinine and creatine quantification by capillary electrophoresis diode array detector. Analytical Biochemistry 2005;342(2):186.

Ephedra, Ephedrine, Compounds:





AbuLathou A, Hamdan II, Tahraoui A. A new HPLC approach for the determination of hydrophilic and hydrophobic components: The case of



pseudoephedrine sulfate and loratadine in tablets. Drug Development and Industrial Pharmacy 2005;31(6):577. Amini A, Barclay V, Rundlof T, Jonsson S, Karlsson A, Arvidsson T. Determination of ephedrine, pseudoephedrine, and caffeine in a dietary product by capillary electrophoresis. Chromatographia 2006;63(3-4):143. An OY, Gao XY, Baeyens WRG, Delanghe JR. Determination of ephedrine and related compounds in pharmaceutical preparations by ion chromatography with direct conductivity detection. Biomedical Chromatography 2005;19(4):266. Avula B, Khan IA. Separation and determination of ephedrine enantiomers and synephrine by high performance capillary electrophoresis in dietary supplements. Chromatographia 2004;59(1-2):71. [Microgram Editor’s Notes: The title study was applied to E. Sinica and various dietary supplement products. The enantiomers of norephedrine, norpseudoephedrine, ephedrine, pseudoephedrine, Nmethylephedrine, and N-methylpseudoephedrine were separated. Contact: Univ Mississippi, Sch Pharm, Natl Ctr Nat Prod Res, Res Inst Pharmaceut Sci, University, MS 38677.] Bell DS, Cramer HM, Jones AD. Rational method development strategies on a fluorinated liquid chromatography stationary phase: Mobile phase ion concentration and temperature effects on the separation of ephedrine alkaloids. Journal of Chromatography A 2005;1095(1-2):113. Chan KH, Pan RN, Hsu MC. Simultaneous quantification of six ephedrines in a Mahwang [sic] preparation and in urine by high-performance liquid chromatography. Biomedical Chromatography 2005;19(5):337. Chain WJ, Myers AG. A convenient, NMR-based method for the analysis of diastereomeric mixtures of pseudoephedrine amides. Org Lett, Jan 2007; 9(2): 355-7. Cohen WS. Ephedra used as a precursor in methamphetamine manufacturing. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(2):21. [Microgram Editor’s Notes: Abstract details withheld in accordance with Microgram policy. Note that JCLICA is a law enforcement restricted journal. Contact: Contra Costa County-Coroner’s Office, 1960 Muir Road, Martinez, CA 94593.] Crantz BS. Observations of the mixed fusions of (+) and (-) pseudoephedrine and ephedrine hydrochloride. Microscope 2004;52(3/4):119. Dijiba YK, Zhang AD, Niemczyk TM. Determinations of ephedrine in mixtures of ephedrine and pseudoephedrine using diffuse reflectance infrared spectroscopy. International Journal of Pharmaceutics 2005;289(1-2):39. Dijiba YK, Niemczyk TM. Determination of ephedrine hydrochloride in mixtures of ephedrine hydrochloride and pseudoephedrine hydrochloride using near infrared spectroscopy. Journal of Near Infrared Spectroscopy 2005;13(3):155. 232

Dinc E, Ozdemir A, Aksoy H, Ustundag O, Baleanu D. Chemometric determination of naproxen sodium and pseudoephedrine hydrochloride in tablets by HPLC. Chem Pharm Bull (Tokyo), Apr 2006; 54(4): 415-21. Ding LL, Shi SS, Cui J, Wang SC, Wang ZT. [Advances in research of chemical constituents and pharmacological activites of Ephedra]. Zhongguo Zhong Yao Za Zhi, Oct 2006; 31(20): 1661-4. Dong XC, Wei WA, Ma SJ, Sun H, Li Y, Guo JQ. Molecularly imprinted solid-phase extraction of (-)-ephedrine from Chinese Ephedra. Journal of Chromatography A 2005;1070(1-2):125. Dong YM, Chen XF, Chen YL, Chen XG, Hu ZD. Separation and determination of pseudoephedrine, dextromethorphan, diphenhydramine and chlorpheniramine in cold medicines by nonaqueous capillary electrophoresis. Journal of Pharmaceutical and Biomedical Analysis 2005;39(1-2):285. Gay ML, Niemann RA, Musser SM. An isotopically labeled internal standard liquid chromatography-tandem mass spectrometry method for determination of ephedrine alkaloids and synephrine in dietary supplements. J Agric Food Chem, Jan 2006; 54(2): 285-91. Grippo AA, Hamilton B, Hannigan R, Gurley BJ. Metal content of ephedracontaining dietary supplements and select botanicals. Am. J. Health Syst. Pharm., Apr 2006; 63: 63 -644. Gu XC, Li HT, MacNair KR, Simons FER, Simons KJ. Simultaneous analysis of the H-1-antihistamine acrivastine and the decongestant pseudoephedrine hydrochloride by high-performance liquid chromatography. Journal of Pharmaceutical and Biomedical Analysis 2005;37(4):663. Hou J, Zheng J, Rizvi SA, Shamsi SA. Simultaneous chiral separation and determination of ephedrine alkaloids by MEKC-ESI-MS using polymeric surfactant I: method development. Electrophoresis, May 2007; 28(9): 1352-63. Hou J, Zheng J, Shamsi SA. Simultaneous chiral separation of ephedrine alkaloids by MEKC-ESI-MS using polymeric surfactant II: application in dietary supplements. Electrophoresis, May 2007; 28(9): 1426-34. Kakiuchi N, Nakajima I, Kurita Y, Long C, Cai S, Mikage M. Studies on cultivated ephedra plants in inner mongolia autonomous region and ningxia hui autonomous region. Biol Pharm Bull, Apr 2006; 29(4): 746-9. Kitlinski LM, Harman AL, Brousseau MM, Skinner HF. Reduction of phenylephrine with hydriodic acid/red phosphorus or iodine/red phosphorus: 3-Hydroxy-Nmethylphenethylamine. Microgram Journal 2005;3(3-4):142. [Microgram Editor’s Notes: Presents the title study (phenylephrine-containing products are replacing pseudoephedrine-containing products across the United States). Contact: U.S. 233


Department of Justice, Drug Enforcement Administration, Southwest Laboratory, 2815 Scott Street, Vista, CA 92081.] Kitlinski LM, Harman AL, Brousseau MM, Skinner HF. Reduction of phenylephrine via hydriodic acid - red phosphorus or iodine - red phosphorus: 3-Hydroxy-Nmethylphenethylamine. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(3):12. [Microgram Editor’s Notes: Presents the title study (phenylephrine-containing products are replacing pseudoephedrinecontaining products across the United States). JCLICA is a law enforcement restricted journal. A slightly different version of this article was co-published in: Microgram Journal 2005;3(3-4):142. Contact: U.S. Department of Justice, Drug Enforcement Administration, Southwest Laboratory, 2815 Scott Street, Vista, CA 92081.] N-trimethylsilyl-trifluoroacetamide. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2004;811(2):201. [Microgram Editor’s Notes: Includes analysis of ephedrine, pseudoephedrine, cathine, norephedrine, and methylephedrine. Focus is toxicological. Contact: Austrian Res Ctr Seibersdorf Res GmbH, Dept Environm Analyt, Doping Control Lab, A-2444 Seibersdorf, Austria.] Lam JWH, Gardner GJ, McCooeye M, Fraser CA, Sturgeon RE. A systematic approach to quantitation of ephedra alkaloids in natural health products. Analytical And Bioanalytical Chemistry 2005;383(2):268. Lokhnauth JK, Snow NH. Solid phase micro-extraction coupled with ion mobility spectrometry for the analysis of ephedrine in urine. Journal Of Separation Science 2005;28(7):612. Marchei E, Pellegrini M, Pacifici R, Zuccaro P, Pichini S. A rapid and simple procedure for the determination of ephedrine alkaloids in dietary supplements by gas chromatography-mass spectrometry. J Pharm Biomed Anal, Aug 2006; 41(5): 1633-41. Marchei E, Pichini S, Pacifici R, Pellegrini M, Zuccaro P. A rapid and simple procedure for the determination of synephrine in dietary supplements by gas chromatography-mass spectrometry. J Pharm Biomed Anal, Jun 2006; 41(4): 1468-72. Morton SC. Ephedra. Statistical Science 2005;20(3):242. Pan ZW, Chen XG, Hu ZD. Continuous capillary electrophoresis with flow injection and its application for determination of ephedrine and pseudoepedrine in Chinese medicinal preparations. Biomedical Chromatography 2004;18(8):581. [Microgram Editor’s Notes: Presents the title technique, and its application to five medicinal preparations. Contact: Lanzhou Univ, Dept Chem, Lanzhou 730000, Peoples R China.]


Phinney KW, Ihara T, Sander LC. Determination of ephedrine alkaloid stereoisomers in dietary supplements by capillary electrophoresis. Journal of Chromatography A 2005;1077(1):90. Reyes E, Vicario JL, Carrillo L, Badia D, Iza A, Uria U. Tandem asymmetric conjugate addition/alpha-alkylation using (S,S)-(+)-pseudoephedrine as chiral auxiliary. Org Lett, Jun 2006; 8(12): 2535-8. Sander LC, Sharpless KE, Satterfield MB, Ihara T, Phinney KW, Yen JH, Wise SA, Gay ML, Lam JW, McCooeye M, Gardner G, Fraser C, Sturgeon R, Roman M. Determination of ephedrine alkaloids in dietary supplement standard reference materials. Analytical Chemistry 2005;77(10):3101. Sun JG, Wang GJ, Wang W, Zhao S, Gu Y, Zhang JW, Huang MW, Shao F, Li H, Zhang Q, Xie HT. Simultaneous determination of loratadine and pseudoephedrine sulfate in human plasma by liquid chromatography-electro spray mass spectrometry for pharmacokinetic studies. Journal of Pharmaceutical and Biomedical Analysis 2005;39(1-2):217. Trujillo WA, Sorenson WR, Laluzerne PS, Scheuerell CR. Comparison of various dilutions and solid-phase extraction cleanup on the determination of ephedrine-type alkaloids and internal standard recovery in ephedra botanical raw material and powdered extract. Journal of AOAC International 2005;88(4):1028. Vasiliades J, Colonna K. Determination of ephedrine/pseudoephedrine in over the counter medications by gas chromatography. Clinical Chemistry 2005;51(Suppl. 6):A148. Wang M, Marriott PJ, Chan WH, Lee AWM, Huie CW. Enantiomeric separation and quantification of ephedrine-type alkaloids in herbal materials by comprehensive two-dimensional gas chromatography. Journal of Chromatography A 2006;1112(12):361. Wang S-M, Lewis RJ, Canfield D, Li T-L, Chen C-Y, Liu RH. Enantiomeric determination of ephedrines and norephedrines by chiral derivatization gas chromatography - mass spectrometry approaches. Journal of Chromatography BAnalytical Technologies in the Biomedical and Life Sciences 2005;825(1):88. Wang W, Li C, Li Y, Hu Z, Chen X. Rapid and ultrasensitive determination of ephedrine and pseudoephedrine derivatizated with 5-(4,6-dichloro-s-triazin-2ylamino) fluorescein by micellar electrokinetic chromatography with laser-induced fluorescence detection. J Chromatogr A, Jan 2006; 1102(1-2): 273-9. Xie JP, Zhang JY, Liu JP, Tian JN, Chen XG, Hu ZD. Rapid and sensitive determination of ephedrine and pseudoephedrine by micellar electrokinetic chromatography with an on-line regenerating covalent coating. Biomedical Chromatography 2005;19(1):9.



Yoshizawa C, Kitade M, Mikage M. [Herbological studies on the Chinese crude drug ma-huang--part 2--on the confusion between ma-huang, Ephedrae Herba, and Equisetum plants in Medieval China and Japan]. Yakushigaku Zasshi, Jan 2006; 41(1): 9-17. Zhao LH, Yan F, Yang LL, Xiang BG. Chromatographic separation of (-)-ephedrine and (+)-pseudoephedrine in the traditional Chinese medicinal preparation Jiketing granule. Chemical & Pharmaceutical Bulletin 2005;53(11):1494.


Abbasi K, Bhanger MI, Khuhawar MY. Capillary gas chromatographic determination of phenylpropanolamine in pharmaceutical preparation. J Pharm Biomed Anal, Jun 2006; 41(3): 998-1001. Azhagvuel S, Sekar R. Method development and validation for the simultaneous determination of cetirizine dihydrochloride, paracetamol, and phenylpropanolamine hydrochloride in tablets by capillary zone electrophoresis. J Pharm Biomed Anal, Feb 2007; 43(3): 873-8. Fukui A, Fujii R, Yonezawa Y, Sunada H. Analysis of the release process of phenylpropanolamine hydrochloride from ethylcellulose matrix granules III. Effects of the dissolution condition on the release process. Chem Pharm Bull (Tokyo), Aug 2006; 54(8): 1091-6.

Other Adulterants/Diluents (including Ephedrine and/or Pseudoephedrine):



Dijiba YK, Zhang AD, Niemczyk TM. Determinations of ephedrine in mixtures of ephedrine and pseudoephedrine using diffuse reflectance infrared spectroscopy. International Journal of Pharmaceutics 2005;289(1-2):39. Forsdahl G, Gmeiner G. Investigation of the silylation of ephedrines using Nmethyl-N-trimethylsilyl-trifluoroacetamide. Journal of Chromatography B Analytical Technologies in the Biomedical and Life Sciences 2004;811(2):201. [Microgram Editor’s Notes: Includes analysis of ephedrine, pseudoephedrine, cathine, norephedrine, and methylephedrine. Focus is toxicological. Contact: Austrian Res Ctr Seibersdorf Res GmbH, Dept Environm Analyt, Doping Control Lab, A-2444 Seibersdorf, Austria.] Gu XC, Fediuk DJ, Simons FER, Simons KJ. Evaluation and comparison of five matrix excipients for the controlled release of acrivastine and pseudoephedrine. Drug Development and Industrial Pharmacy 2004;30(10):1009. Gu XC, Li HT, MacNair KR, Simons FER, Simons KJ. Simultaneous analysis of the H-1-antihistamine acrivastine and the decongestant pseudoephedrine hydrochloride by high-performance liquid chromatography. Journal of pharmaceutical and biomedical analysis 2005;37(4):663.


Gunasekaran S, Natarajan RK, Rathikha R, Syamala D. Fourier transform infrared and Fourier transform Raman spectra and normal co-ordinate analysis of benzocaine. Indian Journal Of Physics And Proceedings of the Indian association for the cultivation of science 2005;79(5):509.

Haller CA, Duan M, Benowitz NL, Jacob P. Concentrations of ephedra alkaloids and caffeine in commercial dietary supplements. Journal of Analytical Toxicology 2004;28:145. [Microgram Editor’s Notes: Presents a novel LC MS/MS technique for performing the title analysis, 35 products were analyzed. Contact: University of California San Francisco, Division of Clinical Pharmacology, Box 1220, San Francisco, CA 94143.] Jacob P, Haller CA, Duan MJ, Yu L, Peng M, Benowitz NL. Determination of ephedra alkaloid and caffeine concentrations in dietary supplements and biological fluids. Journal of Analytical Toxicology 2004;28(3):152. [Microgram Editor’s Notes: No abstract provided. Contact: P Jacob, Univ Calif San Francisco, Div Clin Pharmacol, San Francisco, CA 94110.] Lapitskaya MA, Zatonsky GV, Pivnitsky KK. Enantiomeric NMR analysis of chiral epoxides as addition compounds with d-ephedrine. Mendeleev Communications 2005;(5):175. Liu LB, Zheng ZX, Lin JM. Application of dimethyl-beta-cyclodextrin as a chiral selector in capillary electrophoresis for enantiomer separation of ephedrine and related compounds in some drugs. Biomedical Chromatography 2005;19(6):447. Marin A, Barbas C. CE versus HPLC for the dissolution test in a pharmaceutical formulation containing acetaminophen, phenylephrine and chlorpheniramine. Journal of Pharmaceutical and Biomedical Analysis 2004;35(4):769. Olmo B, Garcia A, Marin A, Barbas C. New approaches with two cyano columns to the separation of acetaminophen, phenylephrine, chlorpheniramine and related compounds. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2005;817(2):159. Walker TA, Schmitt GL. Separation of fexofenadine, pseudoephedrine, potential impurities, and degradation products using ion interaction chromatography. Journal of Liquid Chromatography & Related Technologies 2006;29(1):25.

Theophylline: Miscellaneous:

Abrahamsson C, Johannsson J, Andersson-Engels S, Svanberg S, Folestad S. Timeresolved NIR spectroscopy for quantitative analysis of intact pharmaceutical tablets. Analytical Chemistry 2005;77(4):1055.



Abramovic BF, Guzsvany VJ, Gaal FF. Phosphorus-doped and undoped glassy carbon indicator electrodes in controlled-current potentiometric titrations of bromide- or chloride-containing active ingredients in some pharmaceutical preparations. Journal of Pharmaceutical and Biomedical Analysis 2005;37(2):265. Bagheri H, EsHaghi A, Rouini MR. Sol-gel-based solid-phase microextraction and gas chromatography-mass spectrometry determination of dextromethorphan and dextrorphan in human plasma. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2005;818(2):147. Bartolincic A, Druskovic V, Sporec A, Vinkovic V. Development and validation of HPLC methods for the enantioselective analysis of bambuterol and albuterol. Journal of Pharmaceutical and Biomedical Analysis 2005;36(5):1003. Bucheler R, Gleiter CH, Schwoerer P, Gaertner I. Use of nonprohibited hallucinogenic plants: Increasing relevance for public health. Pharmacopsychiatry 2005;38(1):1. Chan KLA, Kazarian SG. Fourier transform infrared imaging for high-throughput analysis of pharmaceutical formulations. Journal of Combinatorial Chemistry 2005;7(2):185. Cheng YQ, Fan LY, Chen HL, Chen XG, Hu ZD. Method for on-line derivatization and separation of aspartic acid enantiomer in pharmaceuticals application by the coupling of flow injection with micellar electrokinetic chromatography. Journal of Chromatography A 2005;1072(2):259. Childs SL, Chyall LJ, Dunlap JT, Smolenskaya VN, Stahly BC, Stahly GP. Crystal engineering approach to forming cocrystals of amine hydrochlorides with organic acids. Molecular complexes of fluoxetine hydrochloride with benzoic, succinic, and fumaric acids. Journal of the American Chemical Society 2004;126(41):13335. Cimpoiu C, Hosu A, Hodisan S. Analysis of some steroids by thin-layer chromatography using optimum mobile phases. J Pharm Biomed Anal, May 2006; 41(2): 633-7. Constanzer ML, Chavez-Eng CM, Fu I, Woolf EJ, Matuszewski B. Determination of dextromethorphan and its metabolite dextrorphan in human urine using high performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry: a study of selectivity of a tandem mass spectrometric assay. Journal of Chromatography B-Analytical Technologies In The Biomedical And Life Sciences 2005;816(1-2):297. Daniel D, Gutz IGR. Spectroelectrochemical determination of chlorpromazine hydrochloride by flow-injection analysis. Journal of Pharmaceutical and Biomedical Analysis 2005;37(2):281. Deisingh AK. Pharmaceutical counterfeiting. Analyst 2005;130(3):271.


dePablos RR, GarciaRuiz C, Crego AL, Marina ML. Separation of etodolac enantiomers by capillary electrophoresis. Validation and application of the chiral method to the analysis of commercial formulations. Electrophoresis 2005;26(6):1106. Fischer I. Analogue-based drug research: Lead and drug optimization. Medicinal Chemistry Research 2004;13(3-4):218. [Microgram Editor’s Notes: An overview of approximately 350 (legal) drugs, with analysis of their discovery/timing, and commonalities of action. Contact: Gedeon Richter Chem Works Ltd, Res Lab, POB 27, H-1475 Budapest 10, Hungary.] Freed AL, Kale U, Ando H, Rossi DT, Kingsmill CA. Improving the detection of degradants and impurities in pharmaceutical drug products by applying mass spectral and chromatographic searching. Journal of Pharmaceutical and Biomedical Analysis 2004;35(4):727. Galli V, Barbas C. High performance liquid chromatographic analysis of dextromethorphan, guaifenesin and benzoate in a cough syrup for stability testing. Journal of Chromatography A 2004;1048(2):207. [Microgram Editor’s Notes: Includes forced degradation analyses. Contact: Univ Sao Paulo, CEU, Fac CC Expt & Salud, Secc Quim Analyt, Urbanizac Monteprincipe, Madrid 28668, Spain.] Gilpin RK, Zhou W. Infrared studies of the polymorphic states of the fenamates. Journal of Pharmaceutical and Biomedical Analysis 2005;37(3):509. He J, Zhou ZL, Li HD. Simultaneous determination of fluoxetine, citalopram, paroxetine, venlafaxine in plasma by high performance liquid chromatographyelectrospray ionization mass spectrometry (HPLC-MS/ESI). Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2005;820(1):33. Himmelsbach M, Buchberger W, Klampfl CW. Determination of antidepressants in surface and waste water samples by capillary electrophoresis with electrospray ionization mass spectrometric detection after preconcentration using off-line solidphase extraction. Electrophoresis 2006;27(5-6):1220. Jaber AMY, AlSherife HA, AlOmari MM, Badwan AA. Determination of cetirizine dihydrochloride, related impurities and preservatives in oral solution and tablet dosage forms using HPLC. Journal of Pharmaceutical and Biomedical Analysis 2004;36(2):341. Jasper JP, Fourel F, Eaton A, Morrison J, Phillips, A. Stable isotopic characterization of analgesic drugs. Pharmaceutical Technology 2004;28(8):60. [Microgram Editor’s Notes: Drugs not specified in the abstract - appears to be for characterization of commercial pharmaceuticals. Contact: Molecular Isotope Technologies, LLC, Niantic, CT 06357.] Jones OA, Lester JN, Voulvoulis N. Pharmaceuticals: a threat to drinking water? Trends in Biotechnology 2005;23(4):163.



Jones-Lepp TL. Polar organic chemical integrative sampling and liquid chromatography - electrospray/ion-trap mass spectrometry for assessing selected prescription and illicit drugs in treated sewage effluent. Archives of Environmental Contamination and Toxicology 2004;47:427. Kamigauchi M, Kawanishi K, Ohishi H, Ishida T. Inclusion effect and structural basis of cyclodextrins for increased extraction of medicinal alkaloids from natural medicines. Chem Pharm Bull (Tokyo), May 2007; 55(5): 729-33. Kvasnicka F, Biba B, Cvak L, Kratka J, Voldrich M. Separation of enantiomers of butorphanol and cycloamine by capillary zone electrophoresis. Journal of Chromatography A 2005;1081(1):87. Lacy TL, Nichols JH. Therapeutic drugs III: Neuroleptic (antipsychotic) drugs. Principles of Forensic Toxicology (2nd Edition) 2003:315. Lee H. Pharmaceutical applications of liquid chromatography coupled with mass spectrometry (LC/MS). Journal of Liquid Chromatography & Related Technologies 2005;28(7-8):1161. Li CH, Zhang JY, Chen AJ, Xie JP, Chen XG, Hu ZD. Non-aqueous capillary electrophoresis for simultaneous separation and determination of three major active components in traditional medicinal preparations. Biomedical Chromatography 2005;19(5):369. Loehlin JH, Okasako EL. Analysis of structures with saturated hydrogen bonding. Acta Crystallogr B, Feb 2007; 63(Pt 1): 132-41. Majumdar TK. Commonly encountered analytical problems and their solutions in liquid chromatography/tandem mass spectrometry (LC/MS/MS) methods used in drug development. Identification And Quantification Of Drugs, Metabolites And Metabolizing Enzymes By LC/MS (Series: Progress In Pharmaceutical And Biomedical Analysis) 2005;6):35. Marchei E, Pellegrini M, Pacifici R, Palmi I, Pichini S. Development and validation of a high-performance liquid chromatography-mass spectrometry assay for methylxanthines and taurine in dietary supplements. Journal of Pharmaceutical and Biomedical Analysis 2005;37(3):499. Marin A, Barbas C. LC/MS for the degradation profiling of cough-cold products under forced conditions. Journal of Pharmaceutical and Biomedical Analysis 2004;35(5):1035. Michulec M, Wardenck, W. Determination of solvents residues in vegetable oils and pharmaceuticals by headspace analysis and capillary gas chromatography. Chromatographia 2004;60:S273.


Michulec M, Wardencki W. Development of headspace solid-phase microextractiongas chromatography method for the determination of solvent residues in edible oils and pharmaceuticals. Journal of Chromatography A 2005;1071(1-2):119. Natishan TK. Recent progress in the analysis of pharmaceuticals by capillary electrophoresis. Journal of Liquid Chromatography & Related Technologies 2005;28(7-8):1115. Nirogi RVS, Kandikere VN, Shukla M, Mudigonda K, Maurya S, Boosi R, Yeffamilli A. Development and validation of a sensitive liquid chromatography/electrospray tandem mass spectrometry assay for the quantification of olanzapine in human plasma. Journal Of Pharmaceutical and Biomedical Analysis 2006;41(3):935. Okamoto H, Nakajima T, Ito Y, Aketo T, Shimada K, Yamato S. Simultaneous determination of ingredients in a cold medicine by cyclodextrin-modified microemulsion electrokinetic chromatography. Journal of Pharmaceutical and Biomedical Analysis 2005;37(3):517. Otero R, Carrera G, Dulsat JF, Fabregas JL, Claramunt J. Static headspace gas chromatographic method for quantitative determination of residual solvents in pharmaceutical drug substances according to European Pharmacopoeia requirements. Journal of Chromatography A 2004;1057(1-2):193. Perez SC, Cerioni L, Wolfenson AE, Faudone S, Cuffini SL. Utilization of pure nuclear quadrupole resonance spectroscopy for the study of pharmaceutical crystal forms. International Journal of Pharmaceutics 2005;298(1):143. Perez-Ruiz T, Martinez-Lozano C, Tomas V, Galera R. Migration behaviour and separation of acetaminophen and p-aminophenol in capillary zone electrophoresis: Analysis of drugs based on acetaminophen. Journal of Pharmaceutical and Biomedical Analysis 2005;38(1):87. Risley DS, Yang WQ, Peterson JA. Analysis of mannitol in pharmaceutical formulations using hydrophilic interaction liquid chromatography with evaporative light-scattering detection. Journal of Separation Science 2006;29(2):256. Seger C, Godejohann M, Tseng LH, Spraul M, Girtler A, Sturm S, Stuppner H. LCDAD-MS/SPE-NMR hyphenation. A tool for the analysis of pharmaceutically used plant extracts: Identification of isobaric iridoid glycoside regioisomers from Harpagophytum procumbens. Analytical Chemistry 2005;77(3):878. Sharaf MHM, Stiff DD. Determination of guaifenesin in human serum by capillary gas chromatography and electron capture detection. Journal of Pharmaceutical and Biomedical Analysis 2004;35(4):801. Song GX, Deng CH, Wu D, Hu YM. Headspace solid-phase microextraction-gas chromatographic-mass spectrometric analysis of the essential oils of two traditional Chinese medicines, Angelica pubescens and Angelica sinensis. Chromatographia 2004;59(5-6):343. 241


Srinivasu MK, Rao BM, Sridhar G, Kumar PR, Chandrasekhar KB, Islam A. A validated chiral LC method for the determination of Zolmitriptan and its potential impurities. Journal of Pharmaceutical and Biomedical Analysis 2005;37(3):453. Tapsoba I, Belgaied JE, Boujlel K. Voltametric assay of guaifenesin in a pharmaceutical formulation. Journal of Pharmaceutical and Biomedical Analysis 2005;38(1):162. Thompson R. A practical guide to HPLC enantioseparations for pharmaceutical compounds. Journal of Liquid Chromatography & Related Technologies 2005;28(78):1215. Ueno T, Urakami K, Higashi A, Umemoto K, Godo M, Kitamura K. A simple method for quantitative determination of active drug polymorphs and amorphous in drug products by Fourier transform-Raman spectroscopy. Yakugaku Zasshi Journal of the Pharmaceutical Society of Japan 2005;125(10):807. VanderWeerd J, Kazarian SG. Release of poorly soluble drugs from HPMC tablets studied by FTIR imaging and flow-through dissolution tests. Journal of Pharmaceutical Sciences 2005;94(9):2096. Vuletic M, Cindric M, Koruznjak JD. Identification of unknown impurities in simvastatin substance and tablets by liquid chromatography/tandem mass spectrometry. Journal of Pharmaceutical and Biomedical Analysis 2005;37(4):715. Wade N, Miller K. Determination of active ingredient within pharmaceutical preparations using flow injection mass spectrometry. Journal of Pharmaceutical and Biomedical Analysis 2005;37(4):669. Wille SMR, Maudens KE, VanPeteghem CH, Lambert WEE. Development of a solid phase extraction for 13 new generation antidepressants and their active metabolites for gas chromatographic-mass spectrometric analysis. Journal of Chromatography A 2005;1098(1-2):19. Williams JP, Patel VJ, Holland R, Scrivens JH. The use of recently described ionisation techniques for the rapid analysis of some common drugs and samples of biological origin. Rapid Communications in Mass Spectrometry 2006;20(9):1447. Wolf CE, Poklis A. A rapid HPLC procedure for analysis of analgesic pharmaceutical mixtures for quality assurance and drug diversion testing. Journal of Analytical Toxicology 2005;29:711. Xie CH, Hu JW, Xiao H, Su XY, Dong J, Tian RJ, He ZK, Zou HF. Electrochromatographic evaluation of a silica monolith capillary column for separation of basic pharmaceuticals. Electrophoresis 2005;26(4-5):790. Zweig SE. From smart tags to brilliant tags: Advances in drug stability monitoring. BioPharm International 2005;18(11):36. 242

New and/or Improved Instrumental Techniques Issue: Forensic chemists must maintain familiarity with updates in current instrumental techniques and become versant in new, improved methods of analysis. Solution: Improved/existing and new technologies are reviewed and applied to both routine and specialized analyses of drugs. In cases where improved performance is observed, case reports are generated for the forensic community. References:

Capillary Electrophoresis (and Related Techniques, including Tandem Techniques): Al Najjar AO. Enhancement of sensitivity in capillary electrophoresis: Forensic and pharmaceutical applications. Diss. Abstr. Int. B 2005;66(1):246.

Berthier D, Varenne A, Gareil P, Digne M, Lienemann CP, Magna L, OlivierBourbigou H. Capillary electrophoresis monitoring of halide impurities in ionic liquids. Analyst 2004;129(12):1257. Chen XM, Qin F, Liu YQ, Kong L, Zou HF. Preparation of a positively charged cellulose derivative chiral stationary phase with copolymerization reaction for capillary electrochromatographic separation of enantiomers. Electrophoresis 2004;25(16):2817. Chu QC, Guan YQ, Geng CH, Ye JN. Miniaturized capillary electrophoresis with amperometric detection: Fast separation and detection of bioactive amines. Analytical Letters 2006;39(4):729. Denola NL, Quiming NS, Catabay AP, Saito Y, Jinno K. Optimization of capillary electrophoretic enantioseparation for basic drugs with native beta-CD as a chiral selector. Electrophoresis, Jun 2006; 27(12): 2367-75. Ding Y, Garcia CD. Application of microchip-CE electrophoresis to follow the degradation of phenolic acids by aquatic plants. Electrophoresis, Dec 2006; 27(24): 5119-27. Dolnik V, Liu S. Applications of capillary electrophoresis on microchips. Journal of Separation Science 2005;28(15):1994. Evenhuis CJ, Guijt RM, Macka M, Haddad PR. Determination of inorganic ions using microfluidic devices. Electrophoresis 2004;25(21-22):3602.



Fang N, Meng P, Zhang H, Sun Y, Chen DD. Systematic optimization of exhaustive electrokinetic injection combined with micellar sweeping in capillary electrophoresis. Analyst, Feb 2007; 132(2): 127-34. Fang HF, Zeng ZR, Liu L, Pang DW. A novel method for capillary electrophoresis directly analyzing trace amounts analytes in the water-immiscible solution samples. Chemical Journal of Chinese Universities-Chinese 2006;27(5):856. Fradi I, Servais AC, Pedrini M, Chiap P, Ivanyi R, Crommen J, Fillet M. Enantiomeric separation of acidic compounds using single-isomer amino cyclodextrin derivatives in nonaqueous capillary electrophoresis. Electrophoresis, Sep 2006; 27(17): 3434-42. Gao Y, Xiang Q, Xu Y, Tian Y, Wang E. The use of CE-electrochemiluminescence with ionic liquid for the determination of bioactive constituents in Chinese traditional medicine. Electrophoresis, Dec 2006; 27(23): 4842-8. Gillogly JA, Lunte CE. pH-mediated acid stacking with reverse pressure for the analysis of cationic pharmaceuticals in capillary electrophoresis. Electrophoresis 2005;26(3):633. Holzgrabe U, Brinz D, Kopec S, Weber C, Bitar Y. Why not using capillary electrophoresis in drug analysis? Electrophoresis, Jun 2006; 27(12): 2283-92. Huck CW, Stecher G, Scherz H, Bonn G. Analysis of drugs, natural and bioactive compounds containing phenolic groups by capillary electrophoresis coupled to mass spectrometry. Electrophoresis 2005;26(7-8):1319. Huhn C, Neususs C, Pelzing M, Pyell U, Mannhardt J, Putz M. Capillary electrophoresis-laser induced fluorescence-electrospray ionization-mass spectrometry: A case study. Electrophoresis 2005;26(7-8):1389. Lin X, Zhao M, Qi X, Zhu C, Hao A. Capillary zone electrophoretic chiral discrimination using 6-O-(2-hydroxy-3-trimethylammoniopropyl)-beta-cyclodextrin as a chiral selector. Electrophoresis, Feb 2006; 27(4): 872-9. Liu Z, Pawliszyn J. Microdialysis hollow fiber as a macromolecule trap for on-line coupling of solid phase microextraction and capillary electrophoresis. Analyst, Apr 2006; 131(4): 522-8. Mangelings D, Maftouh M, Massart DL, Heyden YV. Enantioseparations by capillary electrochromatography: Differences exhibited by normal-and reversedphase versions of polysaccharide stationary phases. Electrophoresis 2004;25(16):2808. Mangelings D, Tanret I, Matthijs N, Maftouh M, Massart DL, VanderHeyden Y. Separation strategy for acidic chiral pharmaceuticals with capillary electrochromatography on polysaccharide stationary phases. Electrophoresis 2005;26(4-5):818.


Marsh A, Clark B, Broderick M, Power J, Donegan S, Altria K. Recent advances in microemulsion electrokinetic chromatography. Electrophoresis 2004;25(23-24):3970. Michalke B. Capillary electrophoresis-inductively coupled plasma-mass spectrometry: A report on technical principles and problem solutions, potential, and limitations of this technology as well as on examples of application. Electrophoresis 2005;26(7-8):1584. Mohanty A, Dey J. Vesicles as pseudostationary phase for enantiomer separation by capillary electrophoresis. Journal of Chromatography A 2005;1070(1-2):185. Natishan TK. Recent progress in the analysis of pharmaceuticals by capillary electrophoresis. Journal of Liquid Chromatography & Related Technologies 2005;28(7-8):1115-1160 Nieuwland AA. Applications of chromatography, spectroscopy, and capillary electrophoresis to the analysis of forensic samples. Diss. Abstr. Int. B 2005;65(12):6355. Nyholm L. Electrochemical techniques for lab-on-a-chip applications. Analyst 2005;130(5):599. Ohnesorge J, deGriend CSV, Watzig H. Quantification in capillary electrophoresismass spectrometry: Long- and short-term variance components and their compensation using internal standards. Electrophoresis 2005;26(12):2360. Ohyama K, Shirasawa Y, Wada M, Kishikawa N, Ohba Y, Nakashima K, Kuroda N. Investigation of the novel mixed mode stationary phase for capillary electrochromatography I. Preparation and characterization of sulfonated naphthalimido modified silyl silica gel. Journal of Chromatography A 2004;1042(1 2):189. [Microgram Editor’s Notes: Presents the title analysis on a series of barbiturates and benzodiazepines (drugs and matrices not specified in the abstract). Contact: Nagasaki Univ, Course Pharmaceut Sci, Grad Sch Biomed Sci, Analyt Chem, 1 14 Bunkyo Machi, Nagasaki 8528521, Japan.] Pang HM, Kenseth J, Coldiron S. High-throughput multiplexed capillary electrophoresis in drug discovery. Drug Discovery Today 2004;9(24):1072. Sazelova P, Kasicka V, Koval D, Prusik Z, Fanali S, Aturki Z. Control of EOF in CE by different ways of application of radial electric field. Electrophoresis, Mar 2007; 28(5): 756-66. Schmid MG, Koidl J, Wank P, Kargl G, Zohrer H, Gubitz G. Enantioseparation by ligand-exchange using particle-loaded monoliths: capillary-LC versus capillary electrochromatography. J Biochem Biophys Methods, Feb 2007; 70(1): 77-85. SchmittKopplin P, Englmann M. Capillary electrophoresis-mass spectrometry: Survey on developments and applications 2003-2004. Electrophoresis 2005;26(78):1209. 245


Smyth WF, Brooks P. A critical evaluation of high performance liquid chromatography electrospray ionization mass spectrometry and capillary electrophoresis electrospray mass spectrometry for the detection and determination of small molecules of significance in clinical and forensic science. Electrophoresis 2004;25(10 11):1413. [Microgram Editor’s Notes: An extensive review of the title topics for the period 2000-2003. Several controlled substances are included among the wide variety of discussed applications. Contact: School of Biomedical Sciences, University of Ulster, Coleraine, UK.] Smyth WF. Recent studies on the electrospray ionisation mass spectrometric behaviour of selected nitrogen-containing drug molecules and its application to drug analysis using liquid chromatography-electrospray ionisation mass spectrometry. Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences 2005;824(1-2):1 Smyth WF. Recent applications of capillary electrophoresis-electrospray ionisationmass spectrometry in drug analysis. Electrophoresis 2005;26(7-8):1334. Smyth WF. Recent applications of capillary electrophoresis-electrospray ionisationmass spectrometry in drug analysis. Electrophoresis 2006;27(11 SI):2051. Souverain S, Geiser L, Rudaz S, Veuthey JL. Strategies for rapid chiral analysis by capillary electrophoresis. Journal of Pharmaceutical and Biomedical Analysis 2006;40(2):235. Szoko E, Tabi T, Borbas T, Dalmadi B, Tihanyi K, Magyar K. Assessment of the Noxidation of deprenyl, and amphetamine enantiomers methamphetamine by chiral capillary electrophoresis: An in vitro metabolism study. Electrophoresis 2004;25(16):2866. Tagliaro F, Bortolotti F. Recent advances in the applications of CE to forensic sciences (2001-2004). Electrophoresis 2006;27(1):231. Terabe S. Micellar Electrokinetic Chromatography. Analytical Chemistry 2004;76(13):240A. [Microgram Editor’s Notes: A minor overview and review of the title topic. Contact: University of Hyogo, Japan (no further addressing information was provided).] Thormann W, Verpoorte S, Caslavska J, McCord B. Capillary electrophoresis in clinical and forensic analysis. Electrophoresis 2004;25(10 11):U6. [Microgram Editor’s Notes: A minor overview and review of the title topic. Contact: No contact information was provided in the abstract.] Toro I, Dulsat JF, Fabregas JL, Claramunt J. Development and validation of a capillary electrophoresis method with ultraviolet detection for the determination of the related substances in a pharmaceutical compound. Journal of Chromatography A 2004;1043(2):303.


Valette JC, Bizet AC, Demesmay C, Rocca JL, Verdon E. Separation of basic compounds by capillary electrochromatography on an X-Terra RP18((R)) stationary phase. Journal of Chromatography A 2004;1049(1-2):171. Weinberger R. Implementing capillary electrophoresis in a controlled environment: An interview with Ira Lurie of the DEA. American Laboratory 2005;37(1):6. Wistuba D, Banspach L, Schurig V. Enantiomeric separation by capillary electrochromatography using monolithic capillaries with sol-gel-glued cyclodextrinmodified silica particles. Electrophoresis 2005;26(10):2019. Xu Y, Gao Y, Wei H, Du Y, Wang E. Field-amplified sample stacking capillary electrophoresis with electrochemiluminescence applied to the determination of illicit drugs on banknotes. Journal of Chromatography A 2006;1115:260. [Microgram Editor’s Notes: Presents the title study; focus is cocaine and heroin. Baseline resolution was achieved within 6 minutes. Contact: State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Graduate School of the Chinese Academy of Sciences, Changchun, Jilin 130022, China.] Zhao S, Wang H, Pan Y, He M, Zhao Z. 3-[(3-Dehydroabietamidopropyl)dimethylammonio]-1-propane-sulfonate as a new type of chiral surfactant for enantiomer separation in micellar electrokinetic chromatography. J Chromatogr A, Mar 2007; 1145(1-2): 246-9.

Extraction Techniques:

Bergeron C, Gafner S, Clausen E, Carrier DJ. Comparison of the chemical composition of extracts from Scutellaria lateriflora using accelerated solvent extraction and supercritical fluid extraction versus standard hot water or 70, ethanol extraction. Journal of Agricultural and Food Chemistry 2005;53(8):3076. Molins-Legua C, Campins-Falco P. Solid phase extraction of amines. Analytica Chimica Acta 2005;546(2):206. Panno BA, Johnson P, Aide M, Fasnachi MP. Using Li+ extracted from soils at clandestine methamphetamine labs to estimate methamphetamine production. Journal of the Clandestine Laboratory Investigating Chemists Association 2006;16(1):7. PedersenBjergaard S, Rasmussen KE. Bioanalysis of drugs by liquid-phase microextraction coupled to separation techniques. Journal of Chromatography B Analytical Technologies in the Biomedical and Life Sciences 2005;817(1):3. Raynie DE. Modern extraction techniques. Analytical Chemistry 2004;76(16):4659.



Gas Chromatography (and Tandem GC Techniques):

Berzas JJ, Guiberteau C, Villasenor MJ, Rodriguez V. Development of a capillary gas chromatographic procedure. Analytica Chimica Acta 2004;519(2):219. Beyer J, Peters FT, Maurer HH. Screening procedure for detection of stimulant laxatives and/or their metabolites in human urine using gas chromatography-mass spectrometry after enzymatic cleavage of conjugates and extractive methylation. Therapeutic Drug Monitoring 2005;27(2):151. Christensen JH, Mortensen J, Hansen AB, Andersen O. Chromatographic preprocessing of GC-MS data for analysis of complex chemical mixtures. Journal of Chromatography A 2005;1062(1):113. Dimandja J-MD. GC x GC. Analytical Chemistry 2004;76(9):167A. [Microgram Editor’s Notes: An overview and review of two-dimensional GC techniques. Contact: Spelman College (no further addressing information provided).] Gambelunghe C, Rossi R, Ferranti C, Rossi R, Bacci M. Hair analysis by GC/MS/MS to verify abuse of drugs. Journal Of Applied Toxicology 2005;25(3):205. Hodjmohammadi MR, Ebrahimi P, Pourmorad F. Quantitative structure-retention relationships (QSRR) of some CNS agents studied on DB-5 and DB-17 phases in gas chromatography. QSAR & Combinatorial Science 2004;23(5):295. Jacobs P, Dewe W, Flament A, Gibella M, Ceccato A. A new validation approach applied to the GC determination of impurities in organic solvents. J Pharm Biomed Anal, Feb 2006; 40(2): 294-304. Luong J, Gras R, Van Meulebroeck R, Sutherland F, Cortes H. Gas chromatography with state-of-the-art micromachined differential mobility detection: operation and industrial applications. J Chromatogr Sci, May 2006; 44(5): 276-86. Pan C, Liu F, Ji Q, Wang W, Drinkwater D, Vivilecchia R. The use of LC/MS, GC/MS, and LC/NMR hyphenated techniques to identify a drug degradation product in pharmaceutical development. J Pharm Biomed Anal, Feb 2006; 40(3): 58190. Pietrogrande MC, Mercuriali M, Pasti L. Signal processing of GC-MS data of complex environmental samples: characterization of homologous series. Anal Chim Acta, Jun 2007; 594(1): 128-38. Song SM, Marriott P, Kotsos A, Drummer OH, Wynne P. Comprehensive two dimensional gas chromatography with time of flight mass spectrometry (GC x GC TOFMS) for drug screening and confirmation. Forensic Science International 2004;143(2 3):87. [Microgram Editor’s Notes: 78 drugs of interest were analyzed, some forensic samples were also analyzed satisfactorily. Contact: Department of Applied Chemistry, Australian Centre for Research on Separation Science, Building


3, Bowen St., 124 Latrobe St., Rmit University, GPO Box 2476 V, Melbourne 3001, Australia.] Song SM, Marriott P, Wynne P. Comprehensive two-dimensional gas chromatography - quadrupole mass spectrometric analysis of drugs. Journal of Chromatography A 2004;1058(1-2):223. [Microgram Editor’s Notes: 77 underivatized drug standards (not specified in the abstract) were analyzed by the title technique. Appears to be related to a similarly titled article published in Forensic Science International, using TOF mass spectrometry: 2004;143(2-3):87. Contact: Australian Ctr Res Separat Sci, Sch Appl Sci, GPO Box 2476 V, Melbourne, Vic 3001, Australia.] Villamor JL, Bermejo AM, Fernandez P, Tabernero MJ. A new GC-MS method for the determination of five amphetamines in human hair. Journal of Analytical Toxicology 2005;29(2):135.

High-Performance Liquid Chromatography (and tandem HPLC techniques):

Ali Z, Poole C. Insights into the retention mechanism of neutral organic compounds on polar chemically bonded stationary phases in reversed-phase liquid chromatography. Journal of Chromatography A 2004;1052(1-2):199. Balogh MP. DESI, IMS, and resurgent challenges to HPLC-MS. LCGC North America 2006;24(1):46. [Microgram Editor’s Notes: An overview. Contact: LC-MS Technology Development, Waters Corp., Milford, MA (zip code not provided).] Barri T, Jonsson JA. Supported liquid membrane work-up of blood plasma samples coupled on-line to liquid chromatographic determination of basic antidepressant drugs. Chromatographia 2004;59(3-4):161. Bones J, Macka M, Paull B. Evaluation of monolithic and sub 2 microm particle packed columns for the rapid screening for illicit drugs--application to the determination of drug contamination on Irish euro banknotes. Analyst, Mar 2007; 132(3): 208-17. Bosakova Z, Curinova E, Tesarova E. Comparison of vancomycin-based stationary phases with different chiral selector coverage for enantioselective separation of selected drugs in high-performance liquid chromatography. Journal of Chromatography A 2005;1088(1-2):94. Bose D, Durgbanshi A, Capella-Peiro ME, Gil-Agusti M, Carda-Broch S, EsteveRomero J. Determination of drugs in pharmaceuticals and pesticides by micellar liquid chromatography. Indian Journal Of Chemistry Section B-Organic Chemistry Including Medicinal Chemistry 2004;43(9):1973. Brunetto MR, Cayama YD, Garcia LG, Gallignani M, Obando MA. Determination of cocaine and benzoylecgonine by direct injection of human urine into a columnswitching liquid chromatography system with diode-array detection. Journal of Pharmaceutical and Biomedical Analysis 2005;37(1):115.



CapellaPeiro ME, Bose D, GilAgusti M, EsteveRomero J, CardaBroch S. Direct injection determination of benzoylecgonine, heroin, 6-monoacetylmorphine and morphine in serum by MLC. Journal of Chromatography A 2005;1073(1-2):277. Chambers E, Wagrowski-Diehl DM, Lu Z, Mazzeo JR. Systematic and comprehensive strategy for reducing matrix effects in LC/MS/MS analyses. J Chromatogr B Analyt Technol Biomed Life Sci, Jun 2007; 852(1-2): 22-34. Chirica G, Lachmann J, Chan J. Size exclusion chromatography of microliter volumes for on-line use in low-pressure microfluidic systems. Anal Chem, Aug 2006; 78(15): 5362-8. Churchwell MI, Twaddle NC, Meeker LR, Doerge DR. Improving LC-MS sensitivity through increases in chromatographic performance: Comparisons of UPLCES/MS/MS to HPLC-ES/MS/MS. Journal of Chromatography B-Analytical Technologies In The Biomedical And Life Sciences 2005;825(2):134. Cimpoiu C. Qualitative and quantitative analysis by hyphenated (HP)TLC-FTIR technique. Journal of Liquid Chromatography & Related Technologies 2005;28(78):1203. Crockford DJ, Holmes E, Lindon JC, Plumb RS, Zirah S, Bruce SJ, Rainville P, Stumpf CL, Nicholson JK. Statistical heterospectroscopy, an approach to the integrated analysis of NMR and UPLC-MS data sets: application in metabonomic toxicology studies. Anal Chem, Jan 2006; 78(2): 363-71. Dai J, Carr PW. Role of ion pairing in anionic additive effects on the separation of cationic drugs in reversed-phase liquid chromatography. Journal of Chromatography A 2005;1072(2):169. Decaestecker TN, Casteele SRV, Wallemacq PE, Van Peteghem CH, Defore DL, Van Bocxlaer JF. Information-dependent acquisition-mediated LC-MS/MS screening procedure with semiquantitative potential. Analytical Chemistry 2004;76(21):6365. de Villiers A, Lestremau F, Szucs R, Gelebart S, David F, Sandra P. Evaluation of ultra performance liquid chromatography. Part I. Possibilities and limitations. J Chromatogr A, Sep 2006; 1127(1-2): 60-9. Dubois P, Marchand G, Fouillet Y, Berthier J, Douki T, Hassine F, Gmouh S, Vaultier M. Ionic liquid droplet as e-microreactor. Anal Chem, Jul 2006; 78(14): 4909-17. ElGindy A, Emara S, Mostafa A. Application and validation of chemometricsassisted spectrophotometry and liquid chromatography for the simultaneous determination of six-component pharmaceuticals. Journal of Pharmaceutical and Biomedical Analysis 2006;41(2):421. [Microgram Editor’s Notes: Pharmaceuticals included theophylline, guaifenesin, diphenhydramine, methylparaben, propylparaben, and sodium benzoate in a syrup. Detection/quantitation at 222 nm.


Contact: Suez Canal Univ, Fac Pharm, Pharmaceut Analyt Chem Dept, Ismailia 41522, Egypt.] Esteve-Romero J, Carda-Broch S, Gil-Agusti M, Capella-Peiro ME, Bose D. Micellar liquid chromatography for the determination of drug materials in pharmaceutical preparations and biological samples. Trac-Trends In Analytical Chemistry 2005;24(2):75. Forgacs G, Forgacs E, Cserhati T. Simultaneous effect of organic modifier and physicochemical parameters of some steroidal drugs on their retention on a narrowbore C-1 column. Chemometrics And Intelligent Laboratory Systems 2004;72(2)269. Guillarme D, Nguyen DT, Rudaz S, Veuthey JL. Method transfer for fast liquid chromatography in pharmaceutical analysis: Application to short columns packed with small particle. Part I: Isocratic separation. Eur J Pharm Biopharm, Jun 2007; 66(3): 475-82. Guillarme D, Nguyen DT, Rudaz S, Veuthey JL. Recent developments in liquid chromatography--impact on qualitative and quantitative performance. J Chromatogr A, May 2007; 1149(1): 20-9. Huerta-Fontela M, Galceran MT, Ventura F. Ultraperformance liquid chromatography-tandem mass spectrometry analysis of stimulatory drugs of abuse in wastewater and surface waters. Anal Chem, May 2007; 79(10): 3821-9. Hyun MH, Tan G, Cho YJ. Liquid chromatographic enantioseparation of aryl alphaamino ketones on a crown ether-based chiral stationary phase. Biomedical Chromatography 2005;19(3):208. Istvan K, Rajko R, Keresztury G. Towards the solution of the eluent elimination problem in high-performance liquid chromatography-infrared spectroscopy measurements by chemometric methods. Journal of Chromatography A 2006;1104(12):154. Jones-Lepp TL, Alvarez DA, Petty JD, Huckins JN. Polar organic chemical integrative sampling and liquid chromatography-electrospray/ion-trap mass spectrometry for assessing selected prescription and illicit drugs in treated sewage effluents. Archives Of Environmental Contamination And Toxicology 2004;47(4):427. Joyce C, Smyth WF, Ramachandran VN, O'Kane E, Coulter DJ. The characterisation of selected drugs with amine-containing side chains using electrospray ionisation and ion trap mass spectrometry and their determination by HPLC-ESI-MS. Journal of Pharmaceutical and Biomedical Analysis 2004;36(3):465. Kaufmann A. Determination of the elemental composition of trace analytes in complex matrices using exact masses of product ions and corresponding neutral losses. Rapid Commun Mass Spectrom, Jan 2007; 21(13): 2003-13. 251


Kowalska S, Krupczynska K, Buszewski B. Some remarks on characterization and application of stationary phases for RP-HPLC determination of biologically important compounds. Biomed Chromatogr, Jan 2006; 20(1): 4-22. Lambert W. Pitfalls in LC-MS(-MS) analysis. Bulletin TIAFT 2004;34(2):59. [Microgram Editor’s Notes: Discusses the title subject. Includes numerous references. Contact: Laboratorium voor Toxicologie, Universiteit Gent, Harelbekestraat 72, B-9000 Gent, Belgium.] Lambert W. Pitfalls in LC-MS(-MS) Analysis. Toxichem und Krimtech 2004;71(2):64. [Microgram Editor’s Notes: Language not specified in the abstract (may be in German). Presents the title review. Appears to be a re-publication of the article by the same author and title in Bulletin TIAFT 2004;28(6):439. Contact: Laboratorium voor Toxicologie, Universiteit Gent, Harelbekestraat 72, B-9000 Gent, Belgium.] Lane S, Boughtflower B, Mutton I, Paterson C, Farrant D, Taylor N, Blaxill Z, Carmody C, Borman P. Toward single-calibrant quantification in HPLC. A comparison of three detection strategies: Evaporative light scattering, chemiluminescent nitrogen, and proton NMR. Analytical Chemistry 2005;77(14):4354. Lee H. Pharmaceutical applications of liquid chromatography coupled with mass spectrometry (LC/MS). Journal of Liquid Chromatography & Related Technologies 2005;28(7-8):1161. Lorin M, Delepee R, Maurizot JC, Ribet JP, Morin P. Sensitivity improvement of circular dichroism detection in HPLC by using a low-pass electronic noise filter: Application to the enantiomeric determination purity of a basic drug. Chirality, Feb 2007; 19(2): 106-13. Lurie IS. High-performance liquid chromatography of seized drugs at elevated pressure with 1.7 µm hybrid C18 stationary phase columns. Journal of Chromatography A 2005;1100:168. Maralikova B, Weinmann W. Confirmatory analysis for drugs of abuse in plasma and urine by high-performance liquid chromatography-tandem mass spectrometry with respect to criteria for compound identification. Journal of Chromatography B Analytical Technologies in the Biomedical and Life Sciences 2004;811(1):21. Maurer HH. Advances in analytical toxicology: the current role of liquid chromatography-mass spectrometry in drug quantification in blood and oral fluid. Analytical And Bioanalytical Chemistry 2005;381(1):110. Mol R, Kragt E, Jimidar I, de Jong GJ, Somsen GW. Micellar electrokinetic chromatography-electrospray ionization mass spectrometry for the identification of drug impurities. J Chromatogr B Analyt Technol Biomed Life Sci, Nov 2006; 843(2): 283-8.


Natishan TK. Recent developments of achiral HPLC methods in pharmaceuticals using various detection modes. Journal of Liquid Chromatography & Related Technologies 2004;27(7-9):1237. Nordgren HK, Beck O. Multicomponent screening for drugs of abuse - Direct analysis of urine by LC-MS-MS. Therapeutic Drug Monitoring 2004;26(1):90. Novakova L, Solichova D, Solich P. Advantages of ultra performance liquid chromatography over high-performance liquid chromatography: comparison of different analytical approaches during analysis of diclofenac gel. J Sep Sci, Nov 2006; 29(16): 2433-43. Ojanpera S, Ojanpera I. Forensic drug screening by LC-MS - Using accurate mass measurement. LCGC Europe 2005;18(11):607. Pack BW, Risley DS. Evaluation of a monolithic silica column operated in the hydrophilic interaction chromatography mode with evaporative light scattering detection for the separation and detection of counter-ions. Journal of Chromatography A 2005;1073(1-2):269. Petrovic M, Hernando MD, DiazCruz MS, Barcelo D. Liquid chromatographytandem mass spectrometry for the analysis of pharmaceutical residues in environmental samples: a review. Journal of Chromatography A 2005;1067(1-2):1. Porter SE, Stoll DR, Paek C, Rutan SC, Carr PW. Fast gradient elution reversedphase liquid chromatography with diode-array detection as a high-throughput screening method for drugs of abuse. II. Data analysis. J Chromatogr A, Dec 2006; 1137(2): 163-72. Ramstad T. Enantiomeric purity methods for three pharmaceutical compounds by electrokinetic capillary chromatography utilizing highly sulfated-gammacyclodextrin as the chiral selector. J Chromatogr A, Sep 2006; 1127(1-2): 286-94. Rao RN, Nagaraju D, Jena N, Kumaraswamy G. Development and validation of a reversed-phase HPLC method for monitoring of synthetic reactions during the manufacture of a key intermediate of an anti-hypertensive drug. J Sep Sci, Oct 2006; 29(15): 2303-9. Rbeida O, Christiaens B, Hubert P, Lubda D, Boos KS, Crommen J, Chiap P. Integrated on-line sample clean-up using cation exchange restricted access sorbent for the LC determination of atropine in human plasma coupled to UV detection. Journal of Pharmaceutical and Biomedical Analysis 2005;36(5):947. Reepmeyer JC, Woodruff JT. Use of liquid chromatography-mass spectrometry and a hydrolytic technique for the detection and structure elucidation of a novel synthetic vardenafil designer drug added illegally to a natural herbal dietary supplement. J Chromatogr A, Aug 2006; 1125(1): 67-75.



Sanagi MM, See HH. High temperature liquid chromatography on a poly(styrenedivinylbenzene) stationary phase. Journal of Liquid Chromatography & Related Technologies 2005;28(19):3065. Sauvage FL, Saint-marcoux F, Duretz B, Deporte D, Lachatre G, Marquet P. Screening of drugs and toxic compounds with liquid chromatography-linear ion trap tandem mass spectrometry. Clin. Chem., Sep 2006; 52: 1735 - 1742. Schmidt AH. Validated HPLC method for the determination of residues of acetaminophen, caffeine, and codeine phosphate on swabs collected from pharmaceutical manufacturing equipment in support of cleaning validation. Journal of Liquid Chromatography & Related Technologies 2006;29(11):1663. [Microgram Editor’s Notes: Presents the title study. Contact: Steiner & Co, Deutsch Arzneimittel Gessell, Ostpreussendamm 72-74, D-12207 Berlin, Germany.] Shen JX, Wang H, Tadros S, Hayes RN. Orthogonal extraction/chromatography and UPLC, two powerful new techniques for bioanalytical quantitation of desloratadine and 3-hydroxydesloratadine at 25 pg/mL. J Pharm Biomed Anal, Feb 2006; 40(3): 689-706. Stokvis E, Rosing H, LopezLazaro L, Schellens JHM, Beijnen JH. Switching from an analogous to a stable isotopically labeled internal standard for the LC-MS/MS quantitation of the novel anticancer drug Kahalalide F significantly improves assay performance. Biomedical Chromatography 2004;18(6):400. Stoll DR, Paek C, Carr PW. Fast gradient elution reversed-phase high-performance liquid chromatography with diode-array detection as a high-throughput screening method for drugs of abuse. I. Chromatographic conditions. J Chromatogr A, Dec 2006; 1137(2): 153-62. Thompson R. A practical guide to HPLC enantioseparations for pharmaceutical compounds. Journal of Liquid Chromatography & Related Technologies 2005;28(78):1215. Van Gyseghem E, Jimidar M, Sneyers R, Redlich D, Verhoeven E, Massart DL, Vander Heyden Y. Selection of reversed-phase liquid chromatographic columns with diverse selectivity towards the potential separation of impurities in drugs. Journal of Chromatography A 2004;1042(1-2):69. Wiczling P, Markuszewski MJ, Kaliszan M, Galer K, Kaliszan R. Combined pH/organic solvent gradient HPLC in analysis of forensic material. Journal of Pharmaceutical and Biomedical Analysis 2005;37(5 Sp. Iss. SI):871. Wren SA, Tchelitcheff P. Use of ultra-performance liquid chromatography in pharmaceutical development. J Chromatogr A, Jun 2006; 1119(1-2): 140-6. Yu K, Di L, Kerns E, Li SQ, Alden P, Plumb RS. Ultra-performance liquid chromatography/tandem mass spectrometric quantification of structurally diverse


drug mixtures using an ESI-APCI multimode ionization source. Rapid Commun Mass Spectrom, Jan 2007; 21(6): 893-902. Zhou LZ. Applications of LC/MS in pharmaceutical analysis. Separation Science and Technology 2005;6,499.

Inductively Coupled Plasma- Mass Spectrometry (ICP-MS, Also ICP-OES):

Ammann AA. Inductively coupled plasma mass spectrometry (ICP MS): a versatile tool. J Mass Spectrom, Apr 2007; 42(4): 419-27. Bartle EK, Watling RJ. Provenance determination of oriental porcelain using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). J Forensic Sci, Mar 2007; 52(2): 341-8. Benincasa C, Lewis J, Perri E, Sindona G, Tagarelli A. Determination of trace element in Italian virgin olive oils and their characterization according to geographical origin by statistical analysis. Anal Chim Acta, Mar 2007; 585(2): 366-70. Bornhorst JA, Hunt JW, Urry FM, McMillin GA. Comparison of sample preservation methods for clinical trace element analysis by inductively coupled plasma mass spectrometry. American Journal of Clinical Pathology 2005;123(4):578. Bridge CM, Powell J, Steele KL, Williams M, Macinnis JM, Sigman ME. Characterization of automobile float glass with laser-induced breakdown spectroscopy and laser ablation inductively coupled plasma mass spectrometry. Appl Spectrosc, Oct 2006; 60(10): 1181-7. Garcia-Ruiz S, Moldovan M, Fortunato G, Wunderli S, Garcia Alonso JI. Evaluation of strontium isotope abundance ratios in combination with multi-elemental analysis as a possible tool to study the geographical origin of ciders. Anal Chim Acta, May 2007; 590(1): 55-66. Gomez-Ariza JL, Arias-Borrego A, T Garcia-Barrera T. Multielemental fractionation in pine nuts (Pinus pinea) from different geographic origins by size-exclusion chromatography with UV and inductively coupled plasma mass spectrometry detection. J Chromatogr A, Jul 2006; 1121(2): 191-9. Huang JQ, Hu X, Zhang JR, Li KX, Yan Y, Xu XB. The application of inductively coupled plasma mass spectrometry in pharmaceutical and biomedical analysis. Journal of Pharmaceutical and Biomedical Analysis 2006;40(2):227. Lewen N, Mathew S, Schenkenberger M, Raglione T. A rapid ICP-MS screen for heavy metals in pharmaceutical compounds. Journal of Pharmaceutical and Biomedical Analysis 2004;35(4):739.



Marshall PS, Leavens B, Heudi O, RamirezMolina C. Liquid chromatography coupled with inductively coupled plasma mass spectrometry in the pharmaceutical industry: selected examples. Journal of Chromatography A 2004;1056(1-2):3. Michalke B. Capillary electrophoresis-inductively coupled plasma-mass spectrometry: A report on technical principles and problem solutions, potential, and limitations of this technology as well as on examples of application. Electrophoresis 2005;26(7-8):1584. Morgan RM, Bull PA. The philosophy, nature and practice of forensic sediment analysis. Progress in Physical Geography, Feb 2007; 31: 43-58. Pye K, Blott SJ, Croft DJ, Witton SJ. Discrimination between sediment and soil samples for forensic purposes using elemental data: an investigation of particle size effects. Forensic Sci Int, Mar 2007; 167(1): 30-42. Sarin RK, Srivastava S, Srivastava AK, Anil G, Reddy MRP. Multielement determination in gum opium by microwave digestion and inductively coupled plasma optical emission spectroscopy. Chemical Papers 2004;58(2):101. [Microgram Editor’s Notes: Presents the analysis of Indian gum opium by the title technique (13 elements found in quantifiable levels). Contact: Central Forensic Science Laboratory, BPR and D, MHA, GO1, Hyderabad 500 013, India.] Ubelaker DH, Stothert KE. Elemental analysis of alkalis and dental deposits associated with coca chewing in Ecuador. Latin American Antiquity 2006;17(1):77. Wrobel K, DeNicola K, Wrobel K, Caruso J. ICP-MS: Metals and much more. Advances In Mass Spectrometry, Vol 16 (Series: Advances In Mass Spectrometry) 2004;16):229. Zeichner A, Ehrlich S, Shoshani E, Halicz L. Application of lead isotope analysis in shooting incident investigations. Forensic Sci Int, Apr 2006; 158(1): 52-64.

Infrared and Raman Spectroscopy:

Bartlome R, Fischer C, Sigrist MW. Vapor-phase infrared spectroscopy on solid organic compounds with a pulsed resonant photoacoustic detection scheme. Proceedings of SPIE - The International Society for Optical Engineering 2005:5864. Bell SEJ, Beattie JR, McGarvey JJ, Peters KL, Sirimuthu NMS, Speers SJ. Development of sampling methods for Raman analysis of solid dosage forms of therapeutic and illicit drugs. Journal of Raman Spectroscopy 2004;35(5):409. Bell SEJ, Sirimuthu NMS. Rapid, quantitative analysis of ppm/ppb nicotine using surface-enhanced Raman scattering from polymer-encapsulated Ag nanoparticles (Gel-colls). Analyst 2004;129(11):1032. [Microgram Editor’s Notes: Presents the title study. Contact: Queens Univ Belfast, Sch Chem, David Keir Bldg, Belfast BT9 5AG, Antrim, North Ireland.]


Bleisteiner B, Geiger R, Yvon J. Raman micro spectroscopy. Today a routine analytical method. CLB Chemie in Labor und Biotechnik 2005;56(3):74. Borglund N, Astrand PG, Csillag S. Improved background removal method using principal components analysis for spatially resolved electron energy loss spectroscopy. Microscopy and Microanalysis 2005;11(1):88. Causin V, Marega C, Carresi P, Schiavone S, Marigo A. A quantitative differentiation method for plastic bags by infrared spectroscopy, thickness measurement, and differential scanning calorimetry for tracing the source of illegal drugs. Forensic Science International 2006;164(2-3):148. [Microgram Editor’s Notes: 50 bags of types typically used for drug packaging were analyzed. The results indicate that even mass-produced bags have a large degree of variability, and can be differentiated and/or linked. Contact: Dipartimento di Scienze Chimiche dell’Universita, via Marzolo 1, Padua 35131, Italy.] Chan KL, Kazarian SG. Detection of trace materials with Fourier transform infrared spectroscopy using a multi-channel detector. Analyst, Jan 2006; 131(1): 126-31. Clarke SJ, Littleford RE, Smith WE, Goodacre R. Rapid monitoring of antibiotics using Raman and surface enhanced Raman spectroscopy. Analyst 2005;130(7):1019. Lin Z, Zhou L, Mahajan A, Song S, Wang T, Ge Z, Ellison D. Real-time endpoint monitoring and determination for a pharmaceutical salt formation process with inline FT-IR spectroscopy. J Pharm Biomed Anal, Apr 2006; 41(1): 99-104. Noonan KY, Beshire M, Darnell J, Frederick KA. Qualitative and quantitative analysis of illicit drug mixtures on paper currency using Raman microspectroscopy. Applied Spectroscopy 2005;59(12):1493. Patterson BM, Havrilla GJ. Attenuated total internal reflection infrared microspectroscopic imaging using a large-radius germanium internal reflection element and a linear array detector. Appl Spectrosc, Nov 2006; 60(11): 1256-66. Pitt GD, Batchelder DN, Bennett R, Bormett RW, Hayward IP, Smith BJE, Williams KPJ, Yang YY, Baldwin KJ, Webster S. Engineering aspects and applications of the new Raman instrumentation. IEE Proceedings: Science, Measurement, and Technology 2005;152(6):241. Rantanen J, Wikstrom H, Turner R, Taylor LS. Use of in-line near-infrared spectroscopy in combination with chemometrics for improved understanding of pharmaceutical processes. Analytical Chemistry 2005;77(2):556. Reffner JA. Infrared microprobe analysis using reflection methods. Microscope 2005;53(1):33. Reich G. Near-infrared spectroscopy and imaging: Basic principles and pharmaceutical applications. Advanced Drug Delivery Reviews 2005;57(8):1109.



Ricci C, Chan KL, Kazarian SG. Combining the tape-lift method and Fourier transform infrared spectroscopic imaging for forensic applications. Appl Spectrosc, Sep 2006; 60(9): 1013-21. Rodionova OY, Houmoller LP, Pomerantsev AL, Geladi P, Burger J, Dorofeyev VL, Arzamastsev AP. NIR spectrometry for counterfeit drug detection. Analytica Chimica Acta 2005;549(1-2):151. Ryder AG. Surface enhanced Raman scattering for narcotics detection and applications to chemical biology. Current Opinion in Chemical Biology 2005;9(5):489. Wartewig S, Neubert RHH. Pharmaceutical applications of Mid-IR and Raman spectroscopy. Advanced Drug Delivery Reviews 2005;57(8):1144. Zieba-Palus J, Kunicki M. Application of the micro-FTIR spectroscopy, Raman spectroscopy and XRF method examination of inks. Forensic Sci Int, May 2006; 158(2-3): 164-72.

Ion Spectroscopy:

Keller T, Keller A, Tutsch-Bauer E, Monticelli F. Application of ion mobility spectrometry in cases of forensic interest. Forensic Sci Int, Sep 2006; 161(2-3): 130-40. Jiang D, Wei Y, Zhao G, Cheng C. Research of IMS technology and its application in narcotic drugs and explosives detection. Tongweisu 2005;18(1-2):51. [Microgram Editor’s Notes: Narcotics and explosives were not specified in the abstract. This article is written in Chinese. Contact: Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, Peop. Rep. China.] Khayamian T, Jafari MT. Design for electrospray ionization-ion mobility spectrometry. Anal Chem, Apr 2007; 79(8): 3199-205. Tang X, Bruce JE, Hill Jr. HH. Characterizing electrospray ionization using atmospheric pressure ion mobility spectrometry. Anal Chem, Nov 2006; 78(22): 7751-60.

Mass Spectrometry:

Benson S, Lennard C, Maynard P, Roux C. Forensic applications of isotope ratio mass spectrometry - A review. Forensic Science International 2006;157(1):1. Carter JF, Sleeman R, Hill JC, Idoine F, Titterton EL. Isotope ratio mass spectrometry as a tool for forensic investigation (examples from recent studies). Science & Justice 2005;45(3):141. [Microgram Editor’s Notes: An overview and minor review. Includes Ecstasy tablets and heroin samples as examples. Contact: Mass Spec Analytical Ltd., Filton, Bristol BS99 7AR, UK.] Finck Y, Aydin N, Pellaton C, Gorin G, Gulacar F. Combination of gas chromatography-mass spectrometry and mass spectral deconvolution for structural


elucidation of an unusual C-29-steroid detected in a complex sedimentary matrix. Journal of Chromatography A 2004;1049(1-2):227. Halket JM, Zaikin VG. Derivatization in mass spectrometry. On-line derivatisation/degradation. Eur J Mass Spectrom (Chichester, Eng), Jan 2006; 12(1): 1-13. Hopfgartner G, Varesio E, Tschappat V, Grivet C, Bourgogne E, Leuthold LA. Triple quadrupole linear ion trap mass spectrometer for the analysis of small molecules and macromolecules. Journal Of Mass Spectrometry 2004;39(8):845. Koppenaal DW, Barinaga CJ, Denton MB, Sperline RP, Hieftje GM, Schilling GD, Andrade FJ, Barnes, IV JH. MS detectors. Analytical Chemistry 2005;77(21):418A. Kreuzer-Martin HW, Jarman KH. Stable Isotope Ratios and Forensic Analysis of Microorganisms. Appl. Envir. Microbiol., Jun 2007; 73: 3896 - 3908. Maurer HH. Hyphenated mass spectrometric techniques-indispensable tools in clinical and forensic toxicology and in doping control. J Mass Spectrom, Nov 2006; 41(11): 1399-413. Mitchell-Roberts AC. Advanced techniques in mass spectrometry for forensic applications. Dissertation Abstracts International, B 2006;67(1):237. [Microgram Editor’s Notes: Abstract not provided. Contact: Univ. of Florida, Gainesville, FL] Pavlic M, Libiseller K, Oberacher H. Combined use of ESI-QqTOF-MS and ESIQqTOF-MS/MS with mass-spectral library search for qualitative analysis of drugs. Analytical and Bioanalytical Chemistry 2006;386(1):69. [Microgram Editor’s Notes: 319 drugs (therapeutic and illicit) were analyzed. The resulting spectral library was successfully applied to the characterization of 39 forensic casework samples. Contact: Institute of Legal Medicine, Innsbruck Medical University, Muellerstrasse 44, Innsbruck 6020, Austria.] Petrick LM, Wilson TA, Fawcett WR. High-performance liquid chromatographyultraviolet-visible spectroscopy-electrospray ionization mass spectrometry method for acrylic and polyester forensic fiber dye analysis. J Forensic Sci, Jul 2006; 51(4): 771-9. Petucci C, Woodworth R, Hauze D. Structure elucidation and reaction monitoring of synthetic intermediates using an automated accurate mass GC-TOF mass spectrometer in drug discovery. Journal of Mass Spectrometry 2005;40(10):1387. Rubakhin SS, Jurchen JC, Monroe EB, Sweedler JV. Imaging mass spectrometry: fundamentals and applications to drug discovery. Drug Discovery Today 2005;10(12):823. Sakayanagi M, Yamada Y, Sakabe C, Watanabe K, Harigaya Y. Identification of inorganic anions by gas chromatography/mass spectrometry. Forensic Science International 2006;157(2-3):134. 259


Savchuk SA, Simonov EA, Sorokin VI, Dorogokupets OB, Vedenin AN. Retention time locking in the determination of narcotic drugs by chromatography and chromatography - mass spectrometry. Journal of Analytical Chemistry (translation of Zhurnal Analiticheskoi Khimii) 2004;59(10):954. Shao X, Wang G, Wang S, Su Q. Extraction of mass spectra and chromatographic profiles from overlapping GC/MS signals with background. Analytical Chemistry 2004;76(17):5143. [Microgram Editor’s Notes: Presents the title study. The authors indicate that the presented methodology is better than the SIMPLISMA technique. Contact: xshao] Shiea J, Huang MZ, HSu HJ, Lee CY, Yuan CH, Beech I, Sunner J. Electrosprayassisted laser desorption/ionization mass spectrometry for direct ambient analysis of solids. Rapid Communications In Mass Spectrometry 2005;19(24):3701. Sigman ME, Williams MR. Covariance mapping in the analysis of ignitable liquids by gas chromatography/mass spectrometry. Anal Chem, Mar 2006; 78(5): 1713-8. Sleeman R, Carter J, Ebejer K. Drugs on money and beyond: Tandem mass spectrometry in the forensic sciences. Spectroscopy Europe 2005-2006;17(6):10. Watkins MA, WeWora DV, Li S, Winger BE, Kenttamaa HI. Compound screening for the presence of the primary N-oxide functionality via ion-molecule reactions in a mass spectrometer. Analytical Chemistry 2005;77(16):5311. Wen X, Dagan S, Wysocki VH. Small-molecule analysis with silicon-nanoparticleassisted laser desorption/ionization mass spectrometry. Anal Chem, Jan 2007; 79(2): 434-44. Weston DJ, Bateman R, Wilson ID, Wood TR, Creaser CS. Direct analysis of pharmaceutical drug formulations using ion mobility spectrometry/quadrupoletime-of-flight mass spectrometry combined with desorption electrospray ionization. Analytical Chemistry 2005;77(23):7572. Wood M, Laloup M, Samyn N, Del Mar Ramirez Fernandez M, de Bruijn EA, Maes RAA, De Boeck G. Recent applications of liquid chromatography-mass spectrometry in forensic science. J Chromatogr A, Oct 2006; 1130(1): 3-15. Yinon J. Advances in forensic applications of mass spectrometry. CRC Press LLC:Boca Raton, FL, 2004. [Microgram Editor’s Notes: No abstract provided. Contact: USA (no further addressing information provided in the abstract).] Zhang J, McCombie G, Guenat C, Knochenmuss R. FT-ICR mass spectrometry in the drug discovery process. Drug Discovery Today 2005;10(9):635.


Microchip Technology:

Anonymous. Forensic sample analysis on a microchip. Analytical Chemistry 2004;76(7):117A. [Microgram Editor’s Notes: No abstract or contact information provided.] Hompesch RW, Garcia CD, Weiss DJ, Vivanco JM, Henry CS. Analysis of natural flavonoids by microchip-micellar electrokinetic chromatography with pulsed amperometric detection. Analyst 2005;130(5):694. Nyholm L. Electrochemical techniques for lab-on-a-chip applications. Analyst 2005;130(5):599. Schulze P, Ludwig M, Kohler F, Belder D. Deep UV laser-induced fluorescence detection of unlabeled drugs and proteins in microchip electrophoresis. Analytical Chemistry 2005;77(5):1325. Tanyanyiwa J, Hauser PC. Capillary and microchip electrophoresis of basic drugs with contactless conductivity detection. Electrophoresis 2004;25(17):3010.

Nuclear Magnetic Resonance Spectroscopy:

Booy KJ, Wiegerinck P, Vader J, Kaspersen F, Lambregts D, Vromans H, Kellenbach E. The use of C-13 labeling to enhance the sensitivity of C-13 solid-state CPMAS NMR to study polymorphism in low dose solid formulations. Journal of Pharmaceutical Sciences 2005;94(2):458. Castle AL, Fiehn O, Kaddurah-Daouk R, Lindon JC. Metabolomics Standards Workshop and the development of international standards for reporting metabolomics experimental results. Brief Bioinform, Jun 2006; 7: 159 - 165. Hajduk P. NMR-based screening in drug discovery and design. Abstracts of Papers of the American Chemical society 2005;230:U2762. Holzgrabe U, Deubner R, Schollmayer C, Waibel B. Quantitative NMR spectroscopy - Applications in drug analysis. Journal of Pharmaceutical and Biomedical Analysis 2005;38(5):806. Li ZJ, Abramov Y, Bordner J, Leonard J, Medek A, Trask AV. Solid-state acid-base interactions in complexes of heterocyclic bases with dicarboxylic acids: Crystallography, hydrogen bond analysis, and N-15 NMR spectroscopy. Journal of the American chemical society 2006;128(25):8199. Lindon JC, Holmes E, Nicholson JK. Metabonomics in pharmaceutical R & D. FEBS J., Mar 2007; 274: 1140 - 1151. McCormick KR, Seleem S, Ilich PP. NMR spectroscopy analysis in the development of inhibitors to an illicit drug proxy synthesis. Abstracts of papers of the American chemical society 2005;229(Part 1):U408.



Mercier KA, Powers R. Determining the optimal size of small molecule mixtures for high throughput NMR screening. Journal of Biomolecular NMR 2005;31(3):243. Osokin DY, Khusnutdinov RR. Two-frequency composite pulses in NQR. Applied Magnetic Resonance 2006;30(1):7. [Microgram Editor’s Notes: Use of the title technique for detection of narcotics is specifically mentioned in the abstract (NFI). Contact: Kazan Physical-Technical Institute, Russian Academy of Sciences, Kazan, Russia.]

Osmolality: Solid Phase Micro-Extraction (Headspace Techniques and Solvent Analysis):

Andrasko J. A simple microthermal desorption device. J Forensic Sci, Jul 2006; 51(4): 925-8. Bodle ES, Hardy JK. Multivariate pattern recognition of petroleum-based accelerants by solid-phase microextraction gas chromatography with flame ionization detection. Anal Chim Acta, Apr 2007; 589(2): 247-54. Borusiewicz R, Zadora G, ZiebaPalus J. Application of head-space analysis with passive adsorption for forensic purposes in the automated thermal desorption-gas chromatography-mass spectrometry system. Chromatographia 2004;60:S133. Chia KJ, Huang SD. Simultaneous derivatization and extraction of amphetaminelike drugs in urine with headspace solid-phase microextraction followed by gas chromatography-mass spectrometry. Analytica Chimica Acta 2005;539(1-2):49. Follador MJD, Yonamine M, Moreau RLD, Silva OA. Detection of cocaine and cocaethylene in sweat by solid-phase microextraction and gas chromatography/mass spectrometry. Journal of Chromatography B - Analytical Technologies in the Biomedical and Life Sciences 2004;811(1):37. Fu YL, Hu YL, Zheng YJ, Li GK. Preparation and application of poly(dimethylsiloxane)/beta-cyclodextrin solid-phase microextraction fibers. J Sep Sci, Nov 2006; 29(17): 2684-91. Hu X, Hu Y, Li G. Development of novel molecularly imprinted solid-phase microextraction fiber and its application for the determination of triazines in complicated samples coupled with high-performance liquid chromatography. J Chromatogr A, Apr 2007; 1147(1): 1-9. Ji J, Deng CH, Shen WW, Zhang XM. Field analysis of benzene, toluene, ethylbenzene and xylene in water by portable gas chromatography-microflame ionization detector combined with headspace solid-phase microextraction. Talanta 2006;69(4):894.


Klick S, Skold A. Validation of a generic analytical procedure for determination of residual solvents in drug substances. Journal of Pharmaceutical and Biomedical Analysis 2004;36(2):401. Liao L, Yang J, Wang Y, Sun T, Jia J. Study on a novel circulating cooling solid-phase microextraction method. J Chromatogr A, Nov 2006; 1135(1): 1-5. Liu M, Liu Y, Zeng Z, Peng T. Preparation and characteristics of high pH-resistant sol-gel alumina-based hybrid organic-inorganic coating for solid-phase microextraction of polar compounds. J Chromatogr A, Mar 2006; 1108(2): 149-57. Mehdinia A, Mousavi MF, Shamsipur M. Nano-structured lead dioxide as a novel stationary phase for solid-phase microextraction. J Chromatogr A, Nov 2006; 1134(12): 24-31. Rearden P, Harrington PB. Rapid screening of precursor and degradation products of chemical warfare agents in soil by solid-phase microextraction ion mobility spectrometry (SPME-IMS). Analytica Chimica Acta 2005;545(1):13. Rocha SM, Coutinho P, Barros A, Delgadillo I, Coimbra MA. Rapid tool for distinction of wines based on the global volatile signature. J Chromatogr A, May 2006; 1114(2): 188-97. Rodrigues JC, Neto AJ, Fernandes C, Alves C, Contadori AS, Lancas FM. Development of an improved heated interface for coupling solid-phase microextraction to high-performance liquid chromatography. J Chromatogr A, Feb 2006; 1105(1-2): 208-12. Zhao W, Ouyang G, Pawliszyn J. Preparation and application of in-fibre internal standardization solid-phase microextraction. Analyst, Mar 2007; 132(3): 256-61.

Thin Layer Chromatography:

Cimpoiu C. Qualitative and quantitative analysis by hyphenated (HP)TLC-FTIR technique. Journal of Liquid Chromatography & Related Technologies 2005;28(78):1203. Mali BD, Garad MV. Thin-layer chromatographic detection of chloral hydrate in an alcoholic beverage. Journal of Planar Chromatography - Modern TLC 2005;18(105):397. Palamarev CE, Kandinska MI, Palamareva MD. Automatic selection of mobile phases. IV. Thin-layer chromatography on silica of simple and complex organic compounds. Journal of Liquid Chromatography & Related Technologies 2004;27(13):2003. Petruczynik A, WaksmundzkaHajnos M, Hajnos ML. The effect of chromatographic conditions on the separation of selected alkaloids in RP-HPTLC. Journal of Chromatographic Science 2005;43(4):183.



Spangenberg B, Seigel A, Kempf J, Weinmann W. Forensic drug analysis by means of diode-array HPTLC using RF and UV library search. Journal of Planar Chromatography - Modern TLC 2005;18(105):336. Sullivan C, Sherma J. Comparative evaluation of TLC and HPTLC plates containing standard and enhanced UV indicators for efficiency, resolution, detection, and densitometric quantification using fluorescence quenching. Journal of Liquid Chromatography & Related Technologies 2004;27(13):1993. VanBerkel GJ, Ford MJ, Deibel MA. Thin-layer chromatography and mass spectrometry coupled using desorption electrospray ionization. Analytical Chemistry 2005;77(5):1207. Zapala W, WaksmundzkaHajnos M. Retention process in normal-phase TLC systems. Journal of Liquid Chromatography & Related Technologies 2004;27(14):2127.

X-Ray based Techniques:

Kotrly M. Use of X-ray diffraction in forensic sciences. Materials Structure in Chemistry, Biology, Physics, and Technology 2006;13(2):113. [Microgram Editor’s Notes: A review of the title topic. This article is written in Czech. Contact: Kriminalisticky Ustav Praha, Prague 170 89, Czech Rep.] Maurin JK, Plucinski F, Mazurek AP, Fijalek Z. The usefulness of simple X-ray powder diffraction analysis for counterfeit control--the Viagra example. J Pharm Biomed Anal, Mar 2007; 43(4): 1514-8. Nakai I. Recent advances and future of X-ray fluorescence. Oyo Butsuri 2005;74(4):453. Ninomiya T. X-ray spectrometry in forensic research. X-Ray Spectrometry 2004:553. Potts PJ, Ellis AT, Kregsamer P, Streli C, Vanhoof C, West M, Wobrauschek P. Atomic spectrometry update. X-ray fluorescence spectrometry. Journal of Analytical Atomic Spectrometry 2005;20(10):1124.


Botonjic E. Forensic and biological applications of vibrational spectroscopy. Diss. Abstr. Int. B 2005;66(1):257. Cheng YQ, Fan LY, Chen HL, Chen XG, Hu ZD. Method for on-line derivatization and separation of aspartic acid enantiomer in pharmaceuticals application by the coupling of flow injection with micellar electrokinetic chromatography. Journal of Chromatography A 2005;1072(2):259.


Cody RB, Laramee JA, Durst HD. Versatile new ion source for the analysis of materials in open air under ambient conditions. Analytical Chemistry 2005;77(8):2297. Cooks RG, Ouyang Z, Takats Z, Wiseman JM. Ambient Mass Spectrometry. Science, Mar 2006; 311: 1566 - 1570. Cozzi NV, Foley KF, Fontanilla D, Gopalakrishnan A, and Ruoho AE. A novel amphetamine-related photoaffinity probe. FASEB J, Apr 2007; 21: A776. Crifasi JA, Bruder MF, Long CW, Janssen K. Performance evaluation of thermal desorption system (TDS) for detection of basic drugs in forensic samples by GC-MS. J Anal Toxicol, Oct 2006; 30(8): 581-92. Davis J, Reagan R. Method for collecting, extracting and quantifying drugs from saliva samples and surfaces. (Patent) Chemical Abstracts 2006;26:1253644. Delmdahl R, von Oldershausen G. Quantitative solid sample analysis by ArF excimer laser ablation. Journal of Molecular Structure 2005;744(Sp. Iss. SI):255. Evans HK. History of microcrystal tests in forensic science. Microscope 2005;53(1):3. Federici JF, Schulkin B, Huang F, Gary D, Barat R, Oliveira F, Zimdars D. THz imaging and sensing for security applications - Explosives, weapons, and drugs. Semiconductor Science and Technology 2005;20(7):S266. Fedotov AV, Fedotov VV. Detection of narcotics and explosives by nitrogen-14 NQR spectroscopy. (Patent) Chemical Abstracts 2005:248244. Gartsev NA, Semeikin NP, Sharshin YA, Pomozov VV, Nedorezov AV, Nikiforov AA. Detector for detection of explosives and drugs. RU 2234695 C1 20 Aug 2004. CLASS: ICM: G01N024 00. APPLICATION: RU 2003 106186 6 Mar 2003. [Microgram Editor’s Notes: Appears to be based on nuclear quadrupole resonance detection. Drugs not specified. This patent is written in Russian. Contact: Russia (no further addressing information was provided).] Henry KD, Lovell JS. Stroboscopic system and method for detecting substances, such as explosives and/or drugs, using, in part, short bursts of energy light from a relatively low energy strobe. (Patent) Chemical Abstracts 2006;145:350077u. Hollifield JM. Flow chart for the rapid identification of inorganic compounds using PLM. Microscope 2005;53(3):99. Hopen TJ. Microchemical tests: Methods and techniques. Microscope 2005;53(1):5. Houck MM, Bowen R. An argument for light microscopy - A review of forensic microscopy for trace evidence analysis. Forensic Science Reviews 2005;17(1):1.



Kalach AV. Criminalistic identification of explosives and narcotics using gas analyzers. Pribory I Sistemy: Upravlenie, Kontrol, Diagnostika 2005;(5):27. Kanamori T, Tsujikawa K, Iwata YT, Inoue H, Ohtsuru O, Kishi T, Hoshina H, Otani C, Kawase K. Application of terahertz spectroscopy to abused drug analysis. Chemical Abstracts 2005:1273198. Kidwell DA, Riggs LA. Comparing two analytical methods: Minimal standards in forensic toxicology derived from information theory. Forensic Science International 2004;145(2- 3):85. [Microgram Editor’s Notes: Presents an information theory based method for comparing new with existing analytical instrumentation. Contact: Chemistry Division, Naval Research Laboratory, Washington, DC 20375.] Lee H-S, Park S-R, Lee B-Y, Ko S-K, Chung C. Study on detection technique of illicit materials using pulsed fast white neutron analysis. Nuclear Instruments & Methods in Physics Research, Section A: Accelerators, Spectrometers, Detectors, and Associated Equipment 2006;562(2):1076. [Microgram Editor’s Notes: A feasability study. One of the substrates was PMMA. Contact: POSTECH, Pohang Accelerator Laboratory, Pohang, 790-784, S. Korea.] Moorehead W. Practical identity using microcrystal tests. Microscope 2005;53(2):73. Multiple Authors. Analytical Chemistry Fundamental Reviews 2004. Analytical Chemistry 2004;76(12):3251 et seq. [Microgram Editor’s Notes: Presents overviews and reviews of the following topics: Planar Chromatography, Solid State Nuclear Magnetic Resonance, Fiber-Optic Chemical Sensors and Biosensors, Electrochemical Sensors, Thermal Analysis, Atomic Spectroscopy, Environmental Mass Spectrometry (Emerging Contaminants and Current Issues), Chemometrics, Micro Total Analysis Systems (Recent Developments), Gas Chromatography, Inductively Coupled Plasma Mass Spectrometry, Mass Spectrometry of Synthetic Polymers, Scanning Probe Microscopy, and X-ray Spectrometry. See the issue for authors and contact information.] Napoli JD. Device for testing surfaces of articles for traces of explosives and/or drugs. (Patent) Chemical Abstracts 2005:77931. Nguyen DH, Berry S, Christensen DL, Klymowsky C. Laser desorption and detection of explosives, narcotics, and other chemical substances. U.S. Pat. Appl. Publ. US 20040169845 A1 2 Sep 2004. CLASS: ICM: G01N021-01 NCL: 356036000. Application: US 2002- 62135 1 Feb 2002. [Microgram Editor’s Notes: Presents the title patent. Narcotics not specified in abstract. Contact: Can. (No further addressing information was provided).] Pack BW, Risley DS. Evaluation of a monolithic silica column operated in the hydrophilic interaction chromatography mode with evaporative light scattering detection for the separation and detection of counter-ions. Journal of Chromatography A 2005;1073(1-2):269.


Piletska EV, Romero-Guerra M, Chianella I, Karim K, Turner AR, Piletsky SA. Towards the development of multisensor for drugs of abuse based on molecular imprinted polymers Analytica Chimica Acta 2005;542(1):111. Semeikin NP, Sharshin YA, Gartsev NA, Belyi YI, Maksimov EM, Perederii AN, Reznev AA. NQR detector of explosives, narcotics, and metals hidden under people’s clothing. (Patent) Chemical Abstracts 2005:168594. Sinyavskii NY, Kovalenko SG. Nuclear quadrupole resonance based method for detecting explosives and drugs. (Patent) Chemical Abstracts 2005:266821. Srinivas NR. Simultaneous chiral analyses of multiple analytes: Case studies, implications and method development considerations. Biomedical Chromatography 2004;18(10):759. [Microgram Editor’s Notes: A review, includes some illustrative case studies. Contact: Drug Development, Discovery Research, Dr. Reddy’s Laboratories, Hyderabad 500 049, India.] Stewart-Jones A, Poppy GM. Comparison of glass vessels and plastic bags for enclosing living plant parts for headspace analysis. J Chem Ecol, Apr 2006; 32(4): 845-64. Vandrish G, Nguyen DH, Berry S, Klymowsky C, Parent M, Locquaio S. Multi-zonal detection of explosives, narcotics, and other chemical substances. (Patent) Chemical Abstracts 2006:359669. Veuthey JL, Souverain S, Rudaz S. Column-switching procedures for the fast analysis of drugs in biologic samples. Therapeutic Drug Monitoring 2004;26(2):161. Ward TJ, Hamburg DM. Chiral separations. Analytical Chemistry 2004;76(16):4635. White C. Integration of supercritical fluid chromatography into drug discovery as a routine support tool - Part I. Fast chiral screening and purification. Journal of Chromatography A 2005;1074(1-2):163. Wong R, Zoltek R. Combination assay for alcohol and drugs of abuse. (Patent) Chem. Abstr. 2006;144:102247v. Zarzycki P, Kulhanek KM, Smith R, Bartoszuk MA, Lamparczyk H. Planar chromatography versus column chromatography: A performance comparison. Lc Gc North America 2005;23(3):286.

Portable Detection and Analytical Instrumentation Issue: “Free Trade” agreements and the easing of formally restrictive national and international borders have resulted in dramatic increases in cargo transshipments and personal travel, thereby complicating drug inspection and interdiction efforts at POEs. Discovery and confirmational analysis of suspected drugs in cargo or on



individuals is severely hampered by the lack of on-site detection and/or analytical equipment. Solution: Development of portable and highly sensitive detectors for drug detection and analyses allows law enforcement personnel and/or forensic chemists to perform screening type analyses on-site. In those cases where new methodologies have proven effective, case reports are generated for the forensic and enforcement communities. References: Babichenko S, Erme E, Ivkina T, Poryvkina L, Sominsky V. A portable device and method for on-site detection and quantification of drugs. PCT Int. Appl. WO 2005;111,586. Campbell JG, Grossman SI. Apparatus for detecting drugs in a beverage. (Patent) Chemical Abstracts 2005;143:54892g. Capitan-Vallvey LF, Asensio LJ, Lopez-Gonzalez J, Fernandez-Ramos MD, Palma AJ. Oxygen-sensing film coated photodetectors for portable instrumentation. Anal Chim Acta, Jan 2007; 583(1): 166-73. Capitan-Vallvey LF, Asensio LJ, Lopez-Gonzalez J, Fernandez-Ramos MD, Palma AJ. Oxygen-sensing film coated photodetectors for portable instrumentation. Anal Chim material. Neuro Endocrinol Lett, Dec 2006; 27 Suppl 2: 125-9. Chen Y, Pawliszyn J. Solid-phase microextraction field sampler. Analytical Chemistry 2044,76(22):6823. [Microgram Editor’s Notes: Presents the title study. Contact: Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.] Liu XY, Nacson S, Grigoriev A, Lynds P, Pawliszyn J. A new thermal desorption solid-phase system for hand-held ion mobility microextraction spectrometry. Analytica Chimica Acta 2006;559(2):159. Mawatari K, Shimoide K. Reflective thermal lens detection device. Lab Chip, Jan 2006; 6(1): 127-30. Mukhopadhyay R. Portable FTIR spectrometers get moving. Analytical Chemistry 2004;76(19):369A. [Microgram Editor’s Notes: A mini-review of the title instruments, includes a comparative survey of available instruments. Contact: No contact information was provided.] Osan TM, Cerioni LMC, Forguez J, Olle JM, Pusiol DJ. NQR: From imaging to explosives and drugs detection. (Patent) Chemical Abstracts 2006:1348733. Smith PA, Sng MT, Eckenrode BA, Leow SY, Koch D, Erickson RP, Lepage CRJ, Hook GL. Towards smaller and faster gas chromatography-mass spectrometry


systems for field chemical detection. Journal of Chromatography A 2005;1067(12):285. Wan F, Sun HW, Fan SF. Design of a portable UV-Vis spectrophotometer. Spectroscopy And Spectral Analysis 2006;26(4):779. Xu W. Portable type explosive/drugs detector having compact structure, light weight, and convenient application. (Patent) Chemical Abstracts 2006:509864.

Analytical Artifacts:

Bowen RAR, George DT, Hortin GL. False-negative result for cocaine metabolites on a lateral-flow drug test slide corrected by dilution. Clinical Chemistry 2005;51(4):790. Callister SJ, Barry RC, Adkins JN, Johnson ET, Qian WJ, Webb-Robertson BJM, Smith RD, Lipton MS. Normalization approaches for removing systematic biases associated with mass spectrometry and label-free proteomics. Journal of Proteome Research 2006;5(2):277. Tsumura Y, Mitome T, Kimoto S. False positives and false negatives with a cocainespecific field test and modification of test protocol to reduce false decision. Forensic Science International 2005;155(2-3):158. Williams S. Ghost peaks in reversed-phase gradient HPLC: a review and update. Journal of Chromatography A 2004;1052(1-2):1.


Ariyama K, Horita H, Yasui A. Application of inorganic element ratios to chemometrics for determination of the geographic origin of Welsh onions. Journal of Agricultural and Food Chemistry 2004;52(19):5803. Baroni MV, Nores ML, Diaz MP, Chiabrando GA, Fassano JP, Costa C, Wunderlin DA. Determination of volatile organic compound patterns characteristic of five unifloral honey by solid-phase microextraction-gas chromatography-mass spectrometry coupled to chemometrics. J Agric Food Chem, Sep 2006; 54(19): 723541. Berlioz B, Cordella C, Cavalli JF, Lizzani-Cuvelier L, Loiseau AM, Fernandez X. Comparison of the amounts of volatile compounds in French protected designation of origin virgin olive oils. J Agric Food Chem, Dec 2006; 54(26): 10092-101. Cichelli A, Pertesana GP. High-performance liquid chromatographic analysis of chlorophylls, pheophytins and carotenoids in virgin olive oils: chemometric approach to variety classification. Journal of Chromatography A 2004;1046(1-2):141. del Campo G, Berregi I, Iturriza N, Santos JI. Ripening and Changes in Chemical Composition of Seven Cider Apple Varieties. Food Science and Technology International, Dec 2006; 12: 477-487.



Furlanetto S, Lanteri S, Orlandini S, Gotti R, Giannini I, Pinzauti S. Selection of background electrolyte for CZE analysis by a chemometric approach. Part I. Separation of a mixture of acidic non-steroidal anti-inflammatory drugs. J Pharm Biomed Anal, Mar 2007; 43(4): 1388-401. Furlanetto S, Lanteri S, Orlandini S, Gotti R, Giannini I, Pinzauti S. Selection of background electrolyte for CZE analysis by a chemometric approach. Part II. Separation of a mixture of basic beta-blocker drugs. J Pharm Biomed Anal, Mar 2007; 43(4): 1402-8. Garcia JCR, Rodriguez RI, Crecente RMP, Garcia JB, Martin SG, Latorre C. Preliminary chemometric study on the use of honey as an environmental marker in Galicia (northwestern Spain). J Agric Food Chem, Sep 2006; 54(19): 7206-12. Gasteiger J. Chemoinformatics: a new field with a long tradition. Anal Bioanal Chem, Jan 2006; 384(1): 57-64. GonzalezMiret ML, Terrab A, Hernanz D, FernandezRecamales MA, Heredia FJ. Multivariate correlation between color and mineral composition of honeys and by their botanical origin. Journal of Agricultural and Food Chemistry 2005;53(7):2574. Gottlieb DM, Schultz J, Bruun SW, Jacobsen S, Sondergaard I. Multivariate approaches in plant science. Phytochemistry 2004;65(11):1531. Gosav S, Praisler M, Dorohoi DO, Popa G. Structure-activity correlations for illicit amphetamines using ANN and constitutional descriptors. Talanta 2006;70(5):922. [Microgram Editor’s Notes: Compounds not specified in the abstract. “ANN” is an acronym for an artificial neural network; the “constitutional descriptors” were not specified in the abstract. The primary database consisted of GC-FTIR data for a large number of drugs of abuse and related compounds. Contact: Department of Physics, Dunarea de Jos University, Str. Domneasca nr. 47, Galati, Rom.] He J, Rodriguez-Saona LE, Giusti MM. Midinfrared spectroscopy for juice authentication-rapid differentiation of commercial juices. J Agric Food Chem, May 2007; 55(11): 4443-52. Hu Y, Liang YZ, Li BY, Li XN, Du YP. Multicomponent spectral correlative chromatography applied to complex herbal medicines. Journal of Agricultural and Food Chemistry 2004;52(26):7771. Kallithraka S, Mamalos A, Makris DP. Differentiation of young red wines based on chemometrics of minor polyphenolic constituents. J Agric Food Chem, May 2007; 55(9): 3233-9. Japon-Lujan R, Ruiz-Jimenez J, de Castro MD. Discrimination and classification of olive tree varieties and cultivation zones by biophenol contents. J Agric Food Chem, Dec 2006; 54(26): 9706-12.


Leger MN, Ryder AG. Comparison of derivative preprocessing and automated polynomial baseline correction method for classification and quantification of narcotics in solid mixtures. Appl Spectrosc, Feb 2006; 60(2): 182-93. Linnet K. Estimation of the limit of detection with a bootstrap-derived standard error by a partly non-parametric approach. Application to HPLC drug assays. Clinical Chemistry and Laboratory Medicine 2005;43(4):394. Liu L, Cozzolino D, Cynkar WU, Gishen M, Colby CB. Geographic classification of spanish and Australian tempranillo red wines by visible and near-infrared spectroscopy combined with multivariate analysis. J Agric Food Chem, Sep 2006; 54(18): 6754-9. Markopoulou CK, Malliou ET, Koundourellis JE. Application of two chemometric methods for the determination of imipramine, amitriptyline and perphenazine in content uniformity and drug dissolution studies. Journal of Pharmaceutical and Biomedical Analysis 2005;37(2):249. Wang P, Tang H, Fitzgibbon MP, Mcintosh M, Coram M, Zhang H, Yi E, Aebersold R. A statistical method for chromatographic alignment of LC-MS data. Biostat., Apr 2007; 8: 357-367. Xie HP, Jiang JH, Chen ZQ, Shen GL, Yu RQ. Chemometric classification of traditional Chinese medicines by their geographical origins using near-infrared reflectance spectra. Anal Sci, Aug 2006; 22(8): 1111-6.


Bowen RAR, George DT, Hortin GL. False-negative result for cocaine metabolites on a lateral-flow drug test slide corrected by dilution. Clinical Chemistry 2005;51(4):790. McDermott SD, Power JD. Drug smuggling using clothing impregnated with cocaine. Journal of Forensic Sciences 2005;50(6):1423. Messina JP, Delamater PL. Defoliation and the war on drugs in Putumayo, Colombia. International Journal of Remote Sensing 2006;27(1):121.

Counterfeit Drugs:

Bernstein IBG, Shuren J. The Food and Drug Administration's Counterfeit Drug Initiative. Journal of Pharmacy Practice, Aug 2006; 19: 250 - 254. Cohen JC, Mrazek M, Hawkins L. Tackling corruption in the pharmaceutical systems worldwide with courage and conviction. Clin Pharmacol Ther, Mar 2007; 81(3): 445-9. Curbing counterfeit drugs. FDA Consum, Sep 2006; 40(5): 11. Deisingh AK. Pharmaceutical counterfeiting. Analyst 2005;130(3):271.



deKieffer DE. The Internet and the globalization of counterfeit drugs. Journal of Pharmacy Practice, Jun 2006; 19: 171-177. Deus L. Technological roles in combating drug diversion and counterfeiting. Journal of Pharmacy Practice, Jun 2006; 19: 146-152. Fernandez FM, Cody RB, Green MD, Hampton CY, McGready R, Sengaloundeth S, White NJ, Newton PN. Characterization of solid counterfeit drug samples by desorption electrospray ionization and direct-analysis-in-real-time coupled to timeof-flight mass spectrometry. ChemMedChem, Jul 2006; 1(7): 702-5. Kawanishi T. Regulatory perspectives from Japan biopharmaceuticals. Biologicals, Mar 2006; 34(1): 65-8.




Laven DL. Introduction: Drug diversion and counterfeiting, Part I. Journal of Pharmacy Practice, Jun 2006; 19: 135 - 139. Laven DL. Introduction: Drug diversion and counterfeiting, Part II. Journal of Pharmacy Practice, Aug 2006; 19: 191 - 195. Maurin JK, Plucinski F, Mazurek AP, Fijalek Z. The usefulness of simple X-ray powder diffraction analysis for counterfeit control-the Viagra example. J Pharm Biomed Anal, Mar 2007; 43(4): 1514-8. Mukhopadhyay R. The hunt for counterfeit medicine. Drugs manufactured by counterfeiters are infiltrating markets worldwide. Investigators are harnessing a variety of analytical techniques to catch as many of the fakes as they can. Anal Chem, Apr 2007; 79(7): 2622-7. Parfitt T. Russia cracks down on counterfeit drugs. Lancet, Oct 2006; 368(9546): 14812. Rudolf PM, Bernstein IBG. Counterfeit drugs. New England Journal of Medicine 2004;350:1384. [Microgram Editor’s Notes: No abstract provided. Contact: Food and Drug Administration, Rockville, MD (zip code not provided in the abstract).] Vredenbregt MJ, Blok-Tip L, Hoogerbrugge R, Barends DM, de Kaste D. Screening suspected counterfeit Viagra and imitations of Viagra with near-infrared spectroscopy. J Pharm Biomed Anal, Mar 2006; 40(4): 840-9. Willis RC. Noninvasive testing for counterfeit drugs. Anal Chem, Mar 2007; 79(5): 1773.

Dragon’s Blood:

Fu XT, Li Y, Du XW, Zhang XQ, Shi RB. [Study of quality standards on Qianshan Huoxue plaster]. Zhongguo Zhong Yao Za Zhi, Sep 2006; 31(17): 1431-3.


Melo MJ, Sousa M, Parola AJ, de Melo JS, Catarino F, Marcalo J, Pina F. Identification of 7,4'-dihydroxy-5-methoxyflavylium in "Dragon's blood": to be or not to be an anthocyanin. Chemistry, Jan 2007; 13(5): 1417-22. Zhang Q, Cui L, Hu Y-q. HPLC determination of ethyl p-hydroxybenzoate in Dragon’s Blood. Zhongcaoyao 2004;35(2):197.

Drugs on Currency:

EsteveTurrillas FA, Armenta S, Moros J, Garrigues S, Pastor A, delaGuardia M. Validated, non-destructive and environmentally friendly determination of cocaine in euro bank notes. Journal of Chromatography A 2005;1065(2):321. Esteve-Turrillas FA, Armenta S, Moros J, Garrigues S, Pastor A, de la Guardia M. Reply to the comments on "Validated, non-destructive and environmentally friendly determination of cocaine in euro bank notes" by R. Sleeman J.F. Carter K.A. Ebejer. Journal of Chromatography A 2006;1108(2):287. Frederick KA, Pertaub R, Ski Kam NW. Identification of individual drug crystals on paper currency using Raman microspectroscopy. Spectroscopy Letters 2004;37(3):301. [Microgram Editor’s Notes: Presents and discusses the title study, using simulated drugs (isoxsuprine and norephedrine) and two common exicipients (benzocaine and lidocaine). Fluorescence issues with U.S. currency are discussed. Contact: Department of Chemistry, College of the Holy Cross, Worcester, MA 01610.] Keely B. Forensic chemistry. Drugs on money. Chemistry Review 2004;13(4):22. [Microgram Editor’s Notes: A brief review. Contact: Department of Chemistry, University of York, UK.] Lavins ES, Lavins BD, Jenkins AJ. Cannabis (marijuana) contamination of United States and foreign paper currency. Journal of Analytical Toxicology 2004;28(6):439. [Microgram Editor’s Notes: Presents the title study. Contact: The Office of the Cuyahoga County Coroner, 11001 Cedar Road, Cleveland, OH 44106.] Sleeman R, Carter JF, Ebejer KA. Comments on Validated, non-destructive and environmentally friendly determination of cocaine in euro bank notes by F.A. Esteve-Turrillas, S Armenta, J Moros, S Garrigues, A. Pastor, and M. de la guardia. Journal Of Chromatography A 2006;1108(2):285. Xu Y, Gao Y, Wei H, Du Y, Wang E. Field-amplified sample stacking capillary electrophoresis with electrochemiluminescence applied to the determination of illicit drugs on banknotes. J Chromatogr A, May 2006; 1115(1-2): 260-6.


Bradbury J. Silence of the poppies: A new source of drug precursors. Drug Discovery Today 2005;10(1):5.



Degenhardt L, Day C, Gilmour S, Hall W. Patterns of illicit drug use in NSW, Australia following a reduction in heroin supply. International Journal of Drug Policy 2005;16(5):300.

Khat: Legal Issues:

Anonymous. News in Brief: Lawyers and judges need training in forensic science. Chemistry & Industry 2005;(7):8. Brenner JC. Forensic Science: An Illustrated Dictionary. CRC Press: Boca Raton, FL: 2004. Brettell TA, Butler JM, Saferstein R. Forensic science. Analytical Chemistry 2005;77(12):3839. Casale JF. Assessment of the volatility (smokeability) of cocaine base containing 50 percent mannitol: Is it a smokeable form of “crack” cocaine? Microgram Journal 2005;3(3-4):130. [Microgram Editor’s Notes: Presents the title study. Contact: U.S. Department of Justice, Drug Enforcement Administration, Special Testing and Research Laboratory, 22624 Dulles Summit Court, Dulles, VA 20166.] Giannelli PC. Forensic Science. J. Law Med. Ethics, Jun 2006; 34: 310 - 319. Jasanoff S. Just Evidence: The Limits of Science in the Legal Process. J. Law Med. Ethics, Jun 2006; 34: 328 - 341. Kadehjian L. Legal issues in oral fluid testing. Forensic Science International 2005;150(2-3):151. Malkoc E, Neuteboom W. The current status of forensic science laboratory accreditation in Europe. Forensic Sci Int, Apr 2007; 167(2-3): 121-6. Mile B. Chemistry in court. Chromatographia 2005;62(1/2):3. Rohrig TP, Moore CM. Zolpidem. Forensic aspects for the toxicologist and pathologist. Forensic Science, Medicine, and Pathology 2005;1(2):81. Tomlinson JJ, Elliott-Smith W, Radosta T. Laboratory information management system chain of custody: Reliability and security. Journal of Automated Methods & Management in Chemistry 2006;1:21. [Microgram Editor’s Notes: Discusses chain-ofcustody issues associated with LIMS. Contact: ChemWare, Inc., Raleigh, NC 27609 (street address not provided).] Wachowiak R, Strach B. [Analysis of active components of evidence materials secured in the cases of drugs abuse associated with amphetamines and cannabis products]. Arch Med Sadowej Kryminol, Oct 2006; 56(4): 251-7.


Enantiomer Resolution:

Fazlena H, Kamaruddin AH, Zulkali MM. Dynamic kinetic resolution: alternative approach in optimizing S-ibuprofen production. Bioprocess Biosyst Eng, Mar 2006; 28(4): 227-33. Fogassy E, Nogradi M, Kozma D, Egri G, Palovics E, Kiss V. Optical resolution methods. Org Biomol Chem, Aug 2006; 4(16): 3011-30. Gawley RE. Do the terms "% ee" and "% de" make sense as expressions of stereoisomer composition or stereoselectivity? J Org Chem, Mar 2006; 71(6): 2411-6. Kiss V, Egri G, Balint J, Fogassy E. Enantioseparation of secondary alcohols by diastereoisomeric salt formation. Chirality, Feb 2006; 18(2): 116-20. Kmecz I, Simandi B, Szekely E, Lovasz J, Fogassy E. Application of mixtures of tartaric acid derivatives in resolution via supercritical fluid extraction. Chirality, Jun 2007; 19(6): 430-3. McDermott MC, Stephenson GR, Hughes DL, Walkington AJ. Intramolecular asymmetric Heck reactions: evidence for dynamic kinetic resolution effects. Org Lett, Jul 2006; 8(14): 2917-20. Patil PA, Kothekar MA. Development of safer molecules through chirality. Indian J Med Sci, Oct 2006; 60(10): 427-37. Satyanarayana T, Kagan HB. Asymmetric amplification by kinetic resolution using a racemic reagent: example in amine acetylation. Chemistry, Jul 2006; 12(22): 5785-9. Yin J, Huffman MA, Conrad KM, Armstrong 3rd JD. Highly diastereoselective catalytic Meerwein-Ponndorf-Verley reductions. J Org Chem, Jan 2006; 71(2): 840-3.


Anonymous. Anhydrous ammonia thefts and releases associated with illicit methamphetamine production - 16 states, January 2000 - June 2004. Morbidity & Mortality Weekly Report 2005;54(4):359. Bickett T, Eiter F. Dye solutions for use in methods to detect the prior evaporation of anhydrous ammonia and the production of illicit drugs. (Patent) Chemical Abstracts 2005;142:128968q.

Qualitative Tests:

Biermann T, Schwarze B, Zedler B, Betz P. On-site testing of illicit drugs: The use of the drug-testing device Toxiquick. Forensic Science International 2004;143(1):21. [Microgram Editor’s Notes: Presents a study of the use of the title device on suspected impaired drivers in Germany. Contact: Department of Forensic Medicine, University Erlangen-Nuremberg, Universitaetsstrasse 22, Erlangen D-91054, Germany.]



Dasgupta A, Chughtai O, Hannah C, Davis B, Wells A. Comparison of spot tests with AdultaCheck 6 and Intect 7 urine test strips for detecting the presence of adulterants in urine specimens. Clinica Chimica Acta 2004;348(1-2):19. Feldman M, Kuntz D, Botelho K, Ananias DC, Gnezda M, Hoch DK, Jordan SL, Rashid S, Zhao Y. Evaluation of Roche diagnostics ONLINE(R) DAT II, a new generation of assays for the detection of drugs of abuse. Journal of Analytical Toxicology 2004;28(7):593. Kacinko SL, Barnes AJ, Kim I, Moolchan ET, Wilson L, Cooper GA, Reid C, Baldwin D, Hand CW, Huestis MA. Performance characteristics of the Cozart (R) RapiScan oral fluid drug testing system for opiates in comparison to ELISA and GUMS following controlled codeine administration. Forensic Science International 2004;141(1)41. Meyers JE, Almirall JR. A study of the effectiveness of commercially available drink test coasters for the detection of “date rape” drugs in beverages. Journal of Analytical Toxicology 2004;28(8):685. [Microgram Editor’s Notes: Presents the title study. Contact: Department of Chemistry and Biochemistry and International Forensic Science Research Institute, Florida International University, University Park, Miami, FL 33199.] Savoca R, Rentsch KM, Huber A.R. Diagnostic efficiency of different amphetamine screening tests - the search for an optimal cutoff. Clinical Chemistry and Laboratory Medicine 2004;42(9):1063. Yan J, Wang J, Zhao MP, Chang WB. Determination of papaverine by biotin-avidin amplified ELISA. Analytical Letters 2004;37(14):2977. [Microgram Editor’s Notes: Presents the title study (ELISA: Enzyme-linked immuno-sorbent assay). Contact: Beijing Univ, Coll Chem & Mol Engn, Key Lab Bioorgan Chem & Mol Engn, Beijing 100871, Peoples R China.] Zeng L. Test paper for detecting morphine. (Patent) Chemical Abstracts 2005:21218. Zhang S. Kit for combined detection of drugs, its preparation method and blocking agents used for the same. (Patent) Chemical Abstracts 2006;144:144626y.

Quality Assurance:

Clarke J, Wilson JF. Proficiency testing (external quality assessment) of drug detection in oral fluid. Forensic Science International 2005;150(2-3):161. Schaffer M, Hill V, Cairns T. Morphine and 6-monoacetylmorphine in hair of heroin users: Use of invalid extraction procedures generates erroneous conclusions. Journal of Analytical Toxicology 2005;29(1):76. SwitajZawadka A, Konieczka P, Przyk E, Namiesnik J. Calibration in metrological approach. Analytical Letters 2005;38(3):353.


Van Eenoo P, Delbeke FT. Criteria in chromatography and mass spectrometry - a comparison between regulations in the field of residue and doping analysis. Chromatographia 2004;59(Suppl. S):S39. Wilkins DG, Rollins DE, Andrenyak DM, Charles BK, Day JE. Morphine and 6monoacetylmorphine in hair of heroin users: Use of invalid extraction procedures generates erroneous conclusions - Reply. Journal of Analytical Toxicology 2005;29(1):77. Wille SMR, Lambert WEE. Phenmetrazine or ephedrine? - Fooled by library search. Journal of Chromatography A 2004;1045(1-2):259. [Microgram Editor’s Notes: Ephedrine reacted with formaldehyde in solvents to give a compound with a mass spectrum that is similar to phenmetrazine (compound not identified in the abstract). Contact: State Univ Ghent, Toxicol Lab, Harelbekestr 72, B-9000 Ghent, Belgium.] Wilson JF, UKNEQAS drugs abuse urine-the analytical performance of laboratories investigating LSD use. Therapeutic Drug Monitoring 2005;27(2):244.

Sampling Plans:

Budowle B, Schutzer SE, Burans JP, Beecher DJ, Cebula TA, Chakraborty R, Cobb WT, Fletcher J, Hale ML, Harris RB, Heitkamp MA, Keller FP, Kuske C, LeClerc JE, Marrone BL, McKenna TS, Morse SA, Rodriguez LL, Valentine NB, Yadev J. Quality Sample Collection, Handling, and Preservation for an Effective Microbial Forensics Program. Appl. Envir. Microbiol., Oct 2006; 72: 6431-6438. Gilbert R, Pulsipher B. Role of sampling designs in obtaining representative data. Environmental Forensics 2005;6(1):27. Horrocks M. Sub-sampling and preparing forensic samples for pollen analysis. Journal of Forensic Sciences 2004;49(5):1024. [Microgram Editor’s Notes: The applications include a brief discussion of illicit drugs. Contact: Microfossil Research Ltd, 31 Mont Le Grand Rd., Mt. Eden. Auckland, New Zealand.] Nocerino J, Schumacher B, Dary C. Role of laboratory sampling devices and laboratory subsampling methods in representative sampling strategies. Environmental Forensics 2005;6(1):35. Petrisor I. Sampling and analyses - Key steps of a forensics investigation. Environmental Forensics 2005;6(1):1.

Surveys and Overviews:

Anderson WH. Therapeutic drugs II: Antidepressants. Principles of Forensic Toxicology (2nd Edition) 2003:297. Deng F. Effects of glyphosate, chlorsulfuron, and methyl jasmonate on growth and alkaloid biosynthesis of jimsonweed (Datura stramonium L.). Pesticide Biochemistry and Physiology 2005;82(1):16.



Forman RF. Narcotics on the net: The availability of web sites selling controlled substances. Psychiatric Services 2006;57(1):24. Grzybowski S. The black market in prescription drugs. Lancet Supplement Medicine, Crime, and Punishment 2004;364:28. Jaitely V, Sakthivel T, Magee G, Florence AT. Formulation of oil in oil emulsions: potential drug reservoirs for slow release. Journal of Drug Delivery Science and Technology 2004;14(2):113. Janni KD, Bastien JW. Exotic botanicals in the Kallawaya pharmacopoeia. Economic Botany 2004;58(Suppl. S):S274. Khorana N, Pullagurla MR, Dukat M, Young R, Glennon RA. Stimulus effects of three sulfur-containing psychoactive agents. Pharmacology Biochemistry and Behavior 2004;78(4):821. Kintz P, Villain M, Ludes B. Testing for the undetectable in drug-facilitated sexual assault using hair analyzed by tandem mass spectrometry as evidence. Therapeutic Drug Monitoring 2004;26(2):211. Kucht S, Gross J, Hussein Y, Grothe T, Keller U, Basar S, Konig WA, Steiner U, Leistner E. Elimination of ergoline alkaloids following treatment of Ipomoea asarifolia (Convolvulaceae) with fungicides. Planta 2004;219(4):619. Lachance PA. Nutraceutical/drug/anti-terrorism safety assurance through traceability. Toxicology Letters 2004;150(1):25. [Microgram Editor’s Notes: Presents an overview of techniques used to ensure traceability of nutraceutical products. Contact: The New Jersey Agricultural Experimental Station, Food Science and Center for Advanced Food Technology, The Nutraceutical Institute, 65 Dudley Road, New Brunswick, NJ 08901.] Lachenmeier DW. Hemp food products - a problem? Deutsche LebensmittelRundschau 2004;100(12):481. Linnet K. Estimation of the limit of detection with a bootstrap-derived standard error by a partly non-parametric approach. Application to HPLC drug assays. Clinical Chemistry and Laboratory Medicine 2005;43(4):394. Lipscher J. Chemistry and crime - criminalistics in chemistry teaching: An overview. Praxis der Naturwissenschaften, Chemie in der Schule 2004;53(5):2. [Microgram Editor’s Notes: An overview and review of the title subject, includes a review of analytical techniques. This article is written in German. Contact: Kantonsschule Baden, CH-5400 Baden, Switzerland.] Memelink J. Putting the opium in poppy to sleep. Nature Biotechnology 2004;22(12):1526.


Nappo SA, de Oliveira LG, Sanchez ZV, Carlini ED. Trihexyphenidyl (Artane((R))): A Brazilian study of its abuse. Substance Use & Misuse 2005;40(4):473. Rodrigues E, Carlini EA. Ritual use of plants with possible action on the central nervous system by the Kraho Indians Brazil. Phytotherapy Research 2005;19(2):129. Roos G, Roseler C, Buter K.B, Simmen U. Classification and correlation of St. John's Wort extracts by nuclear magnetic resonance spectroscopy, multivariate data analysis and pharmacological activity. Planta Medica 2004;70(8):771. Rothweil M. Bader HJ. Drug analysis: Rapid tests for the analysis of “classical” narcotics. Praxis der Naturwissenschaften, Chemie in der Schule 2004;53(5):23. [Microgram Editor’s Notes: A minor review of the title subject, directed towards high school and college teachers. This article is written in German. Contact: Institut fuer Didaktik der Chemie, Universitaet Frankfurt, 60439 Frankfurt, Germany.] Sajonz P, Wu Y, Natishan TK, McGachy NT, Detora D. Challenges in the analytical method development and validation for an unstable active pharmaceutical ingredient. J Chromatogr Sci, Mar 2006; 44(3): 132-40. Salah SM, Jager AK. Screening of traditionally used Lebanese herbs for neurological activities. Journal of Ethnopharmacology 2005;97(1):145. Savvopoulos MA, Pallis E, Tzatzarakis MN, Dialyna IA, Tzanakakis GN, Tsatsakis AM. Legal issues of addiction assessment: the experience with hair testing in Greece. Journal of Applied Toxicology 2005;25(2):143. Thevis M, Schanzer W. Examples of doping control analysis by liquid chromatography-tandem mass spectrometry: Ephedrines, beta-receptor blocking agents, diuretics, sympathornimetics, and cross-linked hemoglobins. Journal of Chromatographic Science 2005;43(1):22. Tirumalai PS, Shakleya DM, Gannett PM, Callery PS, Bland TM, Tracy TS. Conversion of methamphetamine to N-methylmethamphetamine in formalin solutions. Journal of Analytical Toxicology 2005;29(1):48. [Microgram Editor’s Notes: Focus is on conversion in embalming fluid (formalin). Contact: Department of Basic Pharmaceutical Sciences, School of Pharmacy, West Virginia University, Morgantown, WV] Wang SQ, Fang L, Liu XJ, Zhao K. Design, synthesis, and hypnotic activity of pyrazolo[1,5-a]pyrimidine derivatives. Chinese Chemical Letters 2004;15(8):885. Wang Z, Wen J, Xing J, He Y. Quantitative determination of diterpenoid alkaloids in four species of Aconitum by HPLC. J Pharm Biomed Anal, Mar 2006; 40(4): 1031-4.


Chapter 7 Toxicology S.C.Leung9 W.M. Tam, Ph.D W.C. Cheng Ph.D Florence S.Y. Chan, M.Phil C.W. Hung, M.Phil T.T. Wong, Ph.D. Billy K.O. Leung, Ph.D. W.S. Hui, Ph.D. W.S. Lee, Ph.D. W.L. Mak, Ph.D. Introduction Toxicology is a science that draws upon knowledge, techniques and instrumentation from diverse scientific fields such as biochemistry, chemistry, epidemiology, pharmacology, pathology and physiology. The development of forensic toxicology in recent years is evidenced by the proliferation of professional societies and certification boards emphasizing on research funds and continuing education programs and the large number of research articles covering a large variety of subjects. Forensic toxicology has undergone major changes over the past decade, largely driven by the development of sophisticated instrumental techniques. This advancement has facilitated detection of a wider scope of drugs/poisons with significant improvement in sensitivity and specificity. Thus, drug detection in biological specimens that was hitherto very difficult in the past has been rendered possible. In addition, the appearance of new drugs, both in the form of pharmaceutical preparations and illicit drugs has imposed serious challenges in terms of identification and quantification, as well as in result interpretation. Current Toxicological Issues Driving Under the Influence Driving under the influence of alcohol and drugs is considered to be responsible for a large number of deaths, injuries and accidents every year. Alcohol and drugs, in particular, abused drugs can affect some important skills necessary for the safe operation of a vehicle, such as coordination, judgment, perception, tracking and reaction time. Driving under the influence of drink or drugs may therefore continue to produce major problems in most countries. Whilst the impairing effects of alcohol have been well publicized, those resulted from prescribed drugs and illicit substances have received less attention. Alcohol Alcohol is recognized to be a leading contributor to traffic accidents. Many jurisdictions have adopted per se laws which make it a crime to drive with blood- or breath alcohol concentrations above a prescribed statutory limit (1-3). Legal limits 9

Assistant Government Chemist, Government Laboratory, 7/F, Homantin Government Offices, 88 Chung Hau Street, Ho Man Tin, Kowloon, Hong Kong, China 281


for alcohol in blood were different for different countries ranging from 0.02g/100mL to 0.08g/100mL (4-5) or even down to zero tolerance. In Australia and some European countries, prescribed limits for drivers of commercial transportation are more stringent than those for other drivers. To measure a person’s alcohol level, the most common biological specimens include blood, urine and breath. The breathalyzer, which can be used to correlate breath with blood alcohol concentration, has become the most prevalent device nowadays. With the extensive reliance on breathalyzers in the enforcement of law against drink driving, forensic breath alcohol evidence is often subjected to legal scrutiny and challenges. Several common defense strategies, such as measurement uncertainty in breath alcohol (BrAC) results near statutory limits, biased results due to the presence of interfering substances and their corresponding responses have been reviewed (6). A study on the blood/breath conversion factor (Q) based on results obtained from 390 individuals has shown that Q decreases from 2629 (+/- 455) for a BrAC level of < 0.1 mg/L to 2229 (+/- 160) for a BrAC range of 0.4-0.5 mg/L, and increases again to 2428 (+/- 124) for a BrAC level of > 0.6 mg/L (7). Besides, a study on the relationship of blood alcohol (BAC) and BrAC concentrations in drunken drivers in New Zealand has indicated that the mean BAC/BrAC ratio was 19-26% higher than the adopted ratio of 2000 (8). Participation in proficiency testing can usefully augment the legal admissibility of forensic BrAC testing. An initial effort to develop a proficiency test program appropriate to forensic breath alcohol analysis, in which 11 jurisdictions participated, and 27 modern instruments were evaluated, has been described (9). A number of studies have been carried out to evaluate the performance of breathalyzers in relation to possible interferences (10-11). Laakso and co-workers have studied the effect of eight organic solvents such as acetone, 1-propanol and 2propanol on the ethanol reading of the evidential analyzer (10) and found that while most of the solvents had negligible effects on the test results, the presence of 1propanol and 2-propanol significantly increased the ethanol reading, necessitating prudent interpretation if and when propanol was present. Moore et al. (11) tested the potential interference of breath freshener strips and demonstrated that the interference from a single breath strip was both small and short-lived. Depending on the jurisdictions, some countries allow use of urine alcohol results for prosecution purposes. A review article has discussed the use of urine as a biological specimen for the determination of alcohol in clinical and forensic toxicology cases and the factors that might influence variability in the urine/blood alcohol concentration ratio (12). The Widmark formula is widely adopted in forensic applications to drink driving cases for the last 70 years but its validity in hip-flask defense tactics and back calculation of blood alcohol at the accident time is often challenged. As such, studies have been made to strengthen the legal admissibility of this formula. A study on the uncertainty associated with the use of the Widmark’s equation to estimate either the number of drinks consumed or the corresponding blood or breath alcohol concentration has been reported (13); it concluded that Widmark estimates for the number of drinks should include approximately 25% uncertainty while that of the BAC estimate should be approximately 42%. The direct application of the Widmark factors derived from Caucasians to the calculation of 282

BAC for non-Caucasians often encounters serious challenges. The effect of physiological factors to the Widmark factors (14) and the alcohol elimination rates (15) for the Chinese people have been reported based on pharmacokinetic studies performed on a group of volunteers. Both studies implied that alcohol elimination rates and the Widmark factors of Chinese people are similar to those of the Caucasians. Drugs Although it is well understood that use of drugs can be detrimental to safe driving, it is scientifically and legally a more complex subject than alcohol impaired driving. Driving under the influence of drugs (DUID) is often under-reported or goes unrecognized. Unlike drunk driving, there are no widely accepted drug concentrations above which a person is deemed to be impaired. The complexity of drug impaired driving is compounded by drug-alcohol or drug-drug interactions which could be additive, synergistic or antagonistic in nature. The above complications, coupled with physiological differences amongst individuals, render interpretation of analytical results even more difficult. Therefore, several countries, such as Germany, Belgium, Switzerland and Sweden have adopted zero-tolerance for a number of drugs regardless of whether or not the driving capacity of the person is impaired. Changes in legislation are under discussion in other European countries. Detection of DUID Two basic approaches can be taken to detect DUID drivers, namely the impairment approach and the drug presence approach. Impairment Approach Evaluation based on a variety of observable signs and symptoms, and divided attention tests have been proven to be reliable indicators of drug impairment. The Drug Evaluation and Classification Program (DECP) in the US is considered to be an effective program for law enforcement agencies to identify drug impaired drivers. Many programs used in other countries such as the Field Impairment Test procedures of the United Kingdom are modified or derived from the DECP. Papafotiou et al. studied the relationship between drivers’ performance on the Standardized Field Sobriety Tests (SFSTs) and the level of tetrahydrocannabinol (THC) in blood (16) and suggested that performance on the SFSTs provided a moderate predictor of driving impairment following the consumption of THC On the other hand, Papafotiou et al. found that SFSTs are not efficient in identifying the presence of low levels of amphetamines (17). On the other hand, detection of impairment due to ketamine was found to be effective by utilizing psychophysical tests from the DECP, the typical observable signs and symptoms being a lack of convergence, horizontal gaze nystamus, elevated pulse rate, and general failing the divided attention tests, especially the walk-and-turn and one-leg stand (18). Drug Presence Approach Blood is the preferred specimen for investigating impaired driving. It has been used in many jurisdictions as the ultimate specimen for prosecution, since blood drug concentration is directly related to the administered dosage. However, on-site



collection of blood samples for screening is inconvenient, invasive and requires qualified personnel, who are usually not available at the roadside. Because of the availability of portable urine drug screening devices particularly used for detection of common drugs of abuse, in some countries urine is the favored specimen for screening of drivers in DUID. A study conducted in Belgium has indicated that the number of unnecessary blood analyses in DUID significantly decreased with the use of roadside urine testing (19). There is an increasing interest to explore the use of oral fluid for screening of DUID mainly because of its similarity with blood with respect to both drug detection time and concentration. A number of papers have been published, reviewing: a) the pharmacokinetics of illicit drugs in oral fluid (20), b) the challenges and legal issues relating to oral fluid testing (21, 22) and c) the analysis of illicit drugs in oral fluid (23-28). Generally, drugs attracting the most interest are the amphetamines, cocaine, opiates, cannabis and benzodiazepines. Studies conducted in Germany evaluating oral fluid (29-30) and urine (30) as a predictor for DUID have concluded that the detection of psychoactive substances, such as amphetamine, 3,4methylenedioxymethamphetamine (MDMA), morphine, benzoylecgonine, and THC in oral fluid taken at the roadside is highly predictive for the presence of the corresponding drug or its metabolites in blood or serum. Research into the detection of drugs in oral fluid has accelerated in recent years as methods have been developed to detect increasingly smaller amounts of drugs using modern analytical techniques. These developments have led to the use of oral fluid by police forces to detect a number of drugs, particularly abused drugs, in drivers. At present, a number of on-site oral fluid drug testing devices have become commercially available. Several studies have been carried out to evaluate the testing of various illicit drugs, such as cocaine, amphetamines, benzodiazepines, opiate and cannabis by these devices (31-35). Oral fluid point-of-collection drug-testing devices have been evaluated by Walsh et. al. in 2005 (36) and 2007 (37). Results from the recent assessment have indicated that most devices performed well on the detection of opiates and amphetamines, but approximately half had the amphetamine cutoff concentration greater than that proposed by the Substance Abuse and Mental Health Services Administration (SAMHSA). In an article discussing the progress of oral fluid testing in DUID, Verstraete commented that while progress has been made in toxicokinetics in oral fluid and in sample collection technique, the sensitivity and reliability of on-site screening devices, particularly for cannabis and benzodiazepines, had to be improved (21). Although the detection of cocaine and THC still needed improvement, commercial oral fluid drug testing devices were improving in terms of sensitivity and performance. However, like all specimens, oral fluid does have its limitations; one major disadvantage is that people are sometimes unable to produce sufficient amount for analysis to be made (31-33). Furthermore, roadside screening devices available are not flexible enough to accommodate the analysis of new abused drug(s). For instance, ketamine, which is a popular drug of abuse in South East Asia, cannot be detected by roadside screening devices.


Rosita-2 project The Rosita-2 project (34) was aimed at evaluating the validity, equipment reliability, cost and usability of on-site oral fluid devices for screening drugs of abuse, including amphetamine, methamphetamine, cannabis, cocaine, opiates and benzodiazepines. The project, which lasted until the end of 2006, was a consortium consisting of 6 countries of the European Union (Belgium, Finland, France, Germany, Norway and Spain) and 4 states (Florida, Washington, Utah and Wisconsin) in the US. Nine devices were evaluated and two of them were withdrawn from the market during the study. A high percentage of the devices failed to perform normally due to instrumental malfunctioning, or because the saliva samples collected from drivers were either too little or too viscous. In six of them, the failure rate was unacceptably high at greater than 25%. Three devices were also assessed for identifying benzodiazepines. None of the devices could meet the analytical criteria for an effective testing of amphetamines, benzodiazepines and cannabis proposed during the Rosita-1 project, i.e. sensitivity and specificity >90% and accuracy >95% when compared with results obtained from reference analytical method for oral fluid. At the end of the study, not a single device was considered reliable enough for roadside screening for drug driving. However, experience in the state of Victoria in Australia has shown that random roadside oral fluid testing of drivers for methamphetamine and cannabis had a deterrent effect. Epidemiological Studies Cannabis is the most popular illicit drug in the Western world, the abuse of which has continued to increase considerably during the past few years in European nations (38-39). Apart from ethanol, cannabis is the most frequently detected controlled substance in individuals involved in road accidents or suspected of DUID in Australia (4, 40-41), France (42), Belgium (19) and Switzerland (43). Drummer et al. reported that cannabis, amphetamines and combinations of psychoactive drugs administered together with alcohol significantly increased driver’s risk of a serious road crash (44). In addition, extensive studies have been performed on psychoactive drugs (16-17, 32, 43, 45-54) in drivers involved in traffic accidents. A study in Sweden has revealed that immediately after enforcing the zero-limit law for the use of controlled substances by drivers, the number of DUID cases submitted for toxicological analysis increased sharply and that amphetamine was by far the leading illicit drug, followed by THC and opiates, while sedatives-hypnotics like diazepam and flunitrazepam were the most prevalent prescription drugs detected (55). Although the zero-limit law does not apply to prescription drugs in Sweden, in another study it was suggested that when the concentration of sedatives and hypnotics in drivers exceeded the accepted therapeutic limits, it should be regarded as having a potential of abuse or overdose, thus contravening laws against DUID (56). The result of a questionnaire conducted by Jones et al. (57) revealed that random roadside testing appeared to be a more effective deterrent against DUID than either increasing the severity of sanctions or providing factual information about the risk associated with the behavior.



A 7-year survey on DUID in Greece has shown that abuse of alcohol decreased in 2001-2004 as compared to 1998-2000. Cannabis, benzodiazepines and opiates were each found in 4%, and cocaine in 1% of the total number of cases (58). A study on drivers involved in road crash in the Tilburg region of the Netherlands from May 2000 to August 2001 (59) has concluded that the use of a single drug (especially alcohol and benzodiazepines), as well as multiple drug use and drug-alcohol combinations increased the risk of road accidents requiring hospitalization. In another study conducted in 1998-1999 by the same group on drivers in accidents resulting in hospital admission or death, it was found that the most frequently detected drugs in the Netherlands were the cannabinoids, benzodiazepines and cocaine (60). Based on drug levels in saliva or blood obtained from injured drivers in Denmark, of the 23 drug-positive cases, 15 were found positive for one drug and 5 of them with alcohol present over the legal limit (0.05%). There was strong suspicion of impairment in 9 out of the 23 cases, while in another 6 cases it was likely that the drivers were impaired (61). Terry et al. (62) found that 65% of regular cannabis users in England reported that they were discouraged to drive after smoking cannabis if random roadside testing for drugs was introduced. The pattern of drug and alcohol use in fatally injured drivers in the Washington State of the US has been examined. The data revealed that over the past decade, while the use of alcohol has declined, the abuse of certain drugs, notably methamphetamine, has increased significantly. Combined use of drug and alcohol has become a very significant pattern and has probably been overlooked in DUID enforcement programs (63). An overview in four areas of drug and driving has enlisted: i) epidemiology and prevalence - the methodological shortcomings of extant studies, and recommendations for future research, ii) the effects of medicinal and illicit drugs on driving performance - focused on six classes of drugs most often found in impaired and injured drivers, iii) toxicological issues - the screening and confirmation techniques used by different countries and how roadside testing could be used in association with behavioral and laboratory testing in the identification and prosecution of drugged drivers, and iv) DUID Laws - provides an overview of DUID laws in the United States and Europe and the rationale for developing per se legislation as a strategy to more effectively manage the problem (64). With the legislation to allow the conduct of random roadside saliva testing for the two most prevalent illicit drugs, THC and methamphetamine, roadside screening for these two drugs was started in the State of Victoria, Australia in late 2004 (65). Drivers failing the roadside test were asked to perform a second test conducted within a drug testing vehicle. When both tests indicated the presence of methamphetamine or THC, the oral fluid sample would be sent for evidentiary standard laboratory analysis. Surveys have shown that the level of drivers awareness of random saliva testing increased from 78% to 92% with 33% of illicit drug users avoided taking drugs when they were driving and the proportion of drug-using respondents who drove under the influence of drugs dropped from 45% to 35% (34).


Drug Facilitated Sexual Assaults (DFSA) There has been an increasing trend in the number of reports involving the administration of drug(s), sometimes in conjunction with alcohol, to render victims of sexual assaults physically incapacitated and thus incapable of withholding (or giving) consent to sex. Under the influence of drugs, victims became unconscious during all or part of the sexual assault, and upon regaining consciousness, would experience anterograde amnesia. Realizing the situation, forensic toxicologists in USA (66-70), Canada (71), UK (72), and Australia (73) have addressed the corresponding analytical and toxicological issues. Drugs encountered in DFSA cases A wide variety of drugs can be used to facilitate sexual assaults. They are often odorless, tasteless and colourless, possess amnesic properties and produce impairing effects rapidly. They can be surreptitiously administered in food and beverages (74). Drugs detected in victims of DFSA consist mainly of central nervous system depressants such as benzodiazepines, which are capable of impairing the memories and consciousness of the affected person. Among these drugs, flunitrazepam (Rohypnol) (75) is believed to be the most notorious because of its high potency and rapid onset of effect. Due to easy availability, alcohol is most commonly associated with sexual assaults (66, 70, 76-77). It exerts a potentiated or synergistic effect when administered in combination with other psychoactive drugs. Studies in the US (66, 76, 78-81) and UK (77) have indicated that the most prevalent drugs used in sexual assaults were alcohol, followed by cannabinoids, cocaine, benzodiazepines, and g-hydroxybutyric acid (GHB). More recently, ketamine has also gained notoriety with this type of crime in USA (79, 81). As rave parties have gained popularity, amphetamines have also been detected (66, 72, 82). A review of alleged DFSA cases in a 12-month period concluding in April 2003 in Australia (83) has demonstrated that in addition to the drugs detected, alcohol consumption prior to the assault was high (77%). Detection of drugs Drugs commonly associated with DFSA are usually low-dose preparations; they often have synergistic effects when mixed with alcohol. Since a small amount of these drugs would be sufficient to serve the purpose of seducing an individual, they are difficult to be detected in the blood or urine. Any delay in the sampling of specimens from victims will further exacerbate the difficulty of detecting them as many of these substances are rapidly transformed into their metabolites in a short period of time. The development of highly specific and sensitive analytical methods is therefore necessary. It was reported that solid phase extraction (SPE) coupled with LC-MS/MS could be used for detecting drugs with low concentration in urine samples, especially benzodiazepines (84) and ketamine (85-86). The Society of Forensic Toxicologists (SOFT) created a committee in 2003 to address the issue and has come up with a list comprising about 50 compounds that could be



used in DFSA. A GCMS screening method was developed to detect 30 compounds in urine after one extraction (87). In some situations where, as a result of delay in reporting the crime, natural processes have eliminated the drug from typical biological specimens, hair would be a useful alternative sample. Kintz reviewed the existing literature together with his experience in the analysis of hair for cases involving benzodiazepines, hypnotics, GHB and various sedatives or chemical agents with particular attention to cases dealing with a single dose exposure (88). The expected concentrations in hair were in the low picogram/microgram range for most compounds for which MS/MS technology would be a prerequisite (88). However, much more data would be required to decipher the legally defensible cutoff values of the drugs in hair in DFSA cases. A method using LC-MS/MS for the determination of a single exposure to benzodiazepines and analogs, such as bromazepam, clonazepam and their metabolites in urine and hair samples was developed and applied to forensic cases with satisfactory results (89). The targeted drugs could be determined in urine a short period after the alleged offence and in cut head hair/axillary hair samples in short length proximal segments. A suspected DFSA case in France was reported 6 days after the assault as the victim, suffering from total amnesia, was under intense sedation. By means of LC-MS/MS, zolpidem was detected and quantified not only in the blood and urine samples, but also in the corresponding hair segments (90). DFSA cases in which zopiclone (91), bromazepam (92), lorazepam (93), tetrazepam (94) and alprazolam (95) were found to be present in hair have also been reported. The use of water soluble, low molecular weight compounds such as γ-butyrolactone (GBL), or 1,4-butanediol (BD) in aqueous solution is a concern as there are no general methods for detecting their presence rapidly and reliably. A study on freezing point osmometry as a forensic screening method for detecting adulteration, if any, of commercial beverages with ethanol, GBL, or BD and for detecting dilution of meperidine has been reported (96). A comprehensive list of baseline osmolality values for various commercially available beverages, eye drops, and mouthwashes was also provided. Other potential forensic applications were discussed in the paper (96). Reports of DFSA are increasing at an alarming rate; the victims, medical professionals and law enforcement officers are relying on the forensic toxicologist to conduct the best possible testing of the available specimens. It is imperative to: i) obtain the corresponding biological specimens (blood and urine) as soon as possible; ii) collect hair samples about 1 month after the alleged event; and iii) use sophisticated analytical techniques (GC or LC preferably coupled to tandem mass spectrometry, headspace gas chromatography) (88). This is particularly relevant to those drugs that are eliminated quickly, such as GHB and its related compounds. Workplace Drug Testing Drug testing was introduced in the US in the 1980s to combat misuse of drugs or alcohol in the workplace. Workplace drug testing has since then grown at a phenomenal rate around the world. The analytical findings of workplace drug 288


Unconventional Specimens Urine was traditionally used in workplace drug testing but unconventional samples, such as oral fluid (saliva), hair and sweat have been evaluated. In a recent publication reviewing the drug testing standards of Federal Workplace Drug Testing Programs in the US, it was proposed to allow laboratory testing of hair, oral fluid, and sweat patch specimens in addition to urine for common drugs of abuse. The U.S. Department of Health and Human Services is preparing the Final Notice defining drug testing standards and requirements including: specimen collection procedures, custody and control procedures that ensure donor specimen identity and integrity, testing facility, initial and confirmatory test cutoff concentrations, analytical testing methods, result review and reporting, evaluation of alternative medical explanations for presence of drug or metabolite in the donor's specimen, and laboratory certification issues. The addition of accurate and reliable workplace drug testing using hair, oral fluid, and sweat patch specimens will complement urine drug testing, and aid in combating evasion of detection through adulteration, substitution, and dilution (113). Oral Fluid A review of the use of oral fluid in workplace drug testing reported that it should be able to withstand judicial scrutiny (22). The performance of commercially available immunoassay test kits for oral fluid was evaluated against the GC/MS method (114116). The effect of foodstuff and other adulterants on the test result was investigated (117) and it was found that common foods, food ingredients, beverages, cosmetics and hygienic products did not cause false positive results. As required in the protocol of workplace drug testing, a second test must be performed to verify the result of the first test. LC-MS methods in conjunction with LLE or SPE technique were developed to determine the presence of Δ9-tetrahydrocannabinol and amphetamines in oral fluid (25, 118). Hair Two reviews on the role of hair samples for workplace drug testing were presented (119-120). A two-step approach coupling immunoassay and GC-MS method for the analysis of opiates and cocaine in hair was assessed (121). The successful application of hair analysis in the workplace to demonstrate drug abuse was described (122123). The result of a study on the level of morphine, monoacetylmorphine and codeine in hair in both clinical and workplace subjects was presented (124). Various biological matrices as indicators for recent or ongoing use of cannabis have been discussed (125); the author concluded that the analysis of urine was useful for confirming abstinence from cannabis abuse, while hair analysis lacked the sensitivity for detecting cannabinoids. Sweat Characterization of the excretion profile of illicit drugs in sweat is important for the accurate interpretation of workplace drug testing results. Studies on the disposition of codeine (126) and cocaine (127) in sweat after controlled administration were reported. An evaluation on the efficacy of treatment on opioid dependence, utilizing sweat testing (128) has come to the conclusion that detection of opiates in sweat was less sensitive than in urine and so sweat patch testing in outpatient clinical settings has limited utility. A study on THC excretion in the sweat of 11 daily cannabis users 290

testing in the UK in 2002 were published in 2005 (97), reporting that about 19% of the specimens were positive for abused drugs. Urine The most common specimen for illicit drug testing is urine. Workplace drug tests usually adopt a two-step approach for positive identification: a screening test and a confirmation test. Immunoassay is commonly used for screening because the method is simple and sensitive, takes a short time, and is reasonably cost-effective. Comparison of several commercial test devices has been reported, assessing their relative performance and reliability (98-100). New immunoassay kits developed for the detection of 7-aminofluinitrazepam, oxycodone, buprenorphine and monoacetylmorphine have been evaluated (101-105). Performance of the Roche online kinetic interaction of microparticles in solution (KIMS) with and without beta-glucuronidase treatment was assessed for the detection of benzodiazepines where enzyme hydrolysis was recommended to provide better cross-reactivity for benzodiazepines glucuronide conjugates (106). Along with the scientific development, LC-MS has emerged as a popular tool for the identification of drugs in the workplace. A high-throughput screening method based on SPE-LC-MS/MS with an in-house developed post-analysis data treatment system was developed as the first test for screening abused drugs in urine (107). LC-MS methods for the determination of benzodiazepines and their metabolites in human urine were described (84, 108). Cut-off is required to distinguish between innocent exposures from deliberate drug use. An optimal cut-off of not less than 500 ng/mL for amphetamine screening has been proposed to avoid a high rate of false-positive results (109). Urine adulterants could give rise to false-negative results on primary drug screening methods. The effect of papain, a novel urine adulterant, on the concentration of a number of metabolites of abused drugs in urine was investigated (110): it was demonstrated that the concentrations of 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid (THCCOOH) and nordiazepam in urine decreased after storage for 24 hours at room temperature at a papain concentration of 10mg/mL. A urine specimen that is found presumptively positive for a drug and/or drug metabolite must be tested a second time to confirm the presence of the drug or metabolite. For opiates, morphine is always targeted for the confirmation of opiatepositive samples. Various opiate alkaloids can be treated as potential markers to demonstrate an intake of heroin. However, the analysis of papaverine metabolites was found to be more sensitive than 6-acetylmorphine as a means of demonstrating illicit use of heroin (111). According to the guidelines issued by SAMHSA of the US, GC-MS is the only authorized confirmation method for cocaine, marijuana, opiates, amphetamines, and phencyclidine. Thus, scientists are still developing GC-MS method for detecting abused drugs. A GC-MS method for the simultaneous measurement of a number of amphetamines and their respective metabolites was developed (112).


after cessation of drug use (129) has found that using the proposed US Federal cutoff concentrations (i.e. 1ng THC/patch), most daily cannabis users would have a positive sweat patch in the first week after ceasing drug use and a negative patch after subsequent weeks. Emergence of New Drugs of Abuse Abuse of designer drugs is widespread among young people, especially in the socalled "dance club scene" or "rave scene". Some designer drugs, which are structurally and pharmacologically very similar to their corresponding illicit analogues, are not controlled. Contrary to new medicaments, which are extensively studied on rats and primates combined with human epidemiologic investigations and risk assessment under controlled clinical environments, many designer drugs are consumed without any safety testing. Therefore, knowledge on the metabolism of these substances in the human body is a prerequisite for understanding the potential toxicological risks. In this latter regard, the metabolism of tryptamines, phenethylamines, piperazines and alpha-pyrrolidinophenone-derived designer drugs have been reviewed (130-131). Phenethylamines Designer drugs in close resemblance, both chemically and pharmacologically, with methamphetamine and MDMA often emerge from time to time to substitute these two controlled substances. As the toxicity of these drugs is not well known, reported intoxication, or even fatal cases serve as invaluable references for interpreting the drug levels found. 2,5-dimethoxy-4-bromoamphetamine (DOB), a psychedelic hallucinogenic drug of the phenethylamine class, was first synthesized by Alexander Shulgin in 1967. The first documented DOB overdose case involved two men: one subject with 19 ng/mL of DOB in serum died, while the other with 13ng/mL of DOB in serum survived (132). Methcathinone, a methyl derivative of cathinone, is a CNS stimulant found in the “Khat” plant, Catha edulis, and can be easily synthesized from pesudoephedrine. Although reports on methcathinone intoxication are rare, a case of overdose by methcathinone dissolved in ethanol and used in conjunction with bromazepam has been published (133). Serum analysis revealed 0.50 mg/L of methcathinone and 8.89 mg/L of bromazepam. The report suggested that in spite of a very high bromazepam concentration and the presence of ethanol, the vital respiratory function could be maintained due to the associated presence of methcathinone. Maurer et al. reported a series of studies on the metabolism of 2,5-dimethoxy-4ethylthio-beta-phenethylamine (2C-T-2) (134), 2,5-dimethoxy-4-propylthio-betaphenethylamine (2C-T-7) (135), 4-iodo-2,5-dimethoxy-beta-phenethylamine (2C-I) (136), 4-ethyl-2,5-dimethoxy-beta-phenethylamine (2C-E) (137), 2,5-dimethoxy-4methyl-beta-phenethylamine (2C-D) (138), 2,5-dimethoxy-4-bromo-amphetamine (DOB) and 2,5-dimethoxy-4-bromo-methamphetamine (MDOB) (139), and N-(1phenylcyclohexyl)-3-ethoxypropanamine (PCEPA) (140) in rats by analyzing urine samples using GC-MS after acid hydrolysis, liquid-liquid extraction, and microwave-assisted acetylation. The systematic analytical methods described are useful for screening these drugs. 291


Methylone, methylenedioxymethcathinone, is a beta-ketone analogue of MDMA. It is related to methcathinone as MDMA is related to methamphetamine and 3,4methylenedioxyamphetamine (MDA), to amphetamine. Methylone is an empathogen and a mild stimulant, producing effects similar to, but less intense than, MDMA. The metabolic pathways of methylone in human beings and rats were studied by dosing methylone to human subjects and rats and analyzing the respective urine samples by GC-MS and LC-MS/MS. Two major metabolic pathways were revealed with the formation of methylenedioxycathinone, 4hydroxy-3-methoxymethcathinone (HMMC) or 3-hydroxy-4-methoxymethcathinone in urine. HMMC was found to be the most abundant metabolite and can be used for demonstrating the usage of methylone (141). Tryptamines Appearing in the late 1990s, 5-methoxy-N,N-diisopropyltryptamine, 5-MeO-DIPT (Foxy) is a hallucinogenic tryptamine that produces feelings of euphoria, disinhibition, and auditory and visual hallucinations. It has many adverse effects but no commercial toxicological screening tests are available. Laboratory analysis was made on blood and urine by means of GC-MS; the parent drug (5-MeO-DIPT) was detected and quantified while three metabolites, including 5-methoxy-indole acetic acid, 5-methoxy-N-isopropyltryptamine (5-MeO-NIPT) and 5-methoxydiisopropyltryptamine-N-oxide (5-MeO-DIPT-N-oxide) were detected in the urine (142-143). Using GC-MS and LC-MS/MS to investigate the urinary metabolites of 5MeO-DIPT in human urine, 6-hydroxy-5-methoxy-N,N-diisopropyltryptamine (6OH-5-MeO-DIPT) was detected in addition to 5-hydroxy-N,Ndiisopropyltryptamine (5-OH-DIPT) and 5-MeO-NIPT (144). Of these metabolites, which retain the structural characteristics of the parent drug, 5-OH-DIPT and 6-OH5-MeO-DIPT were found to be more abundant than 5-MeO-NIPT. A case of Foxy intoxication was reported where the patient was presented with sensory hallucination. 5-MeO-DIPT and its metabolites were detected by GC-MS with 5MeO-DIPT at levels of 0.14 and 1.6 mg/mL respectively in serum and urine (145). In another report of Foxy overdose, 5-MeO-DIPT and its two metabolites, 5-OH-DIPT and 5-MeO-NIPT were detected in blood and urine with concentrations of 0.412, 0.327 and 0.020 mg/mL, and 1.67, 27.0 and 0.32 mg/mL, respectively (146). A screening method capable of detecting 5-MeO-DIPT, a-methyltryptamine (AMT), N,N-dimethyltryptamine (DMT), N,N-dipropyltryptamine (DPT), 2C-T-7, and 4bromo-2,5-dimethoxy-beta-phenethylamine (2CB) in blood and urine using GC-MS and LC-MS was developed. The limit of detection was 5-10 ng/mL, exhibiting a linearity between 50 and 1000ng/mL (147). A general method for the screening and confirmation of tryptamines and phenethylamines in blood and urine using GC-MS and LC-MS has been reported (148). Piperazines N-benzylpiperazine (BZP) and trifluoromethylphenyl-piperazine (TFMPP) are amphetamine-like compounds and are active ingredients in a range of products generically known as Party Pills, Legal Herbal Highs, Legal Party Drugs or Social Tonics which are marketed as safe alternatives to illegal drugs, such as MDMA and methamphetamine. In New Zealand, industry sources have estimated a sale of 292

150,000 ‘doses’/month of these Party Pills (149). BZP could cause unpredictable symptoms, such as insomnia, anxiety, nausea, vomiting, palpitations, dystonia, and urinary retention. Serious life-threatening effects of toxic seizures and even status epilepticus and severe respiratory and metabolic acidosis were also recorded in some individuals (150). Detection of BZP and TFMPP, and their major metabolites in urine has been established, using GC-MS accompanied by trifluoroacetyl (TFA) derivatization and LC-MS analyses after enzymatic hydrolysis and solid phase extraction with OASIS HLB (151). Using a similar methodology, the metabolism of BZP in rats was studied where p-hydroxy-BZP (p-OH-BZP) was unequivocally identified as the main metabolite along with a minor metabolite m-hydroxy-BZP (152). The result suggested that p-OH-BZP is the most relevant metabolite detected in urine to prove an intake of BZP. Metachlorophenylpiperazine (mCPP) is a psychoactive substance that appeared in 2004 on the black market of illicit substances in Europe and France. It has a strong affinity for serotoninergic receptors and the serotonin transporter. Although it has been reported that cases of intoxication were generally not serious, the risk of psychiatric disorders, serotoninergic syndrome and the existence of predisposing psychiatric pathologies and pharmacodynamic or metabolic interactions must be taken into account (153). Pyrrolidinophenones 4'-methyl-alpha-pyrrolidinobutyrophenone (MPBP) is a designer drug with assumed amphetamine-like effects. In a series of studies on the metabolism of MPBP in rats, seven metabolites could be identified in urine, suggesting the following metabolic steps: oxidation of the 4'-methyl group to the corresponding alcohol and further oxidation to the respective carboxy compound, hydroxylation of the pyrrolidine ring followed by dehydrogenation to the corresponding lactam or reduction of the keto group to the 1-dihydro compound (154). Survey on Trends of Drug Use Opioids and Opiates A study on opioid analgesics, such as methadone and oxycodone in drug abuserelated deaths in the US has been reported (155). Cases involving opioid analgesics, which increased almost doubled from 1997 to 2002, were noted more frequently than those relating to heroin or cocaine. Dramatic increase in availability has made opioid abuse a growing problem. Concomitant consumption of benzodiazepines and opioids has gained popularity among patients with opioid dependence, imposing a substantial impact on morbidity, mortality and clinical course. Incidents of patients treated with methadone or codeine medications reporting daily intake of benzodiazepines were significantly more than heroin-dependent patients (156). The finding underlines the need to further explore the cause, interaction and consequences of concomitant use of benzodiazepines and opioids. The lack of difference between opiate concentrations in the hair samples from participants in a controlled heroin maintenance program and those from victims of opiate-associated fatalities did not support the hypothesis that an absence of 293


tolerance can be regarded as a potential cause of death (157). In addition, since acetylcodeine was found to be absent in the majority of the deaths, the applicability of this substance as a characteristic marker of illicit heroin consumption is therefore questionable. Cocaine In response to an increase in cocaine abuse, a multi-center, cross-sectional survey on cocaine consumption over the last decade has been conducted in ten EU cities (158). In addition to evaluating the socio-demographic data, urine toxicology results for cocaine in treatment groups undergoing maintenance therapy between 1996 and 2002 were analysed, revealing a significant increase of concomitant cocaine consumption. Furthermore, multiple substances abuse seems to be one of the predominating patterns associated with cocaine consumption. In a study on the risk factor for recurrent diabetic ketoacidosis, active use of cocaine was found to show the strongest association with the disease (159). 3,4-Methylenedioxymethamphetamine (MDMA) MDMA is widely used, notably at rave parties, as a recreational drug. Around 8095% of dancers/ravers in the UK reported using MDMA (160). MDMA is a well established serotonergic neurotoxin; animal research has shown that heat and crowding potentiate the acute effects of the drug. Parrott (160, 161) has recently reported that similar stimulatory environments to clubs and raves would produce the same effect on MDMA users. According to a number of national surveys in the US, namely, Monitoring the Future (MTF) survey (162), the National Institute on Drug Abuse's (NIDA) annual survey of drug use and the National Survey on Drug Use and Health (163) in 2004, occasional use of MDMA by young adults at the age of 18 has decreased from 3.7% in 2003 to 3.1% in 2004. On the other hand, a study recently conducted in the US indicated that MDMA has been added to the spectrum of illicit drugs used by college students. Those college students who were poly-drug users could be mainly grouped into ecstasy users and marijuana users. Comparatively, ecstasy users were found more likely to have used other illicit drugs (164). GHB GHB is a naturally occurring analog of gamma-aminobutyric acid (GABA) which has been used in research and clinical medicine for many years. Since around 1990, GHB has been used in the U.S. for its euphoric, sedative, and anabolic (body building) effects. Coma and seizures can occur following the use of GHB. Combined usage with other drugs such as alcohol can result in nausea and breathing difficulties. GHB may also produce withdrawal effects, including insomnia, anxiety, tremors, and sweating. GHB and two of its precursors, gamma butyrolactone (GBL) and 1,4 butanediol (BD) have been reported to have been involved in poisoning, overdose, date rape, and even death (165-166). According to a study by Carter et al (167) comparing the effects of GHB and two sedative/hypnotic drugs, triazolam (a benzodiazepine) and pentobarbital, GHB could cause a steeper dose-effect function for sedation and produce significantly


greater negative effects than the other drugs. Additionaly, the possibility of accidental overdose with GHB appeared to be higher. Epidemiological Study of Postmortem Cases Much of the knowledge in post-mortem toxicology comes from case studies (168). Systematic collection of data from toxicological findings in postmortem cases is useful for identifying the current trend in drug misuse so that appropriate preventive measures can be imposed. A study based on toxicological findings in children and adolescents in Virginia of the US has reported that use of antidepressants was more common among youths committing suicide than those dying of accidents or homicides (169). However, the use of selective serotonin reuptake inhibitors (SSRIs) did not appear to be more common among youths committing suicide by poisoning than those by hanging or by using gun. Another study on suicidal cases in Kentucky has shown that 3 times as many women had taken antidepressants and more than twice as many had consumed opioids (170). While drug toxicity ("overdose") ranked the third leading cause of suicide after firearm injury and hanging, women succumbed to drug toxicity more than men (27.5% versus 5.9%). Of the overdose deaths, 66.5% were found negative in blood alcohol, while antidepressants, opioids, and benzodiazepines were the three most common drugs detected in blood. A variety of over-the-counter (OTC) cold medications were encountered in a series of infant deaths in Montgomery of the US (171). The OTC cold medications either directly caused the majority of these deaths, or they were contributory factors to the cause of death. A study on alcohol-related poisoning or death involving amitriptyline, propoxyphene and promazine in Finland has suggested that in the presence of alcohol, a relatively small overdose of these drugs could result in fatality (172). Furthermore, analysis of postmortem toxicology data in Finland from 1995-2002 revealed that venlafaxine, mianserin, moclobemide, and mirtazapine were responsible for significantly more deaths than expected (173). The fatal toxicity indices of the above mentioned substances were higher than those of the SSRIs but lower than those of tricyclic antidepressants. It was concluded that among the newer antidepressants, differences are present in terms of both toxicity and interaction potential with alcohol. Quality Assurance and Accreditation One of the goals of accreditation is to enhance reliability, traceability and ultimately, the comparability of test data generated from individual laboratories. There has been a common consent that most, if not all, accreditation programs are moving towards generating a harmonized protocol in order to meet the International Organization for Standardization (ISO/IEC 17025:2005) requirements (174-175), or redrafting into a single cohesive document (176). An overview of the existing standards and guidelines for analytical toxicology, which included forensic toxicology, workplace drug testing, clinical toxicology, point-of-care testing, and an area of overlap, e.g. brain death, sexual assault, drugs of abuse, was published (177). The guidelines can be issued by government agencies, e.g. SAMHSA of the US, and the European Workplace Drug Testing Society (EWDTS) of the European Union, or 295


recommended by professional associations or scientific societies e.g. World AntiDoping Agency, German Society for Toxicological and Forensic Chemistry, and the American Academy of Forensic Sciences. Penders et. al. (177) opined that a laboratory could choose the best-fitted guidelines, depending on its situation, area of activities, and the legal and regulatory requirements. Also, all guidelines were recommended to be regularly updated as technological improvements are ongoing and new drugs emerging. The application of analytical techniques in postmortem toxicology is often more difficult than in other forms of forensic toxicology owing to the variable and often degraded nature of the specimens and the diverse range of specimens available for analysis (178). A review relating to the requirements for bioanalytical procedures in postmortem toxicology pointed out that all methods for the particular postmortem specimen(s) used should be fully validated. To maximize the chance of obtaining meaningful analytical findings to help determine the cause of death, collection of specimens must be standardized to minimize site-to-site variability and should, if available, include a peripheral blood sample and at least one other specimen. Urine and vitreous humor are good specimens to complement blood (178). An article has provided guidelines for sample collection, labeling, transport and storage of specimens obtained during a postmortem examination (179). Of the various specimens to be collected for toxicological examination, important specimens include peripheral blood (preferably from femoral veins), urine, vitreous humor, stomach contents, and liver (the right lobe). Validation of new methods in analytical toxicology constitutes an important prerequisite for the correct interpretation of toxicological findings, both in scientific research and in routine work. The importance of validation parameters, such as selectivity, linearity, accuracy and precision, limit of detection and quantitation, recovery and ruggedness, matrix effect etc. have been discussed (180). With the increasing popularity of hair analysis in toxicology, the basic aspects of method development and validation of hair testing procedures have been reviewed (181). Advances in Toxicological Analysis Instrumental Techniques - General Unknown Screening GC The first step of toxicological analysis is the identification of unknown drugs and poisons in body fluids. A general unknown screening procedure is necessary to allow simultaneous detection of as many intoxicants as possible. In recent decades, GC-MS procedures have been universally applied for general screening, owing to their specificity and the availability of standardized electron-impact mass spectra libraries, some of which being specialized in drugs, toxic compounds, and their metabolites. With diethyl ether as the extraction solvent followed by acid backextraction, a procedure for the screening and semi-quantitation of 14 basic drugs in postmortem blood using GC-MS (ion-trap) was established (182). A simultaneous semi-quantitative/quantitative screening of 51 drugs of toxicological interest as silylated derivatives in whole blood was developed; detection of the drugs was achieved by a combination of two different GCs with both electron capture detection


(ECD) and mass spectrometry operating in a selected ion-monitoring (SIM) mode (183). Chromatographic screening of drugs and poisons has been reviewed (184). Although some drugs require derivatization, GC-MS especially in the electron impact full-scan mode, is still regarded as the method of choice. LC-DAD is often used for screening, but its separation power and specificity are inferior to GC-MS. LC-MS (either single stage or tandem MS) has been shown to be an ideal supplement to GC-MS, especially for detecting and quantifying more polar, thermolabile or low-dosed drugs in blood or plasma (184-185). LC-MS LC-MS screening for drugs has made progress, with the advent of the in-source collision induced dissociation (CID) mass spectral library, either in a single MS or in the form of MS/MS. With a hybrid linear ion-trap LC-MS/MS system using 3 alternated collision energies during each scan, a library containing 1000 enhanced product ion-tandem mass spectra in the positive mode and 250 in the negative mode was created by injecting pure solutions of drugs and toxic compounds (186). Compared with LC-DAD and GC-MS in the analysis of 36 clinical samples, this LCMS/MS system could identify most of the compounds. Using a similar strategy, a multiple reaction monitoring database of 301 forensically important drugs after either liquid-liquid extraction (LLE) or solid phase extraction (SPE) was constructed (187). In another study, a library of over 100 drugs for screening and identification purposes was established by way of a simple protein precipitation method followed by a multi-target screening procedure on postmortem whole blood samples (188). The results indicated a promising direction of using a hybrid linear ion-trap LCMS/MS system to develop a comprehensive and efficient method for the general screening of drugs and toxic compounds in blood or urine. One of the problems often faced by toxicology laboratories is the availability of analytical reference standards, particularly for new drugs and their metabolites. Thus, a new strategy in the screening of drugs and poisons in urine was proposed using liquid chromatography-time of flight mass spectrometry (LC-TOFMS). Mass spectral identification is based on matching monoisotopic masses and isotopic patterns (SigmaFitTM) of a sample component with those in the database (735 entries) representing the elemental formulae of reference drugs and their metabolites (189). A routine mass search window of 20-30 ppm for LC-TOFMS was successfully applied to the identification of drugs and poisons in urine samples. The ultimate reference technique, liquid chromatography-Fourier transform mass spectrometry (LC-FTMS), is capable of confirming the findings within a 3 ppm mass accuracy using a target database of 7640 compounds (190). The application of LC coupled with single-stage or tandem mass spectrometry in drug quantification in blood serum and oral fluid was reviewed. The pros and cons of such LC-MS procedures, including sample work-up and ion suppression effect were critically discussed (191).



Analysis by Capillary Electrophoretic Techniques Capillary electrophoresis (CE) and capillary electrochromatography (CEC) possess inherent advantages of having the selectivity and versatility of LC and the high separation efficiency of GC. In forensic toxicology, drugs or poisons of interest exhibit limited polarity because highly polar or highly ionic compounds have difficulties passing the gastrointestinal system and/or the blood-brain barriers (192). With the introduction of novel pharmaceutical formulation techniques that could facilitate effective delivery of polar or even ionic compounds into the body, the analysis of such compounds in biological specimens imposes problems to GC methods, and for very polar compounds, even common LC methods would encounter difficulties. As the separation mechanism of CE is different from that of LC and GC, CE renders the separation of a wider scope of compounds including polar and ionic compounds possible. While an indirect capillary zone electrophoretic method for determining GHB in biological fluids (urine and serum) had been reported with an LOD of 3 mg/mL (193), a direct detection method for GHB in urine using CE-MS has recently been reported with an LOD of 25 mg/mL (194). Although a review has shown that a majority of papers using CEC for biomedical analysis relating to steroids, antidepressants and some other basic drugs in urine and plasma samples have published over the past decades, the number of applications to the analysis of biological fluids is very limited (195). In order to increase the applicability of CEC, it was suggested that an improvement in CECcolumn technology with regard to versatility and ruggedness will be vital for the future development of this new technique (195). Extraction Techniques Solid Phase Extraction (SPE) and Liquid-Liquid Extraction (LLE) Compared with LLE, SPE technique has the advantages of low solvent consumption, provision of cleaner extracts, ease of automation, high extraction efficiency for certain specific drugs and small sample volume. It provides an excellent alternative to the traditional LLE of biological samples. The use of SPE for sample clean-up in blood, urine and/or plasma followed by GC-MS analysis was reported for quinine (196), heptaminol (197), strychnine (198), pesticides such as carbofuran and carbaryl (199), organochlorine pesticides (200), furosemide (201), and opiate related drugs (202). In addition, a method for determining 30 abused drugs in oral fluid, using a mixed mode SPE with appropriate derivatization followed by GC-MS was developed (203). One of the claims for the widespread use of LC-MS is the simpler sample preparation in different biological fluids like blood, serum, plasma, urine and oral fluid. Isolation can be performed by: i) LLE in the analysis of sulfoureas (204), doxacurium and its breakdown products (205), metaxalone (206), anticoagulants (207), hypnotics and sedatives (26, 208-209), superwarfarins and vitamin K antagonists (210), flocoumafen and brodifacoum (211), tadalafil (212), tacrolimus (213), mosapride (214) and zaltoprofen (215), or ii) by SPE in the analysis of hypnotics and sedatives (84, 108, 216), antidepressants (217), illicit drugs (28, 107), dimethylamphetamine and its metabolites (218), ropinirole (219), aconitium alkaloids (220-221), ribavirin and its phosphorlated metabolites (222).


Solid Phase Micro Extraction (SPME) SPME, being a solvent free and concentrating extraction technique, is considered to be an alternative to LLE and SPE. In a review on recent advances in SPME and related techniques, it was shown that direct immersion, headspace and in-tube SPME were popular techniques for the extraction of a wide range of drugs and poisons in hair, urine, saliva, blood, serum and plasma, using mainly GC-MS for the analysis (223). Methods employing SPME/GC-MS for the quantification of a series of volatile organic compounds (224), such as halogenated alkanes, alkenes and aromatic compounds, halomethane (225), pesticides such as dimethoate (226), quinalphos (227), parathion (228), and organochlorine pesticides (229) in biological specimens have been reported. Other drugs like strychnine (230), selegiline (231) were also reported. Although SPME is mainly used for GC-MS, procedures for analyzing benzodiazepines in conjunction with LC/MS have also been reported (232). Direct Injection Whilst many extraction techniques require the removal of matrix compounds, such as proteins in biological samples, to avoid instrumental contamination, ion suppression in the MS and/or clogging of the HPLC column, they are also criticized as being time-consuming, requiring pre-concentration prior to instrumental analysis, and imposing potential environmental and health problems in respect of extensive use of organic solvents. With the use of an MSpak GF column, an LC-MS/MS method for the separation of four anti-allergic drugs, ketotifen, olopatadine, cetirizine, and ibudilast was established by direct injection of human plasma without the need of applying off-line extraction or column switching techniques (233). A method of direct urine analysis by LC-MS/MS to detect 23 analytes, covering phenylethylamines, benzylpiperazine, and non-benzodiazepine hypnotics, has been developed and served as a robust alternative for screening drugs of abuse (234). Analysis of Specific Drugs Markers for Ethanol Consumption Since ethanol is rapidly eliminated, the time span for its detection, possibly in the range of hours, is relatively short. Therefore recent consumption can be detected only with certainty by direct measurement of ethanol concentration in blood or urine. Several new markers have been proposed to extend the detection interval of ethanol, namely, ethyl glucuronide (EtG) (235) and ethyl sulphate (EtS) (236) in urine, the ratio of 5-hydroxytryptophol (5-HTOL) to 5-hydroxyindole acetic acid (5HIAA) metabolites of serontonin, and fatty acid ethyl esters (FAEEs). In addition to the analysis of EtG in urine, detection of EtG in other tissues (such as liver, muscle and bile) and rib bone marrows showed promising results as a proof of alcohol consumption before death (237). Although EtG and EtS were commonly detected by LC-MS methods (237-240), a CE method for the determination of EtS in urine was reported (241). A study on the concentration of EtG in the hair of known alcoholics has indicated that it correlates with the daily intake of alcohol (242). An LC-MS method for the detection of 5-HTOL glucuronide, a major excretion form of 5-HTOL has been reported to be useful for demonstrating recent alcohol intake (243). In a recent study, sixteen heavy alcohol drinkers were tested in a single, 2-day long 299


session to examine the effects of an acute dose of ethanol on serum FAEEs concentrations and the urinary 5-HTOL/5-HIAA ratio (244). The mean ratio of urinary 5-HTOL/5-HIAA was found to have significantly elevated 5 and 9 hrs after ethanol administration, but returned to the baseline after 13 hrs. This ratio was twice as high for the high dose group compared with the low dose group. On the other hand, serum levels of FAEEs were significantly elevated after 5 hrs, but not 13 hrs after ethanol administration. Two direct ethanol metabolites, EtG and cocaethylene in the hair of cocaine users were compared (245); EtG was found to be a more sensitive and specific marker for non-moderate alcohol users than cocaethylene. Cyanide Methods for the analysis of small molecules of toxicological interest, such as carbon monoxide and cyanide, are usually different from those for the other organic poisons. The use of isotope dilution-mass spectrometry coupled with headspace GC has been reported as a method for an accurate determination of cyanide in blood. Using the isotopic internal standard K13C15N, concentration of cyanide in blood can be accurately determined down to ng/mL (246-247). Drugs of abuse Cocaine An LC-MS/MS method after solid phase extraction has been developed for determining cocaine and its metabolites (ecgonine methyl ester, benzoylecgonine, norcocaine and ethylene cocaine) in whole blood and urine where quantification was performed using deuterated internal analytes of cocaine, benzoylecgonine and ecgonine methyl ester (248). A GC-MS method for the detection of cocaine and 10 metabolites, including pyrolytic products (methyl ecgonidine, ecgonidine, ethylecgonidine and nor-ecgonidine) in blood and urine has been established and was applied for the analysis of post-mortem blood and urine, as well as urine collected from living individuals (249). It was found that ecgonidine, the major metabolite of methyl ecgonidine, was present predominantly in postmortem blood and in the urine of living subjects, indicating smoking as the major route of cocaine administration. MDMA A new method using desorption/ionization on porous silicon (DIOS) mass spectrometry for profiling MDMA impurities has been developed to trace the origin of MDMA pills (250). An LC-MS/MS method for the determination of amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), MDMA, N-ethyl-MDA (MDEA), N-methyl-1-(3,4-benzodioxol-5-yl)-2-butanamine (MBDB) and paramethoxyamphetamine (PMA) in urine after LLE can be accomplished in an 8-min run time (250). A GC-MS method for determining 12 amphetamines in serum by on-line trifluroacetylation has been developed with LODs of 2.5-6.9 ng/mL with a linear range of 5-100 ng/mL (252). Enantiomeric separation of amphetamines in urine is sometimes necessary to differentiate illicit use of (S)-(+)-methamphetamine. A GC-MS method based on a chiral derivatizing agent, (R)-(-)-alpha-methoxy-alpha-(trifluoromethyl)phenylacetyl chloride (MTPA), to prepare the amides of diastereomers of methamphetamine has been developed (253) and can be extended to resolve GC peaks of (R)-(-)- and (S)-(+)-isomers of amphetamine, MDA, MDMA, and MDEA. An optimization for the quantification of 300

urinary metabolites of MDMA has indicated that acid hydrolysis was preferred over enzymatic hydrolysis prior to chromatographic analysis (254). In the analysis of amphetamines in hair, a GC-MS method after pentafluoropropionic anhydride derivatization was established with LODs and LOQs as low as 0.007 and 0.023 ng/mg and has been applied to detect 24 amphetamines positive hair specimens (255). A study on the distribution of MDMA and MDA in postmortem and antemortem specimens showed that the "drug/metabolite" concentration (MDMA/MDA) ratio in hair was not significantly different from the ratios derived from other specimens, such as urine and blood and was consistent with those reported for cocaine/benzoylecgonine or THC/THC-COOH (256). GHB The concentration of GHB in the blood samples of 50 blood donors and 50 postmortem cases was determined by a validated GC/MS procedure following the guidelines of the Society of Toxicological and Forensic Chemistry (STFCh). GHBconcentrations ranging between 0.11 and 1.56 mg/L (mean value 0.54 mg/L) in the donor’s blood, and 2.2 and 116 mg/L (mean value 32.4 mg/L) in the postmortem blood (257). A method using gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) to distinguish between endogenous level in blood/urine and GHB resulting from exposure was proposed. Significant differences in the carbon isotope ratio (d-C13 > 13.5/1000) were found between endogenous and synthetic GHB. Therefore, instead of using the cut-off level for positive postmortem blood GHB concentration, this method should provide an unambiguous indication on the origin of the substance (258). A study focused on two of the most significantly altered transcripts namely, epiregulin and phosphoprotein enriched in astrocytes 15 (Pea-15), in peripheral blood aimed at extending the window of GHB detection has been reported (259). Both genes have increased the ribonucleic acid expression in GHB-dosed mice (1 g/kg) as compared to the control. To confirm these results at the protein level, an intracellular flow cytometric assay is developed to detect protein level changes in the peripheral blood of both these potential biomarkers after GHB exposure and suggested that epiregulin and Pea-15 may prove to be significant surrogate markers for indirect GHB exposure, capable of extending GHB detection from 12 to 48 hours. Ion mobility spectrometry (IMS) was investigated as a method of screening urine and breath for the presence of GHB and the five-carbon analogues, including gamma hydroxyvalerate (GHV) and their degradation products with detection limits down to low ppm range (260). A GC/MS assay for the detection of GHB in hair has been developed; the endogenous level of GHB in guinea pig black hair was 3.01 (+/- 1.41) ng/mg and in human black hair, 1.02 (+/0.27) ng/mg (261). GHB levels in black hair were found to be much higher than those in brown and white hair. Ketamine A technique using SPE and liquid chromatography/TurboIonSpray/tandem mass spectrometry (LC-TIS/MS/MS) for rapid screening and quantitation of ketamine and its metabolite, norketamine in urine was developed, with concentrations of the samples studied ranging from 114 to 2925 ng/mL for ketamine and 453 to 9805 ng/mL for norketamine (85). Another LC-MS method was described using deuterated ketamine as an internal standard for the rapid screening of both ketamine and norketamine in urine and has been successfully used for analyzing 301


urine samples obtained from disco-dancing club participants (262). Recently, an SPME-GC-MS method has been developed and validated for measuring four club drugs – ketamine, GHB, methamphetamine and MDMA in human urine (263). This method has been reported to have the advantage of easy sample preparation, acceptable accuracy and precision for the simultaneous quantitation of these four drugs of abuse with no interference from the urine matrix. Buprenorphine Buprenorphine is becoming more clinically used as an alternative to methadone to treat heroin addiction. Its abuse was detected in many countries soon after it was approved for medical use. Its easy accessibility by a wide spectrum of drug abusers, especially heroin addicts resulted in substantial abuse. Thus, there is an increasing need for methods suitable for high-volume screening. Established methods involve complicated sample extraction procedures (264). A sensitive, yet straightforward method for the simultaneous analysis of buprenorphine and norbuprenorphine in urine using LC–MS/MS was developed (265) while in another report, cloned enzyme donor immunoassay assay (CEDIA) was applied for high-volume screening of buprenorphine in urine (266). Benzodiazepines A technique coupling solid phase micro-extraction with liquid chromatographictandem mass spectrometry (LC-MS/MS) for identifying 21 benzodiazepines and their relevant metabolites in addition to zopiclone and zolpidem at low concentration was developed by Quintela et al (84). Chromatographic separation was achieved within 18 minutes and the limit of detection was less than 0.05 µg/L for all analytes. As benzodiazepines could be measured at low concentration, this method is therefore useful for the analysis of urine in suspected drug-facilitated sexual assault cases. In addition, various LC-MS/MS methods have been developed for the simultaneous determination of benzodiazepines in urine (108, 208), blood (208), hair (208, 267) and oral fluid (25). In general, LLE is the common sample pretreatment method, except for one report on the analysis of benzodiazepines in urine, where enzymatic hydrolysis followed by SPE was employed (108). Methods using LC-DAD/GC-MS for the analysis of clonzapam (268) and flunitrazepam (269) and their corresponding 7-amino analogues with LOQs of 1-5 ng/mL in whole blood have been described. The analysis of a series of benzodiazepines and their alpha-hydroxy metabolites, zaleplon and zopiclone in whole blood has been reported with the use of either GC-negative chemical ionization MS method (270) or GC-MS after tert-butyldimethylsilyl (TBDMS) derivatization (271). Chemical Warfare Agents Organophosphorus nerve agents and sulphur or nitrogen mustard are among the most toxic organic compounds known and continue to be a threat for both military and terrorist use. Sensitive and specific methods for the detection and verification of exposure to nerve agents are required for diagnosis, therapeutic monitoring, health surveillance and forensic purposes.


Analytical protocols have been developed for the quantitation of the urinary metabolites of sarin (GB), soman (GD), VX, Russian VX (RVX) and cyclohexylsarin (GF), utilizing SPE-isotope dilution LC-MS/MS (272) and isotope dilution GCMS/MS after LLE followed by methylation with diazomethane (273). Another method using SPE-GC/MS has been developed for the trace analysis of alkyl alkylphosphonic acids and the metabolites of organophosphorous nerve agents in urine after derivatization to the pentafluorobenzyl esters, achieving an LOD of 0.1 ng/mL in the selected reaction monitoring mode (274). A method has been described for the analysis of the sulfur mustard metabolite 1,1'sulfonylbis[2-S-(N-acetylcysteinyl)ethane] in human urine using LC-MS/MS in negative ion mode with an LOD of 0.5-1 ng/mL (275). Another method with an LOD of 0.1-0.5 ng/mL, using SPE-LC/MS and deuterated internal standard has been established for the analysis of the a-lyase metabolites of the sulfur mustard, 1methylsulfinyl-2- [2-(methylthio)ethylsulfonyl]ethane and 1,1'-sulfonylbis [2(methylsulfinyl)ethane] in human urine (276). By way of isotope-dilution GCMS/MS, a method was developed to quantify trace levels of 1,1'-sulfonylbis [2(methylthio) ethane] in human urine as a mean of assessing exposure to the sulfur mustard agent (277). Alternatively, a GC-MS method based upon the quantitative analysis of thiodiglycol (TDG) released from blood protein adducts has been developed for determining exposure to sulfur mustard. The TDG was derivatized with pentafluorobenzoyl chloride to achieve sensitive detection by negative-ion chemical ionization. The assay provided a sensitive and simple approach for the analysis of TDG cleaved from blood proteins at relatively long time frames (21-45 days) after sulfur mustard exposure (278). A standard operating procedure has been developed for an immunoslotblot assay of sulfur mustard adducts to DNA in human blood and skin. A minimum detectable level of exposure of human blood in vitro (≥ 50 nM) sulfur mustard is feasible with the assay. In the case of human skin, a 1 s exposure to saturated sulfur mustard vapor (830 mg/m-3) could still be detected (279). An improved method was used to measure levels of the urinary metabolites Nethyldiethanolamine (EDEA), N-methyldiethanolamine, and triethanolamine (TEA) in rats dosed with nitrogen mustards and to establish background levels of EDEA, N-methyldiethanolamine, and TEA in human urine samples from a population with no known exposure to nitrogen mustards. The background concentrations for TEA in the human population ranged from below the limit of detection (LOD = 3 ng/mL) to approximately 6500 ng/mL. Neither EDEA (LOD = 0.4 ng/mL) nor MDEA (LOD = 0.8 ng/mL) was detected above the LOD in the human samples (280). Toxic Herbs, Toxins and Venoms Toxic Herbs Traditional medicines prepared from plants, animals or minerals, have been widely used for thousands of year in countries, such as China and India, to treat various diseases (281). They have gained increasing popularity today (282). The chemical components of traditional medicines could not be explicitly elucidated because they contain a complex mixture of compounds, the composition of which could be significantly affected by species variations, geographical sources, harvesting, 303


processing and storage conditions. Quality control is crucial to ensure stability, effectiveness and safety of traditional medicines which although have empirically been considered to have minimal side effects. As a great number of herbal medicines show complicated profiles of constituents, work on the control and quantitative analysis of the active components in traditional medicines have become an important research interest. Modern instrumentation and technology has made the separation, isolation, and characterization of the active ingredients of herbal medicines more practicable. Preparative high-speed counter-current chromatography has been demonstrated to be useful in the isolation and purification of alkaloids from medicinal herbs (283284). The coupling of headspace solid-phase micro-extraction with comprehensive two-dimensional gas chromatography was shown to be a powerful technique for the rapid sampling and analysis of more than 20 marker volatile oils in complex herbal materials belonging to Panax quinquefolius (American ginseng) (285). A novel method based on headspace measurement by proton-transfer-reaction mass spectrometry has been developed for determining the quality of a herbal extract (286). Supercritical carbon dioxide was successfully used for the extraction of the active ingredients, resveratrol (3,5,4 -trihydroxystilbene) and its glycoside piceid, in a traditional Chinese medicinal herb, Polygonum cuspidatum (Hu Zhang in Chinese). The yield obtained by supercritical fluid extraction (SFE) was found to be comparable with traditional organic solvent extraction, indicating that SFE is a good alternative extraction method (287). Among the commonly known toxic plants, aconites, the main toxic diterpenoid alkaloids from plants of the genus Aconitum L, have received much attention in Asia and the Western countries owing to their high potency with narrow therapeutic range. Detection of aconites and their metabolites in biological samples has been made possible by using advanced instrumentation (220-221, 288-290). Taxines are the active, poisonous constituents in yew plants (Taxus spp.) and have been implicated in animal and human poisoning cases, imposing toxic effects on cardiac myocytes and causing heart failure. A recent publication described a new, specific and sensitive SPE-LC-MS/MS method for the detection of both taxine B and isotaxine B, the two main toxic pseudo-alkaloids from yew, in biological samples with LOD and LOQ being 0.4 and 2 ng/g, respectively (291). The method was applied to the determination of taxine B and isotaxine B in four fatal cases (two humans, two horses) with suspected yew intoxication. Intoxications and fatalities due to misidentification and mislabeling of medicinal plants, as well as adulteration/substitution of non-toxic plants by toxic ones are not uncommon. Simultaneous determination of aristolochic acid I, fangchinoline and tetrandrine in medicinal plants by LC-DAD and LC-MS was described (292). It has made possible the detection of adulteration of non-toxic Stephania tetrandra (Fangji) by Aristolochia fangchi (Guang fangji), the latter of which contains the nephrotoxic and carcinogenic aristolochic acid.


Venoms The toad venom (Ch’an Su) or bufonis venenum is a dried concentrated secretion of the parotid and sebaceous glands from either Bufo bufo gargarizans Cantor or Bufo melanosticus Schneider; it is widely applied in China, Japan, and other Asian countries. The preparation contains two groups of toxic compounds: i) the steroid derivatives resembling cardiac glycosides and consisting of bufagenins (bufagins, bufadienolides) and bufotoxins, and ii) the basic components including epinephrine (adrenaline), norepinephrine, serotonin, and bufotenin. Ch’an Su given in minute doses produces stimulation of myocardial contraction, diuresis, pain relief, and antiinflammatory effects; it also has a topical use for skin eruption. Fatal poisoning was occasionally reported (293). The detection and characterization of the major bioactive constituents of Ch’an Su have been extensively studied (293-299). Characterization of the peptide contents in snake venoms can be an important tool for the investigation of new pharmacological lead compounds. A single-step analysis of crude snake venoms for low molecular mass peptides, using matrixassisted laser desorption/ionization time-of-flight mass spectrometry has been demonstrated (300). In another study, a proteomic identification of the venom from the Australian Brown snake using two-dimensional gel electrophoresis, mass spectrometry, and de novo peptide sequencing was presented (301). Toxins Contamination of marine species with various toxins either produced by toxic algal blooms or micro-organisms living in tropical waters has affected aquacultural industries worldwide. It has been reported that paralytic shellfish poisoning has the highest mortality rate (13%) of all marine toxins (302). Efforts have been made to develop rapid, reliable, and sensitive methods for the identification of paralytic shellfish toxins in contaminated shellfish and in biological specimens (303-306). Tetrodotoxin poisoning is an infrequent and yet a considerable health issue in some countries in South-East Asia. Some of the latest work achieved good results on the measurement of the toxin in biological samples, by applying LC-MS/MS after SPE cleanup (307-309). The application of HPLC with post-column derivatization and fluorescence detection was also reported (310). Drugs in sports and doping control Doping refers to the use of performance-enhancing drugs such as anabolic steroids, particularly those that are prohibited under the list published by the International Olympics Committee. Some doping substances, however, are permitted in low doses (alcohol and caffeine). Another form of doping is blood doping, either by blood transfusion or use of the hormone erythropoietin (EPO). Polettini has reviewed LCMS procedures for the screening, identification and quantification of doping agents in urine and other biological samples over a 5-year period. Information relating to: i) the reasons for potential abuse by athletes, ii) requirements for analysis established by the World Anti-Doping Agency (WADA), and iii) the WADA rules for the interpretation of analytical findings for different classes of drugs have been provided (311).



Anabolic androgenic steroids Anabolic androgenic steroids (AAS) were widely abused by athletes. According to the Adverse Analytical Findings by Accredited Laboratories in 2005 published by WADA, AAS accounted for more than 40% of the total positive findings (312). Testosterone was the most common AAS abused. Although traditional methods allow identification and characterization of testosterone and its metabolites in urine, they cannot distinguish between pharmaceutical products and endogenous materials. Detection of testosterone usage in sports can be classified as direct and indirect methods. The indirect method involves the determination of the ratio of testosterone glucuronide and epitestosterone glucuronide in urine where a ratio of >6 would be considered as a positive result for misuse. The stability of testosterone glucuronide and epitestosterone glucuronide in urine stored at various temperature was studied and sodium azide was recommended to be added to preserve the analytes (313-314). The direct method involves the determination of the carbon isotope ratio of testosterone in urine. In this connection, various factors affecting the carbon isotope ratio of testosterone metabolites in urine were studied (315-316). Nandrolone was the second most frequently abused AAS after testosterone (312). However there was argument that nandrolone metabolites could be endogenous. Therefore the excretion pattern of nandrolone after high-intensity exercising was studied by GC-MS (317). A candidate reference measurement procedure for 19-NA, the major metabolite of nandrolone in urine, involving isotope dilution coupled with LC-MS/MS has been developed and critically evaluated (318). By adopting similar methodology, a series of reference measurement procedures for the determination of progesterone (319), estradiol-17 beta (320), total cortisol (321), and total 3,3',5triiodothyronine (322) in human serum, using isotope-dilution LC-MS/MS have been developed. GC-MS was extensively used in the detection of AAS. However, with the emergence of designer anabolic agents such as tetrahydrogestrinone, the focus has shifted to LC-MS because these designer anabolic steroids could not be detected by the existing GC-MS method. Fast and selective LC-MS/MS methods for the screening of four anabolic steroids, including tetrahydrogestrinone have been developed and validated (323). The fragmentation behavior of stanozolol and its metabolites as well as that of their synthetic analogues was investigated after positive electrospray ionization and subsequent collision-induced dissociation utilizing a quadrupolelinear ion trap and a novel linear ion trap-orbitrap hybrid mass spectrometer (324). Conventional GC-MS methods for the detection of AAS in different biological matrices were also developed (325-326). Selective androgen receptor modulators (SARM) have similar pharmacological effects of AAS and their potential misuse in sports is high. A screening method for four synthetic SARMs was developed and validated (327). The detection of a newly emerged AAS, Madol, was described (328). A review concerning the pattern of abuse and the methods for detecting misuse of AAS was published (329). Stimulants Stimulants were the first group of compounds prohibited by most international sports federations. The misuse of stimulants in sport activities was prevalent in 1950 306

to 1980. During these years, because of their volatility, amphetamine-type drugs were commonly analyzed underivatized using GC-NPD. However in modern analysis, GC-MS is required for the confirmation of amphetamines. Since the mass spectra of underivatized amphetamine-type drugs exhibit base peaks at low mass and minor ion intensities at higher masses, derivatization is required when GC-MS is used. To overcome this difficulty, LC-MS methods were developed for the detection of amphetamine-type drugs and their metabolites in urine (330-331). Some of the drugs in the stimulant category, such as strychnine and ephedrine, are commonly found in medicinal preparations. The control of these drugs is different from amphetamines which are strictly prohibited, for example, an athlete would be sanctioned for misuse of ephedrine only when the concentration of the latter in urine exceeds 10mg/mL. Studies on the excretion profile of ephedrine and strychnine have been made (332-333). A study on the use of solid phase microextraction method coupled with GC-MS for the screening of stimulants and narcotic analgesics in urine was presented (334). The method has the advantage of allowing automation, thus increasing analytical capacity. A review on the misuse of stimulants by athletes was also published recently (335). Glycoprotein Hormone Glycoprotein hormone includes chorionic gonadotrophin (hCG), EPO and human growth hormone (hGH). hGH is a naturally occurring substance and so demonstration of abuse relies on the detection of the growth hormone in the athlete’s body at a concentration exceeding the established reference level. Detection of hGH abuse is complicated by the fact that recombinant and endogenous growth hormone (GH) have very similar amino acid sequences. Currently there are two approaches to detect GH abuse. The first is based on the detection of different pituitary GH isoforms whereas the second relies on the measurement of biomarkers. Various biomarkers were identified for detecting GH abuse and factors which could affect their concentrations have been investigated (336-337). Insulin-like growth factor-I (IGF-I) and procollagen type II peptide are the biomarkers for detecting recombinant human growth hormones. Immunoassay methods for the measurement of IGF-I and procollagen type II peptide were evaluated (338). Reviews on the methods for detecting GH misuse in sports were reported (339-340). Recombinant human erythropoietin (rhEPO) increases the maximum oxygen consumption capacity, and is widely abused among athletes of endurance sports. A number of reviews have discussed the methods for identifying misuse of rhEPO (341-343). Methods utilizing matrix-assisted laser desorption/ionization mass spectrometry for detecting rhEPO misuse have been evaluated (344-345). An immunoassay method for the measurement of EPO as an indirect biomarker of rhEPO misuse in sports was assessed (346). The use of hematologic parameters for the detection of misuse of rhEPO was explored (347). Insulin and related synthetic therapeutics are prohibited by WADA for athletes demonstrably not suffering from diabetes mellitus. LC-MS methods for identifying three intact rapid-acting insulin analogues in urine samples and plasma were described (348-349). Horse Racing Horse racing is another battlefield for scientists fighting against doping and LCMS/MS has become an important weapon. The dissociation pathways of anabolic 307


steroid by electrospray ionization tandem mass spectrometry were studied and the proposed fragmentation pathways were helpful for the characterization of new steroids (350). LC-MS methods for the screening of steroids, acidic drugs and basic drugs in horse urine and plasma have been published (351-356). On the other hand, GC-MS is still being used for unveiling the misuse of drugs in horse racing. A GCMS method for the detection of clonidine, a performance-enhancing agent, in equine plasma was reported (357). Fecal matter is considered to be an alternative sample, especially for young horses from which urine samples are more difficult to collect. A method on the detection of non-steroid anti-inflammatory drugs in horse feces has been reported and evaluated (358). Alternative Specimens Blood and urine are the most widely used biological specimens for forensic toxicological examination as well as routine testing of abused drugs. However, recent technological advances have made it possible to use alternative specimens, including oral fluid (359-360), hair (361-362), sweat (363), meconium (364), breast milk (365-367), nail (368-369) and other unconventional biological specimens (370371). The importance of alternative specimens in forensic toxicology has been recognized in the scientific and technical guidelines compiled by the U.S. Department of Health and Human Services (HHS) in 2004 for the Federal Workplace Drug Testing Program, permitting screening of hair, oral fluid, and sweat patch specimens in addition to urine, for abused drugs (113). The application of oral fluid and hair in DUID, work-place drug testing and DFSA has been discussed in detail in previous sections and will not be covered in this section. Oral Fluid Oral fluid is the alternative specimen recently receiving the most interest. It has the advantage of being easy to collect and does not invoke privacy or gender concerns. Moreover, oral fluid has been widely studied for use in therapeutic drug monitoring and abused drug testing (372). In addition to a review on drugs of abuse in oral fluid (20), Drummer published another review on drug testing in oral fluid (373), emphasizing the difficulties associated with this form of testing and illustrating applications of oral fluid testing for specific drugs. The recovery of abused drugs from the oral fluid collection device, Quantisal, (374) was found to be satisfactory for oxazepam, amphetamines and methamphetamines, opioids, cocaine and THC. The same device has been used to collect oral fluid for the determination of propoxyphene using GC-MS and was applied to authentic specimens taken from an individual prescribed with propoxyphene following surgery (375). A study investigating the effect of storage systems on drug stability and the recovery of illicit drugs in oral fluid, using three different collection devices was described. It was found that storage of oral fluid at 5oC or room temperature had no significant effect on drug recovery (376). Understanding the relationship of drug concentration in oral fluid and plasma is important for the interpretation of oral fluid test results. Oral fluid and plasma specimens were collected from 6 subjects following smoking of cannabis cigarettes (377); the similarity of THC concentrations in oral fluid and plasma has indicated physiological correlation between these specimens. Studies on passive cannabis 308

smoke exposure have concluded that the risk of positive oral fluid tests from passive cannabis smoke inhalation was limited to a period of approximately 0.5 – 1 hour following exposure (378-379). The use of LC-MS/MS is explored as a possible replacement for immunoassay screening of drugs of abuse in oral fluid (380). Oral fluid samples collected from 72 subjects attending an addiction clinic were screened for opiates, cocaine, methadone and benzodiazepines, using both enzyme-linked immunosorbent assays (ELISA) and LC-MS/MS. It was found that LC-MS/MS compared favorably with ELISA for the detection of specific drugs or their metabolites in the case of morphine, methadone and the cocaine metabolite, benzoylecgonine. Hair The advantage of hair is obvious: sample collection is easy to perform and is almost non-invasive. Moreover, the window of drug detection is dramatically extended to weeks, months or even years. Thus, hair testing has gained much interest because of the possibility of tracing the history of drug use. Several historically important individuals have had their hair analyzed for drug exposure, namely Napoleon Bonaparte (381), Ludwig van Beethoven, and William Butler Yeats (382). A comprehensive, chronological compilation of scientific literature on hair drug testing up to 2002 by the International Journal of Drug Testing is a useful reference on the Internet (383). Hair testing with respect to physiological basics of hair growth, mechanisms of substance incorporation, analytical methods, result interpretation and practical applications of hair analysis for drugs and other organic substances has been reviewed (119, 384-386). A review on the techniques utilized for hair analysis, including spectrometry and more sophisticated methodologies, with special emphasis on GC-MS and LC has been presented (387). Recent trends in research on hair analysis include the mechanisms of drug incorporation and retention (388), new analytical procedures (119) as well as alternative sample preparation techniques (208, 267, 389-391). Validation, quality assurance and cut-off values were the subject matters in a recent publication and workshop on hair testing (181, 392). Moreover, the possibility of using hair analysis for low-level monitoring of exposure to diazinon, a common pesticide, was demonstrated using GC-negative chemical ionization-MS analysis (393). The application of hair as a biological indicator of drug use/abuse or of chronic exposure to environmental toxicants has been reviewed (394). Sweat Drugs of abuse and their metabolites have long been known to be excreted in sweat. The development of a commercial sweat patch collection device has made possible the detection of drug use over a period of approximately 1 week of patch wear (395399). There has also been an interest in the use of the sweat patch for regulated workplace drug-testing applications (400). The detection of cocaine and its metabolites in sweat patches was extensively studied. Recent work was published on the duration of wear for determining recent 309


or concurrent use (401), the effect of sweat patch location on the drug level (402), comparative studies of analytical methods (403-404), and the disposition of drugs after administration (405). Sodium and potassium, being physiologically present in sweat, can be used as internal reference for estimating the volume of sweat. To this end, a capillary electrophoresis method with indirect ultra-violet detection has been developed for the determination of sodium and potassium in sweat. Commercial sweat patch was found to be suitable for the collection of cations, while sodium was a useful internal standard for determining the volume of sweat accumulated in a patch (406). Meconium Meconium is a newborn’s first stool. It is formed over the last trimester of pregnancy, and thus can represent exposure to drugs over a 16-20 week prepartum (407). Detection of drugs and metabolites such as oxycodone (408), m- and phydroxybenzoylecgonine (409), methadone and EDDP (410), metabolites of dronabinol (411) and even multiple classes of pesticides (412) in human meconium has been reported. It provides a crucial indication of neonatal exposure or maternal drug use. LC-MS/MS methods for the simultaneous determination of 6 opiates: codeine, morphine, hydrocodone, hydromorphone, oxycodone, and 6acetylmorphine (6-AM) in different biological specimens have been developed (413). The positive detection of 6-AM in meconium has been reported for the first time, providing a definitive proof of illegal heroin abuse by the pregnant mother. Interpretation of Toxicological Results Drug Levels in Postmortem Specimens To assist in the interpretation of drug levels found in post-mortem cases, a review of seemingly similar cases can assist in understanding the role of these substances under the circumstances presented. Alcohol Jones have performed an extensive literature review on the postmortem aspects of ethanol and problems associated with the correct interpretation of the results (414). It was recommended that the urine/blood concentration ratio could provide a clue relating to the stage of alcohol absorption and distribution at the time of death. In addition, vitreous humor was strongly recommended to be used for deciphering whether the deceased had consumed alcohol before death (414); other specimens, such as in the case of skull trauma, an intracerebral or subdural clot could also be used. Biomedical tests or markers recently introduced for detecting postmortem production of alcohol were discussed (414). In two studies on a series of postmortem cases comparing vitreous humor alcohol with blood alcohol (415, 416) and urine alcohol (416), the benefit of analyzing multiple specimens, particularly vitreous humor, to arrive at a more appropriate interpretation on the analytical results was demonstrated. Volatile Organic Compounds By way of analyzing n-tetradecane, the amount of diesel fuel No. 2 in a suicide case was estimated to be 9.1 mg/L in heart blood and 3500 mg/L in the abdominal contents (417). In two fatal cases of sniffing cigarette lighter fluid (418), toxicological 310

investigations revealed the presence of isobutane in the heart blood and brain tissue of both cases (case 1: heart blood 0.1 µg/g, brain tissue 2.3 µg/g; case 2: heart blood 4.6 µg/g, brain tissue 17.4 µg/g) and the presence of its metabolite 2-methyl-2propanol in the heart blood of both cases (0.5 and 1.8 µg/g, respectively). In another report on 3 sudden death cases involving inhalation of butane or propane, headspace GC was used as an analytical tool and n-butane was found in 2 cases as the major volatile substance detected at concentrations of 0.52 and 0.11 µL/mL in blood, while 10.19 µL/mL propane was detected in the blood of the third case (419). Abused Drugs A simple SPE/GC-MS method for the simultaneous determination of thebaine, 6monoacetylmorphine and 6 opiates in post-mortem fluid from one extraction was developed with LODs ranging from 0.78 to 12.5 ng/mL and a linear dynamic range of 6.25-1600 ng/mL (420). In a case of unusually high postmortem morphine concentrations following the use of a continuous infusion pump, the free and total morphine in blood were found to be 96 and 421 mg/L respectively (421); records indicated that the infusion pump could have continued to deliver the drug for 15-45 min following death, thus contributing to the elevated morphine level. A fatality due to acute intoxication of alpha-methyltryptamine (AMT) revealed 2.0 mg/L in blood, a total amount of 9.6 mg in the gastric contents, 24.7 mg/kg in liver, and 7.8 mg/kg in the brain. AMT was isolated using solid-phase extraction, derivatized with pentafluoropropionic anhydride, and analyzed using GC-MS (422). The distribution of GHB in tissues and biological fluid following a fatal overdose was analyzed by GC-MS as the trimethylsilyl derivative. The case demonstrated the importance of determining GHB in urine and vitreous fluid in death investigation in the light of a significant postmortem production of GHB in blood (423). In a study to discriminate between endogenous level from exogenous exposure of GHB, 71 autopsy cases with the cause of death unrelated to GHB exposure were examined (424). The result has shown that in 14 cases where the GHB concentration was greater than 50mg/L was due to postmortem formation. Thus, a postmortem blood GHB concentration of >50 mg/L alone cannot provide support for an exogenous GHB exposure; it is essential to analyze for GHB in other specimens, including peripheral blood (femoral blood in particular), and vitreous humor. Other Drugs In a case involving an acute fatal overdose of tramadol and amitriptyline, the tissue and fluid distribution of tramadol, amitriptyline, and their metabolites in 12 matrices were reported (425). A male who died after ingesting 12g of fluoxetine has been reported to have a fluoxetine at a concentration of 4500 µg/L, and diazepam at 500 µg/L in blood (426). A fatal trazodone overdose case revealed the presence of 4.9 mg/L of trazodone and 0.6 mg/L of m-chlorophenyl-piperazine (m-CPP), the major metabolite (427) in blood. The medical history and postmortem analytical results of 20 quetiapine cases in Virginia, USA from 1999 to 2004 by using SPE-GC-MS have been reported (428): the average blood concentration in 18 cases in which quetiapine contributed to the cause



of death was 7.95 mg/L (0.4-76 mg/L). In another 2 reports of fatality due to quetiapine, the drug levels in blood were in the range of 5.9–16 mg/L (429) and 0.72–18.37 mg/L (430). In an investigation of 21 death cases due to quetiapine it was determined, after HPLC analysis of the postmortem specimens, that the therapeutic level of quetiapine in blood was less than 1 mg/L and the toxic level was suggested to be greater than 1 mg/L, while a liver concentration of greater than 5 mg/L would be regarded as fatal (431). A study of 30 autopsies in Madrid, Spain related to a widespread antidepressant, citalopram has found that the toxicity of citalopram would be greatly enhanced when other associated psychoactive substances, such as psychotropic drugs, alcohol and opiates were involved (432). Shared with a similar view, a case was ruled acute fatal intoxication by the combined effects of olanazapine and citalopram (433). The drugs were assayed by liquid-liquid extraction followed by GC with nitrogen phosphorus detector, and qualitatively confirmed by electron impact GC-MS. A case of benzocaine toxicity leading to the death of an infant was reported, revealing the presence of benzocaine at a concentration of 3.48 mg/L in blood, which falls within the range of 0.45), 2) independent chromosome location or minimal distances from other informative forensic STR loci (> 1.0 Mb between loci), and 3) low association with populations (Fst 800,000 SNP genotypes in a single day (231, 232). The process design involves PCR amplification, amplicon hybridization with SNP primers, capture of extended primers on an array plate and detection of fluorescence. A parallel system using BeadChip technology has also been used for genotyping a variety of blood groups with full concordance (233). It is highly likely that the larger market for clinical diagnostic tests and the prospect of commercial development will advance the innovation and implementation of rapid screening technologies much faster than 628

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what would be expected for similar tests developed exclusively for forensic applications. Consequently, although there may be a slight delay in the implementation of a clinical diagnostic tool for forensic use, the similar validation, rigorous quality control, ease of use as well as low cost and high benefit characteristics of such tests should enable the rapid adoption and implementation of clinical diagnostic technologies for forensic purposes. A detailed and comprehensive review of automated forensic sample processing has been published by Leclair and Scholl (245). This report leveraged the authors’ extensive experience in criminal and clinical genotyping as well as mass disaster victim identification which allowed them to develop effective best practices guidelines for the creation and implementation of a casework sample processing system. The authors reinforced the primary expectations of increased sample flow, creation of robust and computer-based chain of custody, improvement of the timeliness of processing and cost reduction. The attributes of automated fluid handling with different pipette tips (fixed and disposable) were illustrated by numerous examples and clearly demonstrated the validation and implementation steps required to achieve a successful automated extraction and processing system. The basic automated liquid class protocols were also discussed with respect to integrating volume verification steps (246) to improve data quality by capitalizing on the precision and accuracy afforded by automation. This review also discussed the need for continued development and improvement of new technologies to safeguard against over-capacity and under-utilization, such that the maximum efficiency and best performance is gained through high-utilization. This single paper presents the process and strategic considerations of forensic automation along with advantages and disadvantages in a manner that will ensure its place as a key reference for many years to come. Low Copy Number and Sensitive DNA Detection In the field of DNA analysis the expectation of obtaining more probative information from smaller amounts of evidence (251) must be balanced with valid and reliable processes, not exceeding the limits of technology. This is particularly relevant in obtaining DNA profiles from trace evidence transferred by touch and casual contact which contains low amounts of template DNA or what many refer to as using “low copy number” (LCN) analysis (259, 263). LCN DNA typing has been defined as “the analysis of any results below the stochastic threshold for normal interpretation”. Samples containing < 100 pg DNA fall into this category and require specialized techniques and rules of interpretation (259). Many aspects of LCN enhancements have been reported in the past few years, most of which fall into the categories of: 1) raising the number of amplification cycles (254, 268) 2) using whole genome amplification (265,266,269,270) 3) developing special guidelines for the interpretation and statistical analysis of data (258, 259, 267) and 4) more recently, enhancements of extraction procedures to recover better quality DNA (253, 264). LCN no doubt may be the last recourse to solving a challenging older case (252) but strategies dealing with allele dropout and drop-in, higher stutter peaks and sporadic contamination must be fully appreciated. From a more practical consideration, knowledge of shed evidence and understanding the crime scene may have as much relevance to using LCN as any technical or scientific consideration. 629

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How much DNA is enough and how did it get there in the first place? The forensic scientist has faced the same problems as anthropologists regarding authentication and plausibility of results (255). In some instances guidelines for the interpretation of STR profiles derived from less than 100 pg have contributed to better use of evidence but have also raised cautionary issues (258, 259), and in the end, guidelines alone may not distinguish true identity from contamination. Several recent studies highlight our lack of understanding regarding the potential for casual contact DNA being present at the crime scene. Although experiments on LCN represent difficult control challenges (absence of DNA), Port and coworkers (260) have demonstrated that a person speaking less than 30 seconds from a distance ranging between 69-115 cm can deposit sufficient amounts of DNA that the speaker can be identified from objects or persons directly in front of them. Our basic understanding of casual contact and transfer of DNA biological material has also been investigated using experimental designs originally described by Lowe et al (262). Phipps and Petricevic (261) attempted to characterize the variables associated with “shedding” (loss or shedding of DNA containing cellular material from individuals) with 60 volunteers tested under different conditions of hand washing and time that elapsed since touching. Their findings proved to be more complex than expected and the authors conclude that they do not know what makes a good or bad “shedder” but such knowledge is very important prior to the interpretation of trace DNA evidence. In reviewing LCN results it is important to recognize the difference between contamination and biological evidence that may contain a mixed DNA profile. Contamination or the introduction of new material (i.e. biological material) that was not originally at the crime scene may be caused by the investigator or laboratory personnel. Elimination databases of DNA profiles composed of profiles from police and laboratory members who collect and process evidence is a key strategy to interpret LCN or any DNA results. One recognizes the potential for LCN contamination concerns after recent studies conducted by van Oorschot (256) which report the transfer of DNA from fingerprint brushes that were used to powder over biological stains (blood or saliva). In contrast to other studies, the authors noted (256) that some fingerprint powders can inhibit PCR amplification. In other experiments, material accumulated on one brush after powdering a biological stain was enough to transfer DNA to other brushes stored together, and derive STR identification. This study concluded that fingerprint brushes should be a consideration in the interpretation of unknown profiles derived from evidence and the authors made a detailed 15 point set of recommendations regarding prevention. Although the prospect of truly “negative controls” or the complete absence of any DNA in the laboratory has been discussed (275), contamination from plastic ware and water as an exogenous source of DNA remains concerning. Tamariz (257) reported on successful STR amplification results following contamination studies with limited amounts of DNA. The longevity and accumulation of DNA that was found on “mocked-up” tubes following routine laboratory extraction and PCR practices was evaluated. They found that very close exposure to ultraviolet irradiation from a commercial UV cross linker (Stratagene, La Jolla, CA) for 30 630

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minutes could greatly diminish the carryover of DNA from lab ware and water used for subsequent PCR amplification. Unfortunately, such a prolonged exposure and the potential loss of intensity over time of many UV irradiation devices (UV tube decay) make this a challenging solution to prevent contamination for many routine DNA analysis procedures. One approach not always taken into consideration for processing limited amounts of DNA evidence is better extraction and use of amplified products. Smith and Ballantyne (253) compared several commercially available nucleic acid ultra filtration devices as well as enzyme hydrolysis mediated purification procedures to concentrate the post PCR fluorescently labeled STR product. They found that 28 cycle amplified products purified by the Qiagen MiniElute silica column resulted in a fourfold increase in fluorescent signal intensity over unpurified product. The net result from this and other studies by Hutchinson (264) clearly demonstrate that a simple procedure which enhances signal intensity of STR amplified products obtained from standard amplification protocols may provide equivalent or better results than LCN analysis. Interpretation of the results and presentation in court would follow the precedent set for standard STR DNA evidence practices. Software Assistance for DNA Analysis and Interpretation of STR DNA Evidence An expert system is any type of artificial intelligence software that uses a preprogrammed set of rules to provide interpretation or conclusions and tries to parallel the human logic decision making process derived through experience and expertise (293). One of the more challenging aspects of forensic science is the interpretation of DNA evidence from a crime scene which can be compounded in complexity by multiple donors. The use of expert computer systems has become more prevalent as high throughput analytical systems generate large amounts of data which are time consuming to process (273, 278, 281). This has been particularly noted in mass disaster victim identification as well as a fundamental addition for growing criminal offender databases (294, 279). There are two major approaches taken in expert systems: 1) the probabilistic approach which uses information contained in large databases to formulate the probabilities of alleles being present or not present based on prior knowledge and 2) the graphical simulation model that is designed to replicate all aspects of the DNA process and can be used to predict the outcome of specific scenarios based on the quality of the DNA data sets. Typically, any number of alleles may be observed in a sample of unknown origin (i.e. crime scene) but if only one or two alleles per locus are observed, then the sample is considered to come from a single donor. Degradation of the evidence which could lead to an incomplete DNA profile (i.e. fewer loci giving results), a mixture with one donor representing less than ten percent of the amplified product or the overall recovery of low amounts of DNA could lead to masking of a second or multiple donor(s) making it difficult to determine the number of overall potential contributors (271). Recent studies by Buckleton and coworkers (272) have assessed the risk associated with current practices of using likelihood ratios to interpret mixed DNA profiles and reject the Paoletti et al. (271) argument that 631

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no assessment of such evidence can be made. The effect of masking on the number of alleles presented in a mixture is evaluated with simulation studies performed on actual data sets composed of the Profiler Plus set of loci from Australian forensic laboratories and SGM+ from New Zealand and the United Kingdom. The true risk of the incorrect assignment of numbers of contributors was evaluated with both STR systems and specific recommendations are made based on past work conducted on STR interpretation guidelines (273). Considerations for mixture interpretation have posed an interesting challenge for low levels of DNA detection (259), and indicate that repeat measurements of DNA evidence for multiple donors and population substructure can be invaluable to address concerns (274). A further extension of interpretation of low copy number (LCN) STR profiles was described by Gill (258) with the development and testing of an expert interpretation system (LoComationN) which uses probabilistic theory to calculate numerous alternative explanations for the likelihood of origin of specific STR profiles. Unlike the consensus method which requires allele concordance demonstration from separate PCR analyses, LoComationN is intended to maximize the full potential of limited DNA evidence which is particularly relevant to enhanced or sensitive detection of STR data from touched evidence or environmentally challenged biological exhibits. The mixture complexity issue will undoubtedly be a contentious topic of future discussions and has also been addressed as a priority for review by a working subgroup of the SWGDAM (July 2007). A novel forensic approach for evaluating expert systems for STR interpretation was developed by Gill et al. (281, 276) and uses a graphical model to simulate stochastic variation associated with the entire DNA process starting from extraction of the sample followed by PCR preparation and the STR results following amplification. The authors have derived specific input efficiency parameters for each step of the DNA process and the expected output parameters of a quality STR profile (heterozygote balance, PCR slippage mutations or stutter and allelic drop-out) are evaluated from a perspective of improving the overall DNA profile results and the performance of the process. Several statistical methods have been introduced in the past to aid interpretation (273, 277, 278) but the models developed are primarily based on STR results typically derived from an optimal DNA process. The Gill model (276) based on a Bayes Net specifically focuses on predictive scenarios that allow for data input for less than optimal DNA processing and allows input from conditions involving low copy number DNA amplification, minor contributions and highly variable stutter with significant heterozygote imbalance. The overall concept of this innovative approach was to derive a formal statistical model with a computer application called PCRSIM that enables test data sets to be developed from allele frequency databases and that takes into account the most difficult DNA processing parameters. In theory, this should enable the faster validation of new methods and better optimization of multiple DNA processing parameters. How this approach will be incorporated into current forensic research and development with actual test scenarios across different laboratory systems should prove to be both an exciting challenge as well as providing a new way of evaluating future techniques and critiquing past experiences to achieve better optimization.


Biological Evidence and Forensic DNA Profiling

The availability of computer software to carry out systematic mathematical analysis using available STR profile characteristics (peak heights, heterozygous ratios, presence and absence of alleles etc.) is expected to reduce the time required for DNA profile interpretation and improve its consistency. Studies that have been presented in recent years involve the interpretation of mixtures based on quantitative allele peak data and recommendations are based on observation and experience from operational casework. A group at Forensic Science Services (FSS) have developed PENDULUM (273) which is marketed as i-Stream, part of their I3 software package which is based on the previous guidelines established by Clayton (280). Perlin and Szabady (278) have reported on the linear mixture analysis method (LMA) in actual forensic scenarios depending on what is known about the genotype of the potential contributors. A probabilistic expert system developed in conjunction with quantitative peak data was also discussed by Mortera (282) that also takes into account the number of known genotype donors. Wang et al. (283) have also developed a framework for interpretation (Leastsquares Devolution-LSD) that is guided by the least square analysis of results of the quantitative peak data of either peak area or height of the STR profile results and a set of heuristic rules for best fit mass proportion ratios of genotype contributors. All of the methods make assumptions. For example, the LSD method (283) assumes correct allele calls, no artifacts (no stutter or pull up) and no peak overloading or saturation, and all peak proportionality is based on alleles amplified to the same consistency. The natural evolution of interpretation software development is validation and concordance studies performed by end users of the software. Ryan and coworkers (284) have developed and used a concordance analysis system (CompareCallsSM) to specifically compare STR databases in order to assist in meeting the US Department of Justice’s (CODIS - Combined DNA Index System) public compliance for “100% technical review” of vendor generated STR data. CompareCallsSM was applied to 290,676 CODIS STR markers generated from unreviewed data from Genotyper (Applied Biosystems, Foster City, CA) with human-reviewed data from SurelockIDSM (Myriad Genetics Laboratories, Salt Lake City, UT). The automated allele concordance system simplified the comparison and flagged any potential questionable allele calls demonstrating an efficient means to review high-quality data for CODIS. The validation conducted by the New York State Convicted Offender DNA Databank Group (285) was the first US laboratory validation of TrueAllele® and clearly demonstrated that human intervention and expert review was only required for low-quality STR data. Consequently, laboratories engaged in adopting some form of artificial intelligence or software- driven guidelines will need to assess the best approach based on their specific needs and the quality of the data sets produced in their own laboratory. This will involve a benchmark set of acceptable assumptions. At the very least, software assistance could be used as an evaluation tool for casework, with a level of objectivity based on mathematics and accumulated simulations from large data sets to achieve some form of consistency in interpretation and the potential for an unbiased review. How this will unfold in years to come will depend on rigorous evaluations and acceptance within international working groups. It is interesting 633

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to note that the sub-committee SWGDAM (July 2007 Quantico VI) has recently recommended that forensic interpretation software could be used for the standalone interpretation of STR profiles from single source donors such as samples collected for criminal offender databases but was not acceptable at this time for samples of unknown origin that could be composed of multiple donors and the use of these types of software systems should be used only as a data evaluation tool. Unrelated to statistical interpretation of STR profiles but equally important is the development and documentation of validation studies conducted on forensic DNA processes. Although larger laboratories may have the benefit of specifically trained project managers, the average forensic laboratory must assign this responsibility to select operational scientists. Recently, Applied Biosystems has introduced a software package (VALID) which is specifically designed to assist in validation studies required by SWGDAM. The software is based on a traditional project management approach which allows the end-user to design, implement, document/archive all findings and data and write up the final study results. This software should reduce the amount of time and labour required to validate new technologies. The software was recently introduced and there are no current reports on its functionality in an operational laboratory at this time. Further interpretation challenges in STR DNA casework have also been addressed in potential laboratory contamination simulations by Gill and Kirkham (275). In particular the issue of negative controls for monitoring tube-specific contamination was determined to be an inadequate assurance that an associated batch of extracted casework material is contaminant-free. The authors discuss in detail the different types of contamination, detection and the potential impact by empirical review of interpretation guidelines for STR analysis and real data sets taken from the operations of the Forensic Science Services. An estimation of expected contamination of false positive results can be established and mitigation of risk was discussed with respect to regular and low level DNA evidence and the use of expert systems to analyze negative controls. DNA in Mass Disasters and Mass Screening/Kinship Analysis Primarily due to tragic circumstances on a very large scale (9/11 World Trade Center Attack and 2004 Tsunami disaster in South East Asia), considerations over the processing and use of DNA evidence, biological collection, kinship comparisons and the overall logistics of processing large complex data sets have recently been a major endeavour of many forensic laboratories. Numerous detailed reference guides concerning all aspects of evidence collection and incident-specific mass disaster management or mass screening have been written. The principal rationale for forensic scientists engaged in DNA analysis following a mass disaster or large scale criminal investigation is to derive DNA evidence and affect individualization of biological material for missing persons and unsolved casework. This task is complex and challenging from a scientific as well as from an ethical perspective raising privacy and security issues. Budowle, Bieber and Eisenberg (295) have noted that law enforcement/and or public safety and health officials often have a primary responsibility for 634

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identifying human remains found at the scene so the missing individuals can be identified and returned to their families and loved ones. Although DNA has been used in the past to identify victims of aircraft or natural disasters, the large scale utility for developing reference databases and associating many separated remains or body parts has been unprecedented. These authors derive a set of general guidelines from a very logical step-by-step action plan that incorporates all aspects of sample collection (preservation, shipping and storage), documentation/tracking of samples, laboratory facilities, quality assurance practices and controls, work packages, laboratory processes and use of automation, bioinformatics, governance and advisory panels, education as well as communication messages, and privacy and security issues. A particularly relevant comment made by the authors is the reminder that any information that supports a correct identification is invaluable, which is sometimes forgotten by specialists who are primarily trained in a single forensic discipline. Alonso et al (296) have also identified the main challenges of identifying victims in several large incidents such as the South Asian Tsunami disaster, Madrid bombings of March 11, 2004 and an aircraft accident. A practical description of the logistics and management of an incident are noted in an expanded discussion on database searching and concordance kinship analysis with respect to match significance and the need for interpretation criteria for biostatistical evaluation of joint autosomal and haploid DNA data. The DNA Commission of the ISFG published a set of 12 recommendations which cover in detail the main considerations for forensic genetics and mass victim identification (297). The US Department of Justice also published a mass fatality incident guideline for forensic identification which is written from the perspective of a first responder and was co-authored by numerous experts specifically experienced in mass disasters (298). Although many presentations at professional conferences have been made on the forensic work involved in the 9/11 World Trade Center Attack, publications have only recently become available, with undoubtedly many more to come. The lessons learned from such a tragic event will have a major impact on all future responses to man-made or natural tragedies. To date, three articles stand out. The US Department of Justice Lessons Learned from the 9/11: DNA Identification in Mass Fatality Incident is written directly from the experience of those involved (279). The information is factual and covers the scope from before the incident to the completion of the project, captured in 14 chapters with major points highlighted in bullet fashion. Key to future success is the lessons learned which this publication highlights with real data, practical comparisons such as types of samples collected from the World Trade Center Response and the resulting profiles derived from each type of sample. It is important to note that this report builds from past experience and publications (298) to derive a scalable response and disaster planning guide, culminating in the actual approach formulated and implemented during the aftermath of the World Trade Center Attack. It is anticipated that a similar guide may evolve from the South Asian Tsunami disaster with additional lessons associated on an even larger scale with respect to numbers of victims and countries involved.


Biological Evidence and Forensic DNA Profiling

Significant DNA bioinformatics and sample continuity challenges occurred with victim identification of the World Trade Center terrorist attack. To mitigate the risk associated with rapid and continuous software development throughout the life of this large complex identification task or initiative, three different software packages were used (299). Early reports by Cash and coworkers (299) describe the challenges facing the development of the Mass Fatality Identification System (MFYSis) during the time the identifications were being made. STRs, mtDNA, miniSTRs and SNPs were all used to assist in the identification and software crosscomparison tools did not exist prior to their immediate need. Large scale likelihood cluster probability estimates were produced by Brenner (300) using DNAView, a specialized software that assisted in the identification of the victims. Leclair et al. in a recent report (301) describe the continuity cross-checks, sample documentation and large scale genotyping kinship analysis challenges imposed by the thousands of samples processed. Leclair et al. also describe in detail the logic behind management of kinship relationships through detailed sample tracking and frequent comparisons made during the course of the investigation. The large numbers of samples demonstrated a real concern regarding the discrimination of the data sets as aptly demonstrated by a 13 STR loci profile making a fortuitous trio match involving non-related individuals amongst the victims. The large scale of the identification task which involved significant numbers of comparisons clearly presents the issue of having sufficient numbers of STR loci to reduce the risk of identification errors and also confirmed the usefulness of rapid screening using less discriminating marker sets such as mtDNA and Y-STRs. These DNA analytical techniques have specific characteristics useful to an investigation such as sensitivity or the availability of reference samples from blood relatives. At the time of the terrorist attack on the World Trade Center, there was no infrastructure for rapid and effective victim identification in large mass disasters. One of the key strategies developed by the US National Institute of Justice for the identification project was the formation of a specialized group of scientific and medical experts called the Kinship and Data Analysis Panel (KADAP- 123). This group played an advisory role for all the DNA identification efforts (123). Experts in forensics, bioinformatics, molecular and medical statistics and population genetics recognized the “open” fatality list of an estimated 3,000 victims which was in marked contrast to a “closed” or “fixed” number of victims that would have an access to a specific area where the disaster occurred (e.g. passenger manifest on a specific aircraft). The Science article summarized the use of STRs, followed by mtDNA and miniSTRs and SNP technologies. The rationale regarding the minimum random match probability is briefly discussed along with issues regarding software and collection strategies (~ 1/6 of the initial reference data sets had to be re-sampled due to poorly thought out design parameters and lack of assistance). Considering that 52,000 STR, 44,000 mtDNA and 17,000 SNPs were developed more than 850 of the 1,594 victim identifications established for the 2,749 victims were made by DNA alone. In spite of the intense heat and significant co-mingling of the human remains, STRs proved to be the key protocol followed by miniSTRs and SNPs. No direct mtDNA-based identifications were acknowledged. There is little doubt that better preparedness will enhance the rapid and effective identification of future victims of future incidents.


Biological Evidence and Forensic DNA Profiling

Although the direct comparison of DNA profiles from known individuals to crime scenes is the most common use of forensic analysis, indirect analyses using the DNA from biological relatives are often used for humanitarian identification. In the past few years, the Forensic Science Services and other police investigations (302) have offered moderate matches or less stringent comparisons between potential relatives and DNA profiles developed from evidence. This has also led to mass screenings of potential candidate volunteers for similar DNA profiles that could suggest a close relative was involved with a case (124, 304, 303). Simulation studies have indicated that kinship analysis would reveal genetic similarities and provide an invaluable tool for detecting potential suspects who are parents, children or siblings of persons whose profiles are found in national forensic databases. This raises compelling questions about the rights of the individual with respect to security and individual privacy. Bieber et al (124) highlight the improved match rate as a result of familial searching (estimated from the CODIS database, the match rate would increase by 40 %). In addition, the issues and assumptions involving kinship matching from simulations are discussed as well as specific questions about genetic surveillance and the shift in interest from an individual to a family unit. North Americans concerned over civil liberties and kinship searching of forensic databases have been very vocal and presented in a number of media accounts. A detailed and informative discussion regarding the practical use of and ethical concerns regarding missing persons DNA registries, kinship matching and mass screening for casework was summarized in a special project and conference hosted by the American Society of Law, Medicine and Ethics (304). A symposium collection of 25 key articles on how to treat DNA forensic information by leading experts in the fields of science, ethics and law represents the most informative single publication on this topic and sets the foundation for all future discussions regarding society’s drift towards genetic surveillance and the individual’s rights to privacy and security. Budowle (295) discussed in detail sample collection, particularly at the scene of an incident and family reference topics as well as considerations over best process techniques initially starting with STR analysis followed by miniSTRs or SNP-based technologies where warranted. The primary method of analysis will be the technology predominantly used in the forensic laboratory at the time of the mass disaster and routine standard operating procedures should be attempted first. Any new technology requires additional resources for evaluation and a laboratory engaged in a mass disaster response may not have the ability to assess the efficacy of the new technologies. In the end, the question of technology and the use of DNA must also be balanced with a careful consideration of the utility of familial searching and use of criminal as well as humanitarian DNA databases such that policy development takes into account the legal and ethical implications of privacy and security. New Technologies for DNA and Biology Evidence Screening For the past decade, the quest for faster and more efficient biology evidence processing has been focused primarily on DNA analysis. The advancements made in the micro fabrication field, developed as an offshoot of the electronics industry, have promised more sensitive detection of forensic DNA profiles in a shorter period of time and at a significantly reduced cost. A summary article published in 637

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1999 (305) on the miniaturization of chemical analysis and synthesis on microchips, reported the additional advantages of maximizing genetic information from smaller amounts of biological sample with minimal sample handling which would reduce the potential for contamination. In retrospect, it is interesting to note that many of the principal investigators in the 1999 article reported that progress had been good, but eight years later are still challenged by the quality and variety of crime scene samples and only recently started to publish encouraging reports on adapting the “lab-on-a-chip” (LOC) or micro-total analysis systems (µTAS) principles for forensic science needs. There is no doubt that significant advancements have been made in this field. However, compared to the larger and more lucrative economic incentives offered by the clinical diagnostic markets, forensic applications involving DNA, RNA or proteomics are often a secondary goal or an application that has not yet attracted the research and funding required making this technology fully functional for forensic science needs (317, 319, 312). Hair examiners and other trace experts have taught us over many years that one of the most powerful methods in forensic investigation is the visual analysis of a sample. Finding biological evidence, and in particular spermatozoa, from sexual assault samples is time-consuming, difficult to quantitate and is subjective, based on the expertise of the examiner. Recently Buel and coworkers (321) have begun preliminary studies to develop expert system software that can self-direct the stage of a microscope to scan and record potential hits for different cell types, in particular, female epithelial cells and male spermatozoa from slides differentially stained and prepared from sexual assault evidence. Although the system does not replace the forensic trace expert, faster quantitative measurement of the many features of the image could potentially assist in automating preliminary screening of sexual assault evidence to find candidate matches. This should enable the forensic analyst to rapidly confirm the majority of matches while allowing more time for the review of challenging evidential results. It is noted that automated identification and measurement of a variety of microscopic images has been carried out for many years in the clinical diagnostic field. Automated screening has been developed for yeast colony counting and classifying, cell micro array annotation, tumour cell quantitation, wound healing assays and tissue topology measurements (306). Some may consider that a more automated process for the rapid detection and quantitation of spermatozoa could be a potential stop-gap before automated extraction and separation can be accomplished by micromachine devices. However, it is important to remember that the visual identification of cell and tissue types has a long legal precedence that is long lasting and often requested by the investigator and expected by the courts. The potential to incorporate sample processing steps (DNA extraction, quantitation, amplification, separation and detection of labeled products) is the ultimate goal of many forensic investigators (312). A key decision in developing microdevices for any application, including those for forensic investigations, is choosing the overall design principle. There are currently two basic categories: 1) modular design - which uses different chips for specific steps in a process or for different sample preparations or 2) integrated design - a seamless step-wise process such that all DNA sample preparation and recovery processes as well as 638

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STR analysis would be carried out on a single chip. The integrated design principle promotes the concept of “sample-in-answers-out” capability (i.e. LOC, µTAS). To date a fully validated forensic chip based on either design principle is still remote, but several promising prototype chips that carry out some steps in the forensic process have been reported (307,308,309,310,313,317,320). Although some laboratories have reported separation of complex human DNA mixtures using high performance liquid chromatography (311), until recently this has not been successfully performed on a micromachine device. Bienvenue (307) and coworkers have reported microchip-based cell lysis and DNA extraction from sperm cells using glass micromachined slides containing silica beads and a fluorescent based monitoring system to follow the process. This lysis chip has the potential to integrate with another chip developed by the same laboratory (320) which can separate sperm and epithelial cells in mocked up sexual assault samples. Other investigators have concentrated on rapid detection of labeled fluorescent STR products using a variety of miniaturized electrophoresis and/or electrochemical separation processes to track and identify the size of amplified products. Goedecke (308) has used a 16-lane micromachined 10-15 cm glass micromachined device that enabled rapid single base resolution of amplified products using standard commercial STR amplification kits and linear polyacrylamide matrices. The compact “uni-block” nature of the device has excellent thermal/mechanical stability and is ideal for rapid sensitive detection of STR profiles developed from low copy DNA samples or from samples composed of multiple donors (308). The device is completely mobile and is not prone to vibration interference, but it is large and does not fit the concept of a micromachine. A commercial version of the device called the GeneBench (312) conducts 16 tests simultaneously and can be scaled up to 96 and potentially 384 well formats. In contrast, the Mathies group (309) has developed a 96-channel micro fluidic device that has integrated amplification and detection. Amplification is performed in a 160-nL chamber and the labeled STR fragments are separated in 7-cm long microcapillary array electrophoresis (µCAE) wells etched on a circular 15 cm wafer containing 96 wells in prototype versions of the same device. STR fragments labeled with commercially available kits, have been evaluated and the researchers report excellent resolution and the ability to detect simple two donor mixtures. Yeung and coworkers (310) originally reported full STR multiplex detection with 0.17 ng of amplified target DNA and minor allele mixture detection in 3:1 female to male mixtures. A year later with slight modifications to their procedures, Liu reported (309) similar results but with a resolution improvement that enabled detection of minor STR profiles amplified from 10:1 female to male, DNA mixtures. Although sensitivity was excellent, it was noted that below 100 pg or 33 copies of DNA, the stochastic effects of low target thresholds affected reproducibility. This finding is not surprising, and is similar to results obtained from current STR mixture analysis using conventional STR protocols. A series of non-probative casework samples were evaluated with the device and found to be concordant with results developed with conventional STR amplification and electrophoresis fluorescent based detection systems (228, 309). 639

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Microarrays from commercial manufacturers such as Affymetrics (Santa Clara, CA, USA) may be the first exposure many forensic laboratories have to this new technology (317). The GeneChip Human Mitochondrial Resequencing Array contains 5 arrays, and has a sequence capacity of 16kb and delivers a complete sequence in 48 hours. The advent of miniaturization and refinements for rapid HVI and HVII sequencing and SNP variant detection in multiple redundant processing steps on a single chip is presumably within current manufacturing capabilities. The 2100 Bioanalyzer (Agilent, Santa Clara, CA, USA) microchip electrophoresis systems were evaluated by Alonso and coworkers (316). Forensic and ancient DNA samples were interrogated with assays developed for detection of the mitochondrial hyper variable regions as well as cytochrome b and 16S ribosomal genes. The Alonso laboratory reported that they achieved fast and sensitive detection of human and animal DNA amplified fragments derived from hair and bone samples and amplicon sizes down to 100 bp. The combination of rapid analysis and sensitive detection for smaller sized STR fragments proved to be an excellent quantitative tool and was used to validate different DNA extraction strategies. The prospect of faster DNA analysis for forensic samples and a more rapid biological detection process may receive significant support from work ongoing in microbial forensics (315, 318). There is little doubt that recent terrorist events have acted as a catalyst to derive rapid detection processes for potential bioweapons. Initial work to collect, isolate and decontaminate forensic evidence has been described (322). Investigations conducted in specialized laboratories designed to isolate and protect the investigator as well as the public, will undoubtedly create special conditions of use. However, as described by Ecker and coworkers (314), mass spectrometry derived composition signatures from PCR amplified regions of pathogen genomes can be automated to rapidly identify organisms and potential subspecies of the same bacteria and virus that contain engineered DNA components. This approach plus its miniaturization using micromachined devices for detection and identification for microbial forensics will create new expertise and experiences which benefit the forensic community as a whole. Summary The past three years have demonstrated progress in the field of forensic DNA typing and, most recently, advances in enhanced biology evidence screening protocols. If the probative biological evidence can be found, it should be possible to integrate the laboratory process to ensure the best use of the evidence in subsequent DNA analysis. The capacity to process more samples using automated procedures should enable DNA backlogs to be diminished and provide information in real-time for complex and high profile casework. With automated rapid processing of significant amounts of evidence, the complexity of the data and interpretation of results has grown exponentially. Fortunately, expert systems and highly refined documentation of results should provide some assistance in the final interpretation of the forensic biological evidence. Validity and reliability of new technology or equipment rests significantly with peer review and collaborative research evaluations as noted in the numerous 640

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studies documented over the past three years. In many ways, DNA analysis is pushing the limits of detection and the ability to derive more probative data from smaller or more degraded samples must be balanced with the realistic interpretation of the information. As forensic scientists, we are also balancing significant investigative information such as biological characteristics and physical markers or kinship family relationships with an individual’s rights for privacy and security of personal information. For the first time, the heightened expectations promised by micromachine technology has been partially realized with the demonstration of cell separation and cell lysis, STR amplification and detection of fluorescent tagged alleles from non-probative casework samples. As always, there will be more advances and future developments to enhance our abilities to process biological evidence, but the last three years has been very exciting with a promise of much more to come. Acknowledgments: We thank Louise Richer and Nerine Waldron for assistance in preparation of this manuscript and Brian Yamashita, Chantal Frégeau, Ted Lukaszewski, Hiron Poon and Barbara Oattes for their many helpful comments. We are also indebted to the many laboratories who participated in our biology evidence survey. References 1.

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