Applications of Time-of-Flight and Orbitrap Mass Spectrometry in Environmental, Food, Doping, and Forensic Analysis [1st Edition] 9780444635730, 9780444635723

Table of contents :
Content:
Applications of Time-of-Flight and Orbitrap Mass Spectrometry in Environmental, Food, Doping, and Forensic AnalysisPage i
Advisory BoardPage ii
Front MatterPage iii
CopyrightPage iv
Contributors to Volume 71Pages xiii-xv
Series Editor's PrefacePage xviiD. Barceló
PrefacePages xix-xxiSandra Pérez, Peter Eichhorn, Dami`Barceló
Chapter 1 - Orbitrap Mass Spectrometry: Evolution and ApplicabilityOriginal Research ArticlePages 3-18C.P.B. Martins, M. Bromirski, M.C. Prieto Conaway, A.A. Makarov
Chapter 2 - Advances in Time-of-Flight Mass SpectrometryOriginal Research ArticlePages 19-49J.C. Fjeldsted
Chapter 3 - Ambient Ionisation–High-Resolution Mass Spectrometry: Environmental, Food, Forensic and Doping analysisOriginal Research ArticlePages 51-88R. Seró, Ó. Núñez, E. Moyano
Chapter 4 - High-Resolution Mass Spectrometry in Doping ControlOriginal Research ArticlePages 91-117G. Balcells, O.J. Pozo, R. Ventura
Chapter 5 - Application of LC-Time-of-Flight and Orbitrap-MS/MS for Pesticide Residues in Fruits and VegetablesOriginal Research ArticlePages 119-154Ł. Rajski, M.M. Gómez-Ramos, A.R. Fernández-Alba
Chapter 6 - Identification of Sildenafil Designer Analogues Found in Dietary SupplementsOriginal Research ArticlePages 155-197X. Ge, C.-L. Kee, Y. Zeng, M.-Y. Low
Chapter 7 - High-Resolution Mass Spectrometry in Metabolite IdentificationOriginal Research ArticlePages 199-229M.K. Ladumor, S. Tiwari, A. Patil, K. Bhavsar, S. Jhajra, B. Prasad, S. Singh
Chapter 8 - LC-TOF-MS for the Identification of Environmental Metabolites and Degradation ProductsOriginal Research ArticlePages 231-261I. Ferrer, J.H. Writer, O.S. Keen, Y. Lester, J.A. Padilla-Sánchez, C. Fernández-Ramos, E.M. Thurman
Chapter 9 - Application of Orbitrap Mass Spectrometry for the Identification of Transformation Products of Trace Organic Contaminants Formed in the EnvironmentOriginal Research ArticlePages 263-282C. Prasse, T.A. Ternes
Chapter 10 - High-Resolution Mass Spectrometry Identification of Micropollutants Transformation Products Produced During Water Disinfection With Chlorine and Related ChemicalsOriginal Research ArticlePages 283-334I. González-Mariño, I. Carpinteiro, R. Rodil, I. Rodríguez, J.B. Quintana
Chapter 11 - Discovery of New Emerging DBPs by High-Resolution Mass SpectrometryOriginal Research ArticlePages 335-356S.D. Richardson, C. Postigo
Chapter 12 - Suspect Screening of Pharmaceuticals and Related Bioactive Compounds, Their Metabolites and Their Transformation Products in the Aquatic Environment, Biota and Humans Using LC-HR-MS TechniquesOriginal Research ArticlePages 357-378J. Aceña, N. Heuett, P. Gardinali, S. Pérez
Chapter 13 - Nontarget Analysis of Environmental Samples Based on Liquid Chromatography Coupled to High Resolution Mass Spectrometry (LC-HRMS)Original Research ArticlePages 381-403P. Gago-Ferrero, E.L. Schymanski, J. Hollender, N.S. Thomaidis
Chapter 14 - Nontargeted Analysis of Persistent Organic Pollutants by Mass Spectrometry and GC×GCOriginal Research ArticlePages 405-431X. Ortiz-Almirall, M. Pena-Abaurrea, K.J. Jobst, E.J. Reiner
Chapter 15 - High-Resolution Mass Spectrometry in the Effect-Directed Analysis of Water ResourcesOriginal Research ArticlePages 433-457M. Krauss
Chapter 16 - Conclusions and Future DirectionsOriginal Research ArticlePages 461-480P. Eichhorn, S. Pérez
IndexPages 481-501

Citation preview

Comprehensive Analytical Chemistry Volume 71

Applications of Time-of-Flight and Orbitrap Mass Spectrometry in Environmental, Food, Doping, and Forensic Analysis

Advisory Board Joseph A. Caruso University of Cincinnati, Cincinnati, OH, USA Hendrik Emons Joint Research Centre, Geel, Belgium Gary Hieftje Indiana University, Bloomington, IN, USA Kiyokatsu Jinno Toyohashi University of Technology, Toyohashi, Japan Uwe Karst University of Mu¨nster, Mu¨nster, Germany Gyro¨gy Marko-Varga AstraZeneca, Lund, Sweden Janusz Pawliszyn University of Waterloo, Waterloo, Ont., Canada Susan Richardson US Environmental Protection Agency, Athens, GA, USA

Comprehensive Analytical Chemistry Volume 71

Applications of Time-ofFlight and Orbitrap Mass Spectrometry in Environmental, Food, Doping, and Forensic Analysis Edited by

Sandra Pe´rez

Institute of Environmental Assessment and Water Research e Spanish National Research Council (IDAEA-CSIC), Barcelona, Spain

Peter Eichhorn

Institute of Environmental Assessment and Water Research e Spanish National Research Council (IDAEA-CSIC), Barcelona, Spain

Damia` Barcelo´

Institute of Environmental Assessment and Water Research e Spanish National Research Council (IDAEA-CSIC), Barcelona, Spain

AMSTERDAM l BOSTON l HEIDELBERG l LONDON NEW YORK l OXFORD l PARIS l SAN DIEGO SAN FRANCISCO l SINGAPORE l SYDNEY l TOKYO

Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, USA Copyright © 2016 Elsevier B.V. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. ISBN: 978-0-444-63572-3 ISSN: 0166-526X For information on all Elsevier publications visit our website at https://www.elsevier.com

Publisher: Zoe Kruze Acquisition Editor: Poppy Garaway Editorial Project Manager: Shellie Bryant Production Project Manager: Radhakrishnan Lakshmanan Designer: Alan Studholme Typeset by TNQ Books and Journals

Contributors to Volume 71 J. Acen˜a, Institute of Environmental Assessment and Water Research e Spanish National Research Council (IDAEA-CSIC), Barcelona, Spain G. Balcells, Hospital del Mar Medical Research Institute (IMIM); Pompeu Fabra University, Barcelona, Spain K. Bhavsar, National Institute of Pharmaceutical Education and Research (NIPER), Punjab, India M. Bromirski, Thermo Fisher Scientific, Bremen, Germany I. Carpinteiro, University of Santiago de Compostela, Santiago de Compostela, Spain; Universite´ de Bordeaux-CNRS, Talence, France P. Eichhorn, Institute of Environmental Assessment and Water Research e Spanish National Research Council (IDAEA-CSIC), Barcelona, Spain A.R. Ferna´ndez-Alba, University of Almerı´a, Almerı´a, Spain C. Ferna´ndez-Ramos, Charles University, Hradec Kra´love´, Czech Republic I. Ferrer, University of Colorado, Boulder, CO, United States J.C. Fjeldsted, Agilent Technologies, Santa Clara, CA, United States P. Gago-Ferrero, National and Kapodistrian University of Athens, Athens, Greece P. Gardinali, Florida International University, Miami, FL, United States X. Ge, Health Sciences Authority, Singapore M.M. Go´mez-Ramos, University of Almerı´a, Almerı´a, Spain I. Gonza´lez-Marin˜o, University of Santiago de Compostela, Santiago de Compostela, Spain; IRCCS d Istituto di Ricerche Farmacologiche “Mario Negri”, Milan, Italy N. Heuett, Florida International University, Miami, FL, United States J. Hollender, Eawag: Swiss Federal Institute of Aquatic Science and Technology, Du¨bendorf, Switzerland; Institute of Biogeochemistry and Pollutant Dynamics, Zu¨rich, Switzerland S. Jhajra, Johnson & Johnson Private Limited, Mumbai, India K.J. Jobst, Ontario Ministry of the Environment and Climate Change, Etobicoke, ON, Canada; McMaster University, Hamilton, ON, Canada C.-L. Kee, Health Sciences Authority, Singapore O.S. Keen, University of North Carolina, Charlotte, NC, United States M. Krauss, Helmholtz-Centre for Environmental Research e UFZ, Leipzig, Germany xiii

xiv Contributors to Volume 71 M.K. Ladumor, National Institute of Pharmaceutical Education and Research (NIPER), Punjab, India Y. Lester, Tel Aviv University, Tel Aviv, Israel M.-Y. Low, Health Sciences Authority, Singapore A.A. Makarov, Thermo Fisher Scientific, Bremen, Germany C.P.B. Martins, Thermo Fisher Scientific, San Jose, CA, United States E. Moyano, University of Barcelona, Barcelona, Spain ´ . Nu´n˜ez, University of Barcelona; Serra Hu´nter Program, Generalitat de Catalunya, O Barcelona, Spain X. Ortiz-Almirall, Ontario Ministry of the Environment and Climate Change, Etobicoke, ON, Canada J.A. Padilla-Sa´nchez, University of Almerı´a, Almerı´a, Spain A. Patil, National Institute of Pharmaceutical Education and Research (NIPER), Punjab, India M. Pena-Abaurrea, Cepsa Research Center, Madrid, Spain S. Pe´rez, Institute of Environmental Assessment and Water Research e Spanish National Research Council (IDAEA-CSIC), Barcelona, Spain C. Postigo, Institute for Environmental Assessment and Water Research e Spanish National Research Council (IDAEA-CSIC), Barcelona, Spain O.J. Pozo, Hospital del Mar Medical Research Institute (IMIM), Barcelona, Spain B. Prasad, University of Washington, Seattle, WA, United States C. Prasse, UC Berkeley, Berkeley CA, United States M.C. Prieto Conaway, Thermo Fisher Scientific, San Jose, CA, United States J.B. Quintana, University of Santiago de Compostela, Santiago de Compostela, Spain Ł. Rajski, University of Almerı´a, Almerı´a, Spain E.J. Reiner, Ontario Ministry of the Environment and Climate Change, Etobicoke, ON, Canada; University of Toronto, Toronto, ON, Canada S.D. Richardson, University of South Carolina, Columbia, SC, United States R. Rodil, University of Santiago de Compostela, Santiago de Compostela, Spain I. Rodrı´guez, University of Santiago de Compostela, Santiago de Compostela, Spain E.L. Schymanski, Eawag: Swiss Federal Institute of Aquatic Science and Technology, Du¨bendorf, Switzerland R. Sero´, University of Barcelona, Barcelona, Spain S. Singh, National Institute of Pharmaceutical Education and Research (NIPER), Punjab, India T.A. Ternes, Bundesanstalt fu¨r Gewa¨sserkunde (BfG), Koblenz, Germany N.S. Thomaidis, National and Kapodistrian University of Athens, Athens, Greece

Contributors to Volume 71 xv

E.M. Thurman, University of Colorado, Boulder, CO, United States S. Tiwari, National Institute of Pharmaceutical Education and Research (NIPER), Punjab, India R. Ventura, Hospital del Mar Medical Research Institute (IMIM); Pompeu Fabra University, Barcelona, Spain J.H. Writer, University of Colorado, Boulder, CO, United States Y. Zeng, Health Sciences Authority, Singapore

Series Editor’s Preface I am glad to introduce this new volume on Applications of TOF and Orbitrap Mass Spectrometry in Environmental, Food, Doping and Forensic Analysis edited by Sandra Pe´rez, Peter Eichhorn and myself. The reason for having such a book in the Comprehensive Analytical Chemistry series is quite obvious: I was able to convince both co-editors to do it. I should say it was not so difficult to convince Sandra and Peter since both they are old friends of mine since mid1990s. In addition Sandra, a former PhD student, did a postdoctoral stay at the University of Buffalo, and recently she got a permanent job in my research group. This CAC book can be considered complementary to other two related books in the CAC series: Advanced Techniques in Gas ChromatographyeMass Spectrometry (GC-MS-MS and GC-TOF MS) for Environmental Chemistry (volume 61), and TOF-MS in Food and Environmental Analysis (volume 58). This book, mainly containing liquid chromatographyebased approaches combined with high-resolution MS, contains 16 chapters and it is organized in three sections: (1) Instrumentation with three chapters describing the evolution and advances of TOF and Orbitrap; (2) Target Analysis with nine chapters covering a comprehensive variety of application in environmental, food, doping and forensic analysis; and (3) Nontarget Analysis applications mainly in the environmental field. That being said, with the publication of this new title the CAC series offers a unique list of books on organic mass spectrometry that will be very helpful to the Analytical Chemistry community. The book can be used as an academic text and as reference book for those working in chemical analytical laboratories who want to learn more about today’s most widely used high-resolution MS systems: time-of-flight and Orbitrap. Finally I would like to thank to both co-editors again and to all the authors of this book, well-known experts, for their time and efforts in preparing this excellent and useful book on applications of TOF and Orbitrap MS techniques. Prof. D. Barcelo´ Barcelona, Spain, 21 March 2016

xvii

Preface There is little doubt, if any, that the commercial availability of powerful and cost-efficient instrumentation in conjunction with the development of userfriendly data acquisition and processing tools have been decisive factors in the successful implementation of high-resolution mass spectrometry (HR-MS) in highly diverse fields of application. Although the use of HR-MS techniques in small-molecule analysis has been around for quite some time, with prominent examples being magnetic sector instruments in academic settings at an early stage and later on time-of-flight (ToF) MS platforms used in the pharmaceutical industry for drug metabolite identification, many routine laboratories have nowadays recognised the potential, and are actually taking advantage of the power of HR-MS not only for qualitative analysis, but also increasingly for quantitative measurement of organic trace components with its high demands on instrumental sensitivity, selectivity and robustness. In fact, all of the major manufacturers with a solid history in developing and producing low-resolution MS instrumentation based on quadrupole or ion-trap technology for ion analysis and detection now offer a comprehensive portfolio of (hybrid) HRMS instruments to provide solutions to their customers for even the most complex of analytical tasks. And with the introduction of the first commercial Orbitrap mass analyser in 2005 and its subsequent triumphal procession, manufacturers of ToF-based HR-MS instruments took up the challenge of coming up with innovative solutions to defend, and ideally expand their market share. With the ever-growing popularity of HR-MS techniques and the continuous technological development in mind, in this book we set out to provide a snapshot on the current state-of-the-art in HR-MS analysis of small organic molecules, to describe workflows in analytical laboratories dealing with the detection and characterisation of environmental pollutants, food contaminants and doping agents in biological samples, and to identify the strengths and limitations of hardware and software solutions available to the HR-MS user community. To this end, we invited experts from academic institutions, public research organisations, and industry as well as instrument manufacturers to share their experience and views on their specific area of expertise. We feel confident that the selection of contributions in this book e ranging from broad overviews on technical developments or the various MS acquisition modes suitable for quantitative analysis down to the assignment of fragment ions for

xix

xx Preface

structure elucidation of metabolites e will allow the reader to gain a thorough impression on the very many areas of application of HR-MS in small-molecule analysis. As in our view HR-MS coupled to liquid chromatographic (LC) separation has experienced in recent years by far more important developments than those witnessed in hyphenation of gas chromatography (GC) to HR-MS, the majority of chapters have their focus on LC-MS applications for compounds of moderate or high polarity. Nonetheless, readers with a stronger interest in GC-HR-MS will find chapters dealing partially or even exclusively with GC-based techniques. This book is divided into three parts. The three chapters composing the first part ‘Instrumentation’ provide a concise overview of the history and fundamentals of Orbitrap MS and ToFMS. The two chapters dedicated to each principle of ion analysis are written by expert scientists from instrument vendors. They both provide a detailed yet unbiased account of the technological advances, current challenges and future directions in further development. The third chapter constituting the first part describes in a very comprehensive manner the hyphenation of the various ambient ionisation techniques with HR-MS in a vast field of applications covered in this book. The second part on ‘Target Analysis, Identification, and Suspect Screening’ illustrates in the first two chapters the possibilities of HR-MS in the detection of doping agents in biological samples of human origin and the determination of pesticide residues in fruits and vegetables. In the former the authors highlight the invaluable power of HR-MS full-scan acquisitions for retrospective analysis of novel banned substances. The two following chapters provide a useful guide on the acquisition modes that can be used in (drug) metabolite identification and give an example on how HR-MS analysis with multiplestage fragmentation leads to the successful identification of designer drugs present in herbal supplements. The structural elucidation of environmental transformation products by either Orbitrap or ToF-based LC-MS platforms is the topic of two further chapters in which the authors present their approaches towards proposing and confirming structure identities. What follows are two detailed literature reviews on the application of HR-MS for the identification of transformation products formed from organic micropollutants during the process of water disinfection with chlorine or related agents. Although LC separations with HR-MS detection are the key technique for studying most of the degradation pathways, there is a clear window of opportunity for GC-HRMS wherever sufficiently volatile species are formed. In the last chapter of this part of the book, a brief introduction to ‘suspect screening’ is provided and, by way of example, the workflow of this relatively new approach in environmental analysis is described. The purpose of the third part of this book is to portray the state-of-thescience in the ‘nontarget screening’ of organic compounds of environmental relevance. The three contributions in this last part use different approaches for

Preface

xxi

the identification of truly unknowns: the first one capitalises on a combination of LC-HR-MS data with in silico tools for the prediction of MS fragmentation and LC retention behaviour; the second one targets halogen-bearing persistent organic pollutants that are resolved by two-dimensional GC-GC followed by various data analysis tools for tracking down homologue series; and the third one aims to identify those compounds in environmental water samples which are actually of toxicological relevance. After an iterative process of sample fractionation and assessment of biological effects, the ultimate goal of this approach is to identify key effectors. In the concluding chapter of this book the key aspects of each of the chapters are highlighted allowing the reader to get a quick overview of how environmental analysis, doping control, pesticide analysis in foodstuff and forensics have exploited the capabilities of HR-MS for the detection, quantification and identification of organic compounds. While stressing the undeniable strengths of accurate mass measurements, weaknesses, particularly with respect to the need for more efficient and automated data processing tools, are identified. This summary is thought to help instrument and software developers come up with innovative solutions which will pave the path for the continuous success of HR-MS analysis. Last but not least, we wish to express our gratitude to all of the authors who accepted our invitation to contribute to this exciting volume of the ‘Comprehensive Analytical Chemistry’ series. We deeply appreciate their major level of dedication shown in delivering their outstanding contributions in a timely manner. Without the efforts of all the authors, this book would never have materialised in its current form. Sandra Pe´rez, Peter Eichhorn, Damia` Barcelo´ Barcelona, April 2016

Chapter 1

Orbitrap Mass Spectrometry: Evolution and Applicability C.P.B. Martins,1, * M. Bromirski,2 M.C. Prieto Conaway1 and A.A. Makarov2 1

Thermo Fisher Scientific, San Jose, CA, United States; 2Thermo Fisher Scientific, Bremen, Germany *Corresponding author: E-mail: [email protected]

Chapter Outline 1. Introduction 2. Evolutionary Route of the Orbitrap Technology 3. Ion Source Capabilities Associated with Orbitrap Technology

3 4

4. Working Modes in Quantitative Analysis 5. Conclusion References

12 16 16

9

1. INTRODUCTION While mass spectrometry is rightfully considered as one of the most (if not the most) powerful methods of analysis in environmental, food, antidoping and forensic laboratories, its further expansion depends on its ability to keep up with analytical challenges, such as the growing variety of analytes and the increasing stringency on limits of detection and quantitation. Over the recent decade this ability was enabled by increasing speed of liquid and gas separations that in its turn has driven requirements on throughput and quality of analysis provided by mass spectrometry instrumentation. Developments addressing analytical challenges and increased performance have focused not only on ion sources, especially those employing an atmospheric-to-vacuum interface such as electrospray (ESI) and atmospheric pressure chemical ionisation (APCI), but also on the transition to the use of high-resolution mass spectrometry (HRMS). The latter trend started with

Comprehensive Analytical Chemistry, Vol. 71. http://dx.doi.org/10.1016/bs.coac.2016.01.001 Copyright © 2016 Elsevier B.V. All rights reserved.

3

4 SECTION j I Instrumentation

time-of-flight (TOF) instruments and has continued with the newest of mass spectrometric techniques: Orbitrap mass spectrometry. The combination of targeted and nontargeted analysis, increased selectivity with less sample preparation and compound optimisation, and retrospective analysis are crucial factors contributing to the increase interest in the use of HRMS coupled to liquid chromatography (LC). Ever since the introduction of commercial orthogonal acceleration-time-of-flight (oa-TOF) instruments in the mid-1990s, significant improvements have been made in order to produce a high-performance instrument with modest power requirements, size and most importantly, able to operate at reduced costs. Magnetic sector, TOF, Orbitrap, and Fourier transform ion cyclotron (FTICR) are viable options, but TOF and Orbitrap mass analysers are probably the most commonly used with LC or UHPLC systems. In general, TOF instruments show a mass resolving power of approximately 10,000e60,000 FWHM (full width at half maximum) with a mass measurement accuracy of 1e5 parts per million (ppm), while the mass resolving power of the latest Orbitrap instrument can reach up to 450,000 FWHM at m/z 200 with