Persistent Organic Chemicals in the Environment - Status and Trends in the Pacific Basin Countries I Contamination Status 9780841231979, 0841231974, 9780841231993, 0841231990, 9780841231962, 9780841231986

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Content: V. 1. Contamination status --
v. 2. Temporal trends

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Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.fw001

Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I Contamination Status

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.fw001 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

ACS SYMPOSIUM SERIES 1243

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.fw001

Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I Contamination Status Bommanna G. Loganathan, Editor Murray State University, Murray, Kentucky

Jong Seong Khim, Editor Seoul National University, Seoul, Korea

Prasada Rao S. Kodavanti, Editor U.S. Environmental Protection Agency, Research Triangle Park, North Carolina

Shigeki Masunaga, Editor Yokohama National University, Yokohama, Japan Sponsored by the ACS Division of Environmental Chemistry, Inc.

American Chemical Society, Washington, DC Distributed in print by Oxford University Press

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.fw001

Library of Congress Cataloging-in-Publication Data Names: Loganathan, Bommanna G., editor. | American Chemical Society. Division of Environmental Chemistry. Title: Persistent organic chemicals in the environment : status and trends in the Pacific Basin countries / Bommanna G. Loganathan, Murray State University, Murray, Kentucky [and three others], editor ; sponsored by the ACS Division of Environmental Chemistry. Description: Washington, DC : American Chemical Society, [2016]- | Series: ACS symposium series ; 1243, 1244 | Includes bibliographical references and index. Contents: v. 1. Contamination status -- v. 2. Temporal trends Identifiers: LCCN 2016054891 (print) | LCCN 2016055072 (ebook) | ISBN 9780841231979 (v. 1) | ISBN 9780841231993 (v. 2) | ISBN 9780841231962 (v.1) (ebook) | ISBN 9780841231986 (v.2) (ebook) Subjects: LCSH: Organic compounds--Environmental aspects--Pacific Area. | Persistent pollutants--Pacific Area. Classification: LCC TD196.O73 P46 2016 (print) | LCC TD196.O73 (ebook) | DDC 628.5/2--dc23 LC record available at https://lccn.loc.gov/2016054891

The paper used in this publication meets the minimum requirements of American National Standard for Information Sciences—Permanence of Paper for Printed Library Materials, ANSI Z39.48n1984. Copyright © 2016 American Chemical Society Distributed in print by Oxford University Press All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Act is allowed for internal use only, provided that a per-chapter fee of $40.25 plus $0.75 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. Republication or reproduction for sale of pages in this book is permitted only under license from ACS. Direct these and other permission requests to ACS Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

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Foreword The ACS Symposium Series was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of the series is to publish timely, comprehensive books developed from the ACS sponsored symposia based on current scientific research. Occasionally, books are developed from symposia sponsored by other organizations when the topic is of keen interest to the chemistry audience. Before agreeing to publish a book, the proposed table of contents is reviewed for appropriate and comprehensive coverage and for interest to the audience. Some papers may be excluded to better focus the book; others may be added to provide comprehensiveness. When appropriate, overview or introductory chapters are added. Drafts of chapters are peer-reviewed prior to final acceptance or rejection, and manuscripts are prepared in camera-ready format. As a rule, only original research papers and original review papers are included in the volumes. Verbatim reproductions of previous published papers are not accepted.

ACS Books Department

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

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Preface Environmental pollution by man-made Persistent Organic Chemicals (POCs) has been a serious global issue for over half a century. Exposure to POCs may result in health effects, including, endocrine disruption leading to birth defects, intellectual disability, low testosterone, childhood obesity, autism and attention deficit hyperactivity disorder (ADHD). Therefore, POCs have been the subject of an intensive regional, national, and international efforts to limit the production, use, and disposal of these chemicals. Since POCs are ubiquitous and recalcitrant, and cause long-term effects on wildlife and humans, trend monitoring studies are valuable in making clear the behavior and fate of these compounds and to protect our environment and living resources. The Pacific Basin is a unique geographical region representing tropical, temperate and polar zones. This region is home to 2/3 of the world’s population and consists of rapidly growing economies (countries) and highly developed countries. Due to this diversity of climatic and socio-economic conditions, environment and biota in different countries in this basin have varying degrees of environmental contamination and effects on wildlife and humans. The Pacific Rim countries play a pivotal role in governing global POC contamination and resulting harmful health effects. Because articles on POCs and their effect on environment and health are published in a large number of different journals, it is useful to have a book that includes original papers and reviews on the latest advances by well-known scientists in the field, especially focusing on the countries in the Pacific Rim. The two volumes of this book satisfies this need. The two volumes are based on the successful symposium on “Status and Trends of Persistent Organic Chemicals in the Environment”. The symposium took place at PACIFICHEM 2015, International Chemical Congress of Pacific Basin Societies, December 15-20, 2015 in Honolulu, Hawaii. The symposium brought together an impressive group of leading experts in the field, covering a broad spectrum of expertise in contamination status and temporal trends of POCs from countries in the Pacific Rim. Eighteen platform presentations and nine posters were presented. The presentations created an exciting and dynamic forum for highlighting current contamination profiles and as well as future trends, which formed the foundation of this two-volume book. All of the symposium speakers were invited to submit chapters to this book. We were pleased that the majority contributed chapters. Other internationally respected researchers contributed additional chapters in order to strengthen the coverage of classical and emerging contaminant statuses and trends in the Pacific Rim countries. A total of 20 chapters are included in the two volumes of the book. Volume 1 focuses on contamination status including human exposure to POCs and Volume 2 focuses on the temporal trends and future perspectives. Topics covered in Volume 1 include an overview of POCs contamination status and trends in the Pacific Basin Countries (Chapter 1); human exposure to brominated flame

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retardants (Chapter 2); persistent toxic substances in Vietnam (Chapter 3); dietary exposure to a variety of organohalogen pollutants and heavy metals in Tokyo, Japan (Chapter 4) and Georgia, USA (Chapter 5); e-waste and associated environmental contamination in the Asia/Pacific Region (Chapter 6), including a case study on dioxin and furan exposure to e-waste workers in India (Chapter 7); POCs in sediments (Chapter 8), soil and atmosphere of South Korea (Chapter 9); and new research on sequestration and redistribution of emerging and classical persistent organic pollutants by polystyrene (Chapter 10). Topics covered in Volume 2 include lessons learned from three decades monitoring contaminants in Pacific Basin wildlife samples from the USA’s Marine Environmental Specimen Bank (Chapter 1); spatial and temporal trends of brominated flame retardants (Chapter 2), PCBs, pesticides, and dioxins/furans, in the environment and biota in the USA, Colombia (Chapter 3), China (Chapter 4), Korea (Chapter 5), and Japan (Chapter 6 and Chapter 7); emission of emerging pharmaceutical contaminants in the USA (Chapter 8) and Vietnam (Chapter 10); and possible application of bio-analytical assays in the biological impact assessment of persistent organic pollutants in Mangrove sediments in Southeast Asia with particular reference to Malaysia (Chapter 9). The collection of chapters in these volumes may serve as a reasonable representation of current and future trends of POCs in the Pacific Basin countries. It is hoped that the book can inspire students and researchers, as well as professionals, to facilitate the understanding of the environmental and biological behavior of these persistent chemicals and to help in the development of strategies and practices for protecting the global environment for future generations. We would like to express our gratitude to all of the authors who took time to prepare their manuscripts and to the many reviewers for their valuable time and expertise in the peer review process. Special thanks to Dr. Kevin Miller for his timely help in reviews and language corrections. Thanks are also due to the editorial team at ACS Books, particularly Bob Hauserman, Elizabeth Hernandez, Arlene Furman, and Aimee Greene for their efficient handling of manuscripts.

Bommanna G. Loganathan Department of Chemistry/Watershed Studies Institute, Murray State University Murray, Kentucky 42017, United States Jong Seong Khim School of Earth and Environmental Sciences, Seoul National University Seoul 08826, Republic of Korea Prasada Rao S. Kodavanti Neurotoxicology Branch, NHEERL/ORD, U.S. Environmental Protection Agency Research Triangle Park, North Carolina 27711, United States Shigeki Masunaga Faculty of Environment & Information Sciences, Yokohama National University Yokohama-240-8501, Japan x Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Chapter 1

Persistent Organic Chemicals in the Pacific Basin Countries: An Overview Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch001

Bommanna Loganathan* Department of Chemistry and Watershed Studies Institute, Murray State University, 1201 Jesse D. Jones Hall, Murray, Kentucky 42071, United States *E-mail: [email protected]

The Pacific Basin is a unique geographical region representing tropical, temperate and polar zones. This region is home to 2/3 of world’s population and consists of rapidly growing economies (countries) and highly developed countries. The Pacific Basin countries have had a history of use of persistent organic chemicals (POCs) at varying proportions during the last five decades. Due to diverse climatic and socio-economic conditions, the environment and biota in different countries in this basin have varying degrees of environmental contamination and effects on wildlife and humans. In this chapter, the historical background of POCs including, discovery, production, use, regulations/restrictions imposed, current status and possible future trends are reviewed especially focusing on the countries in the Pacific Rim.

© 2016 American Chemical Society Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch001

Introduction The first half of 20th century was the dawn of persistent organohalogen compounds. The chlorinated, brominated and fluorinated compounds were discovered and put to use during late 1800s and 1900s respectively. These compounds are being used in consumer products such as cosmetics, medicines, foods, flavors, toiletries, paints, plastics and other industrial products. Many of these compounds protected animals and humans from deadly diseases, improved agricultural food production to meet the demands of increasing population, and improved the overall quality of our lives. Although these man-made chemicals benefitted man-kind, they have led to environmental contamination and have changed the quality of the environment, thus adversely affecting the health of animals and humans worldwide (1). Because these compounds are inert and stable under extreme environmental conditions, they are useful in many industrial, agricultural and public health applications. The chemical stability and recalcitrant properties of organohalogens, coupled with their widespread use, has led to global environmental contamination and harmful effects on wildlife and humans (2). To protect human health and the environment, the Stockholm Convention was adopted and put into practice by the United Nations Environment Program (UNEP) and listed (in 1995) the following persistent organic chemicals that are needed to be addressed globally: aldrin, chlordane, dieldrin, endrin, heptachlor, hexachlorobenzene, mirex, toxaphene, polychlorinated biphenyls (PCBs), dichlorodiphenyl trichloroethane (DDT), dioxins, polychlorinated dibenzofurans, polycyclic aromatic hydrocarbons, and brominated flame retardants. This list was subsequently (since 2001) expanded and new persistent organic compounds added to the Stockholm Convention List are: chlordecone, α-HCH, β-HCH, γ-HCH (lindane), pentachlorobenzene (PeCB), tetrabromodiphenyl ether (tetra-BDE), perfluorooctanesulfonic acid (PFOS), endosulfans and hexabromocyclododecane (HBCD). The Pacific Basin is a unique geographical region representing tropical, temperate and polar zones. This region is home to 2/3 of world’s population and consists of highly developed countries such as the United States, Canada, Japan, Australia and New Zealand etc., and rapidly growing countries, including China, Vietnam Indonesia, Philippines etc. These countries have had a history of use of organohalogens at varying proportions during the last several decades. Due to diverse climatic and socio-economic conditions, the environment and biota in different countries in this basin have had varying degrees of environmental contamination and effects on wildlife and humans. Since these compounds are ubiquitous, are resistant to degradation and cause long-term health effects, most of these compounds are severely restricted/banned from production and use in many countries, including countries in the Pacific Rim, since 1970s. The organohalogen compounds are commonly known as persistent organic pollutants (POPs), persistent organic chemicals (POCs) and persistent, bioaccumulative and toxic chemicals (PBTs). This chapter provides an overview of these synthetic organohalogens including, discovery, production, use, regulations/restrictions imposed, current status and possible future trends especially focusing on the countries in the Pacific Rim. 2 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

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Early History and Timeline of POCs Figure 1 shows the summary of the timeline of persistent organic chemicals. The history of organochlorine pesticides began when Michael Faraday, who reported on June 16, 1825, the formation of “benzene hexachloride” by the reaction of benzene with chlorine in the presence of sunlight (3). Faraday did not recognize at that time that the product actually consisted of a mixture of isomers of hexachlorocyclohexane (HCH). The discovery of insecticidal properties was missed during the early 1930s. In 1942, the name lindane was assigned to the active γ-isomer after Van Linden, discoverer of the δ and γ-isomers (4). The use of HCH isomers, known as technical HCH started in 1943, and the global consumption increased dramatically (estimated 6 million metric tons/year) since then. Also, during this period, in 1939, Paul Muller discovered the insecticidal activity of DDT (dichlorodiphenyl-trichloroethane). DDT was extremely effective against crop and household pests. DDT was used during/after World War II to control mosquitoes that spread malaria, typhoid fever, and cholera (5). Similar to lindane, DDT was first synthesized by Othmar Zeilder in 1873, long before its insecticidal property was found. During the first half of 20th century several other chlorinated pesticides were introduced including, toxaphene, diene-organochlorine insecticides such as chlordane, mirex, Aldrin, dieldrin, endrin, and heptachlor. In addition to the organochlorine insecticides, some other industrial chemicals either intentionally produced, or as resulting by-products of industrial processes are also of concern as POCs. These compounds include, polychlorinated biphenyls (PCBs), polynuclear aromatic hydrocarbons (PAHs), hexachlorobenzene (HCB), polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polybrominated diphenylethers (PBDEs), perfluorinated compounds (PFCs) and chlorinated paraffins, etc. The industrial chemical, polychlorinated biphenyl (PCB) was first synthesized as early as the 1880s by Schmidt and Schultz (6) and large scale commercial production began in 1929. PCBs consist of 209 isomers and congeners from the mono-substituted 2-chlorobiphenyl to the fully substituted decachlorobiphenyl. Commercial PCB mixture range from 21% (Aroclor 1221) to 68% chlorine (Aroclor 1268). PCB mixtures were produced for a variety of uses such as fluids in electrical transformers and capacitors, heat transfer fluids, lubricating and cutting oils, and as additives in plastics, paints, printing inks, adhesives and sealants (1). HCB was produced commercially as a fungicide for wheat in 1933 and also has had industrial uses in organic synthesis as a raw material for a variety of substances including synthetic rubber, a plasticizer for poly (vinyl chloride), an intermediate in dye manufacture etc. (7) In the following paragraphs, the production, use and regulations of select POCs in some Pacific Basin countries are highlighted.

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Figure 1. Timeline of persistent organic chemicals. The arrow indicates an increase in number of chemicals produced over the years. Despite regulations, the number of chemicals detected in environ-mental samples continues to increase in the present century, posing a threat to our environment and health.

Restrictions/Ban on POCs in Some Countries in the Pacific Rim United States and Canada The United States was one of the major producers of PCBs with an estimated >600,000 tons produced between 1930 and 1977 (8). Globally, over one million tons of PCBs were produced before the mid 1970s (8). The manufacture of PCBs stopped in the United States in August 1977. On April 19, 1999, the United States Environmental Protection Agency issued final regulations banning the 4 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

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manufacture of PCBs and the phasing out of most PCB uses. The largest use of PCBs prior to being discontinued in the late 1970s, was in closed systems such as electrical equipment, mainly capacitors and transformers (9, 10). In 1972, DDT was banned in the US for agricultural uses (11). In 1986, Toxaphene was banned in the US due its negative effect on human and animal health (12). Similarly, brominated flame retardants such as polybrominated diphenyl ethers, were also restricted/banned in several States in the US. In April 2007, the state of Washington passed a bill banning the use of PBDEs. The State of Maine Department of Environmental Protection found that all PBDEs should be banned. In August 2003, the State of California outlawed the sale of penta- and octaPBDE and products containing them, effective January 1, 2008. In May 2007, the legislature of the state of Maine passed a bill phasing out the use of DecaBDE. Some of the PBDEs such as penta- or octaBDE have been voluntarily withdrawn by manufacturers in the United States. Also, Minnesota become the first state in the US that proposed a ban on the sale of soaps and cleaning products that contain antibacterial compound triclosan as of January 1, 2017 (13). In addition, in January 2015, the final year of the PFOA (perfluorooctanoic acid) Stewardship Program, the US EPA proposed an additional Significant New Use Rule for C8/PFOA and 25 other long-chain PFCs (14). In Canada, the manufacture, import, and sale of PCBs were made illegal in 1977 and release to the environment of PCBs were made illegal in 1985. However, Canadian legislation has allowed owners of PCB equipment to continue using PCB equipment until the end of its service life. The storage of PCBs has been regulated since 1988. Canada is signatory to several international agreements on the phase-out of a number of persistent toxic substances including PCBs (15). Canada banned DDT in 1972 because of its impact on humans and wildlife. Canada also banned the use of the most toxic PBDE compound (penta-PBDE) in 2005. In 2009, Canada added PFOS to a list of chemicals in legislation that must be eliminated from use. Toxaphene’s effect on human and animal health led to a ban on its use in Canada in 1982 (16). Recently, the federal government of Canada has proposed a ban on microbeads in personal care products such as shower gels, facial scrubs and toothpastes, which will commence July 1, 2018. This Canadian Environmental Protection Act would prohibit the import, manufacture or sale of toiletries that contain microbeads that are 0.5mm diameter or smaller (17). Colombia Colombia is located at the northwestern tip of South America and it is the fourth largest country on the continent. Colombia’s ministry of environment is responsible for the definition of the environmental policies and regulations. In 2008, Colombia signed the Stockholm Convention on persistent organic pollutants. Colombia banned DDT and other organochlorines including, dieldrin, chlordane, mirex, pentachlorophenol, dicofol, BHC, heptachlor, lindane in 1993, and these are no longer in use. Colombia banned PCBs in 2008. According to the Ministry of Environment and Sustainable Development Resolution 222-2011, 30% of the total inventory of PCBs or wastes contaminated with PCBs must be eliminated by December 31, 2017. The 100% of the total inventory of 5 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

PCBs or wastes contaminated with PCBs must be eliminated by December 31, 2028. Other compounds that are partially restricted are PBDEs (Law 1196-2008), perfluorinated compounds (Law 1196-2008), Heroin, methaqualone and meclocualona, and the substances that are listed in the Convention of Psychotropic 1971 (Resolution 826-2003 of Ministry of Social Protection.

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Australia Australia has a history of intensive use of organochlorine insecticides and industrial PCBs, but with gradual phasing out of these compounds through restrictions on agricultural use and the availability of less persistent and bioaccumulative alternatives (18). Australia is a signatory to the Stockholm Convention on Persistent Organic Pollutants. In 2003-2004, the federal agency estimated that 180 tons of deca-BDE product, 20 tons of penta-BDE product, and less than 10 tons of octa-BDE product were imported in raw form into Australia (18). This agency also reported a decrease in the use of about 90% of octa-BDE and approximately 70% penta-BDE was seen in 2003-2004 compared to 1998-1999. From February 2007, octa-BDE was not allowed to be imported/manufactured and penta-, and deca-BDE are under review (18). Malaysia According to the PAN Asia and the Pacific, banned organochlorine pesticides such as DDTs are still in use in Malaysia (19). An article in a 21st Century Science and Technology headline reads, “With DDT Spryaing in Malaysia Can Show the World How to Control Dengue”, the official announcement of the World Health Organization (WHO) in September 2006 gave a clean bill of health to the use of DDT for indoor spraying for controlling malaria reversed 30-year ban on DDT and offered promising way forward for also controlling the spread of mosquito-borne dengue fever (20, 21). According to the Director of WHO (Dr. Arata Kochi), “one of the best tools we have against malaria is indoor residual house spraying (IRS). Of the dozen insecticides WHO has approved as safe for house spraying, the most effective is DDT”. Japan Japan manufactured PCBs under trade name Kanechlor. The total PCB production was estimated to be 60,000 tons until 1971. Japan banned PCBs in the year 1972 (22). Japanese Government enacted special law on PCBs to destroy all of the PCB containing wastes by the year 2023 (23). The cumulative amount of DDT and HCH production was 30,000 and 400,000 tons, respectively, until 1971. Japan imported chlordane compounds for termite control purposes. The use of chlordane in Japan was estimated to be 17,500 tons until it was banned in 1986 (24). HCB was banned in 1979; Aldrin, dieldrin, endrin were banned in 1981; heptachlor was banned in 1986; Toxaphene and mirex were banned 2002; α, β, γ-HCHs were banned in 2010; endosulfan in 2014; pentachlorophenol, its salts and its esters were banned in 2016. PBDEs: tetra-, penta-, hepta-, and hexaBDEs 6 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

banned in 2010. Deca-BDE is still in use. Perfluorinated compounds: PFOS, its salts were restricted in 2010. PCN was banned in 1979; pentachlorobenzene banned in 2010 and HBCD restricted in 2014 (25, 26).

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Republic of Korea (South Korea) DDTs and PCBs were banned in south Korea in 1971 and 1979 respectively. Import of PCBs were prohibited in 1984 (27). Lindane was banned in 1969, however, specific exemption as medicinal use until 2020 (28). Dieldrin was banned in 1971 and no longer used in S. Korea. Heptachlor and HCH were banned in 1979 and endosulfan was banned later in 2010 (29, 30). According to Eco-labeling policy some of the PBDEs were restricted beginning 2006 (31). Also some perfluorinated compounds were also restricted in 2015 with permanent exemption until development of alternatives (until 2025) (30). Reductil, a pharmaceutical chemical was banned in 2010 due to side effects such as stroke and myocardial infarction (32). Polyhexamethylene guanidine, oligo (2-(2-ethoxy) ethoxyethyl guanidine chloride)- humidifier germicides were banned in 2011 (33). Cleaning products containing nonylphenols were banned in 2002, this ban included >0.1% nonylphenol products after 2006 (34). According to Shim et al. tributyltin (TBT) was banned in ships smaller than 4000 tonnage since 2000 and total ban imposed in 2003 (34). Hexabromocyclododecane (HBCD) was restricted in 2015, with permanent exemption chemical until development of alternative until 2020 (37).

Emerging Compounds with Persistent Organic Pollutant-Like Properties Detected in the Pacific Basin Countries Table 1 shows the list of compounds detected in environmental and biological samples from the Pacific Basin countries (38–45). In addition to compounds listed in the Table 1, a class of industrial chemicals used in plastics such as phthalates and phthalate metabolites were also of compounds of concern as endocrine disruptors. In August 2008, the United States Congress passed the Consumer Product Safety Improvement Act (CPSIA). The CPSIA bans the use of Di-n-butylphthalate (DBP), benzylbutyl phthalate (BBP), and Di(2-ethylhexyl)phthalate (DEHP) in amounts greater than 0.1% in all children’s toys and some childcare products (46). In addition, the Congress also restricted, on an interim basis, diisononyl phthalate (DINP), di-n-octylphthalate (DNOP), and diisodecylphthalate (DIDP). The Consumer Product Safety Commission (CPSC) has also recommended banning diisobutylphthalate (DIBP), di-n-pentylphthalate (DnPP), di-n-hexylphthalate ((DHEXP) and dicyclohexylphthalate (DCHP) (46). Pharmaceuticals (with POP-like properties) including, antischizophernics, sedatives, antidepressants, antihypertensions, antihistamines, stimulants were also detected in wastewater treatment plant (47).

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Table 1. Emerging compounds with POP-like properties. Prepared based on references (38–45). Compound Name (CAS Number)

Abbreviation

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(i) Flame Retardants 1,2-Bis(2,4,6-tribromophenoxy)ethane (37853-59-1)

BTBPE

1,2-Bis(tetrabromophthalimido)ethane (32588-76-4)

BTBPIE

5,6-Dibromo-1,10,11,12,13,13-hexachloro-11-tricyclo[8.2.1.02,9]tridecene

DBHC-TCTD or HCDBCO (51936-55-1)

Decabromodiphenylethane (84852-53-9)

DBDPE

Di(ethylhexyl)tetrabromophthalate (26040-51-7)

DEHTBP or TBPH

Dechlorane Plus, Bis(hexachlorocyclopentadieno)cyclo-octane (13560-89-9)

DP

2-Ethylhexyl-2,3,4,5-tetrabromobenzoate (183658-27-7)

EH-TBB or TBB

Hexabromobenzene (87-82-1)

HBB

Hexabromocyclododecane, major isomers are α, β, γ-HBCDD (3194-55-6)

HBCD or HBCDD

Pentabromoethylbenzene (85-22-3)

PBEB

Pentabromotoluene (87-83-2)

PBT

Tetrabromobisphenol A (79-94-7)

TBBPA

Tetrabromobisphenol A diallyl ether (25327-89-3)

TBBPA-DAE

Tetrabromobisphenol A bis(2,3-dibromopropyl) ether (21850-44-2)

TBBPA-DBPE

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (3322-93-8)

TBECH

2,4,6-tribromophenyl allyl ether (3278-89-5)

TBP-AE or ATT

Tris(2-chloroethyl)phosphate (115-96-8)

TCEP

Tris(1,3-dichloroisopropyl)phosphate (13674-87-8)

TDCPP or TDCP

Short-chain chlorinated paraffins (85535-84-8 and 71011-12-6)

SCCP

(ii) PFCs and other Industrial Chemicals Perfluorooctane sulfonyl fluoride (1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluorooctane-1-sulfonyl fluoride) (307-35-7)

POSF

Perfluorooctane sulfonic acid (1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluorooctane-1-sulfonic acid)(1763-23-1)

PFOS

Perfluorooctane sulfonate Potassium salt (1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Potassium salt) (2795-39-3)

PFOS K

Continued on next page.

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Table 1. (Continued). Emerging compounds with POP-like properties. Prepared based on references (38–45). Compound Name (CAS Number)

Abbreviation

N-ethyl-perfluorooctanesulfonamide (1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonamide) (754-91-6)

N-EtFOSA

Perfluorobutanoic acid (2,2,3,3,4,4,4-heptafluorobutanoic acid) (375-22-4)

PFBA

Perfluroropentanoic acid (2,2,3,3,4,4,5,5,5-nonafluoropentanoic acid) (2706-90-3)

PFPeA

Perfluorohexanoic acid (2,2,3,3,4,4,5,5,6,6,6-undecafluorohexanoic acid) (307-24-4)

PFHxA

Perfluroroheptanoic acid (2,2,3,3,4,4,5,5,6,6,7,7,7tridecafluoroheptanoic acid) (375-85-9)

PFHpA

Perfluorooctanoic acid (2,2,3,3,4,4,5,5,6,6,7,7,8,8,8pentadecafluorooctanoic acid) (335-67-1)

PFOA

Perfluorononanoic acid (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9heptadecafluorononanoic acid) (375-95-1)

PFNA

Perfluorodecanoic acid (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10nonadecafluorodecanoic acid) (335-76-2)

PFDA

Perfluoroundecanoic acid (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoroundecanoic acid) (2058-94-8)

PFUnDA

Perfluorododecanoic acid (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-tricosafluorododecanoic acid) (307-55-1)

PFDoDA

8:2 fluorotelomer alcohol (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10heptadecafluoro-1-decanol) (678-39-7)

8:2 FTOH

Components of Fire-Fighting Foams Perfluorooctane sulfonate

PFOS

Perfluorohexanesulphonate

PFHxS

Perfluorobutanesul-phonate

PFBS

Perfluorooctanesulfonamide (PFOSA)Pperfluoro-decanoate

PFDA

Perfluorononanoate

PFNA

Perfluorooctanoate

PFOA

Perfluoro-heptanoate

PFHpA

Perfluoroundecanoate

PFUnDA

Perfluoro-hexanoate

PFHxA

Other Industrial Chemicals Continued on next page.

9 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Table 1. (Continued). Emerging compounds with POP-like properties. Prepared based on references (38–45). Compound Name (CAS Number)

Abbreviation

Bisphenol A, (4,4-dihydroxy-2,2-diphenyl propane) (80-05-7)

BPA

Bisphenol AF (hexafluorobisphenol A), (1,1,1,3,3,3-hexafluoro2,2-bis(4-hydroxyphenyl)propane) (1478-61-1)

BPAF

Bis(2-ethylhexyl)tetrabromophthalate (26040-51-7)

BEHTBP

(iii) Pharmaceuticals

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Macrolide antibiotics Carbamazepine (iv) Personal Care Products Musk Fragrances 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2benzopyrane (1222-05-5)

HHCB

7-acetyl-1,1,3,4,4,6-hexamethyltetrahydeonaphthalene (1506-02-1)

AHTN

UV Stabilizers 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (3896-11-5)

UV-326

2,4-di-t-butyl-6-(5-chloro2H-benzotriazol-2-yl) phenol (3864-99-1)

UV-327

2-(2H-benzotriazol-2yl)-4,6-di-t-pentylphenol (25973-55-1)

UV-328

Temporal Trends of Organohalogens and Emerging Pollutants in the Pacific Basin Trend monitoring studies are valuable in understanding the past history, present status and possible future trends of contamination by persistent organic pollutants (POPs) in the environment. During the last five decades, the production and use of many persistent organic chemicals/persistent organic pollutants have been severely restricted in several countries in the Pacific Rim. Figure 2 show a schematic representation of time trends of chlorinated, brominated, fluorinated compounds as well as emerging compounds of concern with persistent organic pollutant (POP)-like properties. Organochlorine compounds such as PCBs and chlorinated pesticides contaminate the environment and organisms very rapidly during the periods of their use in industries, agricultural or public health purposes. The contamination level declined after a ban or severe regulations on production and use of these chemicals were imposed, especially in the most developed countries. However, some developing countries in southeast Asia and Pacific region still use organochlorines to combat vector borne diseases such as malaria, dengue etc. Therefore, the end point of environmental pollution by 10 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

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chlorinated POPs may not be reached for several decades in the future. In contrast, fluorinated and brominated compounds are still being produced in large quantities (not phased out completely) and used in several consumer products in both developing and developed countries. Therefore, environmental contamination and exposure to wildlife and humans by these compounds continues. Similarly, emerging persistent compounds derived from pharmaceutical and personal care products (PPCP), with persistent organic pollutant-like properties, are detected in environmental and biological samples during the past decade are also of concern. Evidence of PPCP contamination and ecotoxicological effects on aquatic organisms and indirect effect on humans via antibiotic resistant bacteria are mounting. Considering the contamination trends profiles as depicted in Figure 2, it can be predicted that the environmental contamination, human exposure, and health effects of brominated, fluorinated and other compounds with persistent organic pollutant-like properties will continue to be of concern for decades, not only to countries in the Pacific Basin, but also, on a global scale.

Figure 2. A schematic representation of time perspectives of classical POPs and compounds of concern with POP-like properties. Human exposure to environmental pollutants has been attributed to the worldwide prevalence and dramatic increase of obesity and type 2 diabetes over the last four decades. The World Health Organization estimated 1.5 billion adults worldwide are overweight or obese and the number of type 2 diabetes increase from 153 to 347 million between 1980 and 2008 (48, 49). A recent study estimated the human cost of long-term low level chemical exposure to endocrine disrupting chemicals costs the United States $340 billion in annual health care spending and lost wages (50).Typical examples are: PBDE flame retardant exposure leading to IQ points loss and intellectual disability in 43,000 cases with 11 million IQ points loss estimated cost $ 266 billion dollars annually. Phthalates exposure 11 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

and low testosterone resulting in increased early mortality (10,700 attributable dealths) estimated cost annually $ 8.8 billion dollars and multiple exposure with autism and ADHD (attention deficit/hyperactivity disorder) in children (~5,900 cases) estimated annual cost of $2.7 billion (50). Considering the human cost of chemical exposure, it is important to take necessary steps to minimize exposure in a timely way to protect our environment and human health.

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch001

Acknowledgments The author is thankful to the Murray State University Committee on Institutional Studies and Research (MSU-CISR) for awarding the 2016 Presidential Research Fellowship support in this endeavor.

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44. Taniyasu, S.; Yamashita, N.; Yamazaki, E.; Rostkowski, P.; Yeung, L. W. Y.; Kurunthachalam, S. K.; Kannan, K.; Loganathan, B. G. In Water Challenges and Solutions on a Global Scale; Ahuja, S., Andrade, J., Dionysiou, D., Hristovski, K., Loganathan, B. G., Eds.; ACS Sympsoum Series 1206; American Chemical Society: Washington, DC, 2015; pp 221−244. 45. Horii, Y.; Reiner, J. L.; Loganathan, B. G.; Kumar, K. S.; Sajwan, K.; Kannan, K. Occurrence and fate of polycyclic musks in wastewater treatment plants in Kentucky and Georgia, USA. Chemosphere 2007, 68, 2011–2020. 46. Sathyanarayana, S.; Karr, C. J.; Lozano, P.; Brown, E.; Calafat, A. M.; Liu, F.; Swan, S. H. Baby care products: Possible sources of infant phthalate exposure. Pediatirics 2008, 121, e260–e268. 47. Subedi, B.; Lee, S.; Moon, H.-B.; Kannan, K. Psychoactive pharmaceuticals in sludge and their emission from wastewater treatment facilities in Korea. Environ. Sci. Technol. 2013, 47, 13321–13329. 48. Kelishadi, R.; Poursafa, P.; Jamshidi, F. Role environmental chemicals in obesity: A systematic review on the current evidence. J. Environ. Pub. Health. 2013, 2013, 8, Aricle ID. 896789. 49. Ogden, C. L.; Carrol, M. D.; Curtin, L. R. Prevalence of overweight and obesity in the United States, 1999-2004. JAMA, J. Am. Med. Assoc. 2006, 295, 1549–1555. 50. Attina, T.; Hauser, R.; Sathyanarayana, S.; Hunt, P. A.; Bourguignon, J.-P.; Myers, J. P.; DiGangi, J. Exposure to endocrine-disrupting chemicals in the USA: A population-based disease burden and cost analysis. Lancet Diabetes Endorcrinol. 2016, 4, 996–10034.

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Chapter 2

Human Exposure to Brominated Flame Retardants Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Boris Johnson-Restrepo*,1 and Aída L. Villa2 1Chemistry

and Environmental Research Group, School of Exact and Natural Sciences, San Pablo Campus, University of Cartagena, Cartagena 130015, Colombia 2Environmental Catalysis Research Group, Chemical Engineering Department, Engineering Faculty, Universidad de Antioquia, Calle 70 No. 52-21, Medellín, Colombia *E-mail: [email protected]

The aim of this chapter is to examine the human exposure to brominated flame retardants (BFRs) such as polybrominated bisphenyl ethers (PBDEs), hexabromocyclohexane (HBCDs), and tetrabromobisphenol A (TBBPA). BFRs have been measured in several types of samples including adipose tissue, blood, and breast milk. PBDE concentrations from the U.S. population are the highest at 10 to 100-times greater than those reported for the rest of the world. HBCDs and TBBPA concentrations in the U.S. population are lower than the concentrations found in Europe. These exposure differences among different countries were explained by the usage pattern and market demand for BFRs. Several pathway contribute to human body burmen such as food daily intake, dust, and indoor/outdoor air. While Dust and food ingestion are considerated the important contribution to PBDE exposure in adults, breast milk intake is the principal source of exposure to infants.

© 2016 American Chemical Society Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

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Introduction Brominated flame retardants (BFRs) are incorporated into polymers as additives or are bonded chemically through a reaction, for the purpose of reducing the flammability of the materials to reach established fire safety standards (1). BFRs have been used widely in industrial and consumer products since the 1970s with a global annual growing of 4-5%. The worldwide market of BFR in 2011 was estimated at 394,000 metric tons (19.7 %) (www.flameretardants-online.com). BFRs are contained in different polymers such as polyurethane, epoxy resins, polyolefins, polyamides, high impact polystyrene foam, acrylonitrile–butadiene–styrene (ABS), polyurethanes, polycarbonate, styrene copolymers, polyterephthalate, and polyvinyl chloride; these polymers are extensively used in several consumer products including building materials, electronics, carpets, upholstery textile, and car panels (2). Polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA), and hexabromocyclododecanes (HBCDs) were the most widely BFRs used. PBDEs have been commercially produced as penta-BDE, octa-BDE, and deca-BDE technical mixtures (3). Several of the BFR compounds are persistent and bioaccumulative and have become ubiquitous environmental pollutants. PBDEs have been detected in environmental samples since the 1970s (4–7). However, earlier measurements of PBDEs in environmental samples were not isomer-specific because standards were not available until the late 1990s. Örn and coworkers synthesized selected PBDE congeners for isomer-specific analysis for environmental samples and toxicity evaluation (8–10). In addition, it was estimated that PBDE concentrations in Swedish breast milk had increased by 60 fold with a doubling time of 5 years (9). Several other studies have showed the occurrence of PBDEs in a variety of environmental and biological samples. Now, PBDEs are considered ubiquitous due to these compounds are being present in all environmental media including air (11, 12). soil (12), water (13), sediments (14, 15), foodstuffs (16–18), dust (19, 20), wildlife (21, 22), and humans (9, 23–28). PBDEs have been detected in remote areas such as the Arctic (29, 30), and the Antarctic (31–33). BFRs have been reported to elicit toxic effects in model animal studies (34–36).

Brominated Flame Retardants Brominated flame retardants (BFRs) are synthetic organobromide chemicals that have been incorporated into many flammable materials in order to provide longer escape times in case of fire, thus saving lives as well as reducing the damages from the fire. The use of BFRs had been mandated by law in several countries, especially in furnishings used in public places such as cinema theaters (37). Chemicals that have been the most widely used as BFRs include polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA), hexabromocyclododecanes (HBCDs), polybrominated biphenyls (PBBs), and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE). BFRs are classified into two broad categories, based on their usage, as ‘additive’ or ‘reactive’. Additive BFRs are incorporated into the mass of polymers or materials whereas the reactive 18 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

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BFRs are linked covalently to the chemical structure of polymers. Thus, there is a reduced leaching or release of reactive BFRs from source materials into the environment. However additive BFRs are not strongly bound to the matrix and therefore can be leached or released easily from the substrate. BFRs have a characteristic inhibitory effect on combustion and thus make the materials that contain them resisting to flammability. Bromine atoms present in BFRs generate bromine radicals (Br•) at elevated temperatures due to poor thermal stability. These radicals interrupt the propagation of free radical reactions involved in the flame by suppressing the high-energy and exothermic free radicals (hydrogen, H• and hydroxyl, OH•) formed in the gas phase. As a consecuense, radical free species (H• and OH•) are not propagated in the combustion and are reemplaced by less reactive radical species (R•) and thus the fire of materials containing flame retards are slowed, suppressed or eventually extinguished (Figure 1) (38).

Figure 1. Mechanism of action of brominated flame retardants. Although BFRs have beneficial roles when used in several materials including plastics, rubbers, textiles, and building materials, by imparting fire resistance, these chemicals present toxic, persistent and bioaccumulative effects as the organochloride contamiants previously reported (39). Furthermore, some BFRs have occured in various environmental media, wildlife, and human tissues throughout the world showing that they are widespread in the environment (2, 3, 40, 41). BFRs have also been reported to occur in fish from open oceans and in marine mammals (42, 43).

Polybrominated Diphenyl Ether (PBDEs) PBDEs are syntetic organic compounds that have been used as additive BFRs, and resemble polychlorinated biphenyls (PCBs) in their chemical structures. Also PBDEs and their metabolites are structurally similar to thyroid hormones (THs) (Figure 2). PBDEs are diphenyl ether substituted with bromine atoms at different positions resulting in 209 theoretically possible congeners. The general chemical formula for PBDEs is C12H10-nOBrn, (n = 1, 2,..,10). There are 10 homologues of PBDEs depending on the degree of bromination (Table 1). The chemical structure of THs (triiodothyronine, T3 and thyroxine, T4) contains a diphenyl ether backbone but is substituted by iodine instead of bromine. Iodine 19 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

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substitutions on the dipheyl ether ring for T3 and T4 are at the positions 3, 3′, 5 and 3, 3′, 5, 5′, respectively. Additionally, T3 and T4 contain one OH group at the 4′ position and an alanine residue. PBDEs were produced as three types of technical penta-BDE, octa-BDE, and deca-BDE mixtures. The penta-BDE mixture contains tri-BDEs, tetra-BDEs (mainly BDE-47), penta-BDEs (mainly BDE-99 and BDE-100) and hexa-BDEs (BDE-153 and BDE-154); the octa-BDE mixture contains hexa-BDEs, hepta-BDEs (BDE-183), octa-BDEs (BDE-203), nona-BDEs, and BDE-209; and the deca-BDE mixture comprises primarily BDE-209 (~96%) and small amounts of nona-BDEs (Table 1).

Figure 2. Chemical structures of polybrominated diphenyl ether (PBDEs) (x and y are atoms of bromide, x+ y ≤ 10) and thyroid hormones.

20 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Table 1. Brominated diphenyl ether homologues

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Homologues Formula

Homologues Name

Abbreviation

Molecular Weight

No. of Congeners

C12H10O

Biphenyl ether

BDE

170.2

1

C12H9OBr

Monobromodiphenyl ether

MonoBDE

249.1

3

C12H8OBr2

Dibromodiphenyl ether

DiBDE

328.0

12

C12H7OBr3

Thribromodiphenyl ether

ThriBDE

406.9

24

C12H6OBr4

Tetrabromodiphenyl ether

TetraBDE

485.8

42

C12H5OBr5

Pentabromodiphenyl ether

PentaBDE

564.7

46

C12H4OBr6

Hexabromodiphenyl ether

HexaBDE

643.6

42

C12H3OBr7

Heptabromodiphenyl ether

HeptaBDE

722.5

24

C12H2OBr8

Octabromodiphenyl ether

OctaBDE

801.4

12

C12H1OBr9

Nonabromodiphenyl ether

NonaBDE

880.3

3

C12OBr10

Decabromodiphenyl ether

PentaBDE

959.2

1

Technical mixtures have been sold under different trade names. The penta-BDE mixture is known as Bromkal 70-5DE and DE-71; the octa-BDE mixture as Bromkal 79-8DE and DE-79; and the deca-BDE mixture as DE-83R and Satex 102E. The technical mixtures differ in their compositions of specific BDE congeners. The technical mixtures differ in their composition of specific BDE congeners and have been characterized in detail (Table 2) (44–46). The penta-BDE mixture has been mainly used in polyurethane foam (for furniture at levels as high as 30% by weight) in upholsteries, carpet, and insulation panels, whereas the octa-BDE mixture has been used in rigid plastics such as acrylonitrile-butadiene-styrene (ABS) in applications such as electronic goods and appliances. The deca-BDE mixture is used in plastics, including high impact polystyrene for electrical and electronic equipment (televisions, cars, pipes, cables, and wires), polypropylene, poly(butylene terephthalate), unsaturated polyesters, and nylon, as well as in textiles for furniture.

21 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Mixture Penta-BDE

Commercial name DE-71

Bromine atoms (x + y)

IUPAC

3

28

2,4,4′-tri-BDE

0.37

4

47

2,2′,4,4′-tetra-BDE

33.0

49

2,2′,4,5′-tetra-BDE

0.77

66

2,3′,4,4′-tetra-BDE

1.02

85

2,2′,3 4,4′-penta-BDE

3.18

99

2,2′,4,4′,5-penta-BDE

42.5

100

2,2′,4,4′,6-penta-BDE

10.9

102

2,2′,4,5,6′- penta-BDE

0.13

138

2,2′,3,4,4′,5′-hexa-BDE

0.24

139

2,2′,3,4,4′,6- hexa-BDE

0.16

153

2,2′, 4,4′,5,5′-hexa-BDE

3.75

154

2,2′, 4,4′,5,6′-hexa-BDE

3.00

155

2,2′,4,4′,6,6′- hexa-BDE

0.32

138

2,2′,3,4,4′,5′-hexa-BDE

0.6

153

2,2′, 4,4′,5,5′-hexa-BDE

8.7

154

2,2′, 4,4′,5,6′-hexa-BDE

1.1

171

2,2′,3,3′,4,4′,6-hepta BDE

1.8

5

22

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Table 2. Specific congener composition of PBDE mixtures

6

Octa-BDE

DE-79

6

7

Chemical Name

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Concentration (% w/w)

23

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Mixture

Commercial name

Bromine atoms (x + y)

Concentration (% w/w)

2,2′,3,4,4′,5,5′-hepta-BDE

1.7

183

2,2′,3,4,4′ 5′,6-hepta BDE

42.0

196

2,2′,3,3′,4,4′,5,6′-octa-BDE

10.5

197

2,2′,3,3′,4,4′,6,6′-octa-BDE

22.2

203

2,2′,3,4,4′,5,5′,6-octa-BDE

4.4

206

2,2′,3,3′,4,4′,5,5′,6-nona-BDE

1.4

207

2,2′,3,3′,4,4′,5,6,6′-nona-BDE

11.5

10

209

2,2′,3,3′,4,4′,5,5′,6,6′-deca-BDE

1.3

9

206

2,2′,3,3′,4,4′,5,5′,6-nona-BDE

2.2

207

2,2′,3,3′,4,4′,5,6,6′-nona-BDE

0.2

208

2,2′,3,3′,4,5,5′,6,6′-nona-BDE

0.1

209

2,2′,3,3′,4,4′,5,5′,6,6′-deca-BDE

96.8

9

Saytex 102E

Chemical Name

180

8

Deca-BDE

IUPAC

10

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Tetrabromobisphenol A (TBBPA)

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TBBPA is a reactive flame retardant used principally in the circuit boards of electronic goods (e.g., television sets, computers, printers, photocopiers, fax machines, mobile phones) and electrical equipment (e.g., washing machine, dryers) (Figure 3). TBBPA is covalently bound to epoxy resins but in some cases, this is used as a additive BFR on acrylonitrile-butadiene-styrene polymers.

Figure 3. Chemical structures of tetrabromobisphenol A (TBBPA).

Hexabromocyclododecane Isomers (HBCDs) HBCDs are used mainly in expandable and extruded polystyrene foam for thermal insulation, textile coating for upholstery furniture, and high impact polystyrene for electrical and electronic consumer goods (www.bsef.com). HBCD (Figure 4) consists of a non-aromatic ring of 12 atoms, of which 6 asymmetric carbons in the positions of 1, 2, 5, 6, 9, and 10, resulting in 16 possible diastereoisomer structures. There are eight HBCD diastereoisomers found in the technical HBCD mixture, comprising 3 pairs of racemic enantiomers of (±) α- (11.8%), (±) β- (5.8%), and (±) γ- (81.6%) isomers and two meso forms of δ- (0.5%) and ε- (0.3%) isomers (47). When the HBCD technical mixture is heated at temperatures of between 160 and 200°C, α-HBCD prevails due to thermal stereoisomerization of the γ- and β- HBCD isomers (48).

24 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Figure 4. Steroisomer structure of hexabromocyclododecane (HBCDs) (47).

25 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Human Exposure to PBDEs PBDEs have been used in large volumes (up to 30% by weight) in many consumer products and have become ubiquitous pollutants in all environmental compartments, including wildlife and humans. PBDEs became the contaminants of interest among environmental scientists and regulators after earlier studies in the 1990s showed an exponential increase in concentrations in breast milk. The first report was published using breast milk samples from Sweden population. Results showed that PBDE concentrations haven been increasing exponentially with a doubling time every 5 years over a period of 25 years since the 1970s (9). Concentrations of PBDEs in North American human samples were also shown to increase exponentially (2, 49) but increasing concentrations have been also reported in China (50, 51). Therefore, PBDEs have been regarded as a new type of persistent organic pollutants (POPs), similar to PCBs, and the concerns regarding these contaminants are mounting due to the potential impact on human health that these chemicals may pose if the exposure levels and body burdens continue increasing. Although PBDEs can affect thyroid hormone levels in animal models, the levels at which such effects would occur in humans are also reported (52). The mechanisms by which PBDEs cause thyroid dysfunction are not clearly understood. However, PBDEs and their hydroxylated metabolites are structurally similar to THs, as mentioned earlier, and these chemicals can alter the transport of THs, or can directly interact with the thyroid gland (53). Alterations in the homeostasis of THs during the first three months of prenatal development can carry latent effects in the early stages of brain development in neonates. The rising concentrations of PBDEs, their environmental persistence, and the high bioaccumulation potential (similar to that for PCBs and DDTs) in biota and human tissues, resulted in a voluntary phase-out or ban on the usage of penta-BDE and octa-BDE mixtures in Europe and the U.S. Although the concentrations and frequency of detection of decabrominated diphenyl ethers (BDE-209) have been low in biological samples, high and increasing concentrations have been found in environmental abiotic samples (sludge, dust, food, air, soil, water, and sediment). It has been suggested that BDE-209 could be debrominated to more toxic lower-polybrominated diphenyl ether congeners by photolytic, thermal (54) or microbiological processes (55–57). Therefore, the lower brominated congeners will remain in the environment and human exposures will continue to occur in the near-future. Furthermore, products containing PBDEs are still in use and they will continue to be a source of human and environmental exposures. Nevertheless, some important advances in regulations have taken place in Europe and in the Unitted States, including banning or restrictions of manufacturing and use of PBDEs, including the deca-BDE mixture.

26 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Exposure Pathways, Bioaccumulation, Storage, and Excretion Models of BFRs The body burdens of brominated flame retardants occurs by exposure from different sources and physicochemical properties of these chemicals. BFRs, as other organohalogen compounds (DDT, PCBs, PCDDs, etc.), are lipophilic and non-ionized at physiological pH. Thus they readily penetrate cellular barriers and establish a dynamic equilibrium between the blood and adipose tissues which are stored in the body. Storage of these chemicals in adipose tissue is considered as a mechanism of protection to keep the chemicals away from important target organs. The metabolism and elimination of BFRs from the body is slow. For the general population, a lifelong exposure brings consequence to a gradually increasing concentration of the chemicals in the organism. Elimination half-lives of the chemicals from the biological lipid deposits are on the order of several years. However, in females, chemical may again be transported to the blood during the lactactation, making this period the most important route of elimination for such chemicals (Figure 5). Brominated retardant such as PBDEs in.the U.S. general population are much higher than the body burdens reported from the populations in other parts of the world (2, 40, 41). Estimates of daily dietary intake of PBDEs did not appear to be a major pathway of exposure to PBDEs (58–61) (Figure 6).

Figure 5. Exposure pathway, bioaccumulation, storage, and excresion model for organohalogens (BFRs).

27 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

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Figure 6. Important human exposure pahways to BFRs.

Human Biomonitoring of PBDEs A global review of literature on PBDEs in human tissue samples was performed to evaluate the current knowledge and to identify data gaps. In this review, only the research papers that report specific PBDE congener concentrations were selected. For comparison, concentrations were normalized by converting the data to a lipid weight basis, because PBDEs are lipophilic and their concentrations are expected to be proportional to the lipid content in tissues. Furthermore, a geometric mean or median concentrations of specific congeners and total PBDEs (∑PBDE) were used or calculated from the raw data reported. If the year of sampling was not reported on the publication, it was 28 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

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assumed as two years prior to the publication date of the paper. Data reported in the literature are not homogeneous, because much of the data are on congeners found in the penta-BDE mixture, including BDE-47, 99, 100, 153, and 154, and the octa-BDE mixture such as BDE-183 and 203. BDE-209, which is the major component of the deca-BDE mixture, was not included in the studies conducted before 2000. There were difficulties in accurately quantifying BDE-209 in environmental and biological samples using the currently available techniques (62). In addition, it was thought that BDE-209 was degraded to lower brominated congeners in the environment and in biological tissues (54–56). Median or geometric mean concentrations were used in this review, because of their central tendency in the measurement of distributions; furthermore, the environmental data are predominantly log-normally distributed. However, the values of median and geometric mean are almost similar because in a log-normal distribution, the geometric mean is the estimation of the true median (63, 64). Studies of human biomonitoring of PBDEs has provided valuable information on sources of exposures and exposure patterns and the biomonitoring has been accomplished through an array of human matrices, including breast milk, adipose tissues, breast tissue, liver, serum, whole blood, cord blood serum, and placenta. PBDE concentrations are tabulated by congener and the sum of congeners reported by several authors (Table 3).

Adipose Tissue Concentrations of lipophilic organohalogen contaminants, such as PBDEs, in the body are in a dynamic equilibrium between blood and adipose tissue. Concentrations in the adipose tissue reflect the levels of chemical in the body after reaching a steady state. Concentrations in the other tissues depend on the lipid dynamics and storage in the adipose tissue. Concentrations in blood reflect the most recent exposure which can be affected by the ingestion of a recent meal containing the chemical residue in question, inhalation or dermal absorption of the chemicals in proximity of contaminated hazardous sites. Adipose tissue samples contain, on average, over 60% of lipid, and store high levels of lipophilic contaminants; thus, adipose tissue analysis has the advantage over other human tissue samples because a bench-top gas chromatograph with a low resolution quadrupole mass spectrometric detector (GC-MS) is adequate to detect all brominated and chlorinated contaminants. However, adipose tissue samples can only be obtained by invasive techniques, which is a major limitation. Interestingly, one way of obtaining adipose tissue is from waste products of cosmetic surgeries. Recently, liposuction techniques have become popular among healthy overweight people who want to lose weight by removing excessive fat stored in the body. Access to and use of such samples would help in understanding the accumulation of contaminants in a fraction of the total population. Collection of information from several biomonitoring studies on PBDEs in the general population showed widespread global contamination by these compounds (3, 40, 41, 65–67). Stanley et al. detected hexa- to deca-PBDE homologues in U.S. adipose tissues samples collected in 1987 by the National 29 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Human Adipose Tissue Survey (NHATS). This study was a first report on PBDEs in human tissues from the U.S. Median concentrations were: hexa-BDEs, 0.02 ng/g lipid wt (range, < LOD – 1 ng/g lipid wt), hepta-BDEs, 0.1 ng/g lipid wt (range, 0.001 – 2 ng/g lipid wt), octa-BDEs, 0.2 ng/g lipid wt (range, < LOD – 8 ng/g lipid wt), nona-BDE, detected but not quantified, and deca-BDE, < LOD to 0.7 ng/g lipid wt. Median concentrations of sum of hexa- to octa-BDE was 0.49 ng/g lipid wt (range, 0.003 to 0.83 ng/g). It should be noted that concentrations of specific BDE congeners were not reported due to the lack of appropriate standards at that time. This study suggested that people from the U.S. in the late of 1980’s were exposed at low levels of octa-BDE and deca-BDE mixtures. Beginning the new millennium, several studies in the U.S. reported PBDE concentrations by specific congeners including BDE-47, BDE-99, BDE-100, BDE-153, and BDE-154. BDE congener 47 is generally the most prevalent compound in adipose samples. She et al. (23) measured BDE-47, 99, 100, 153, and 154 congeners in adipose tissue samples from 23 women from California collected during 1996-1999. BDE-47 was the predominant congener in all samples. The PBDE congener profile was 42% BDE-47, 13% BDE-99, 8% BDE-100, 15% BDE-153, and 22% BDE-154. BDE-154 was dominant in 3 of 23 women. The median concentration of BDE-47 was 18.3 ng/g lipid wt (range, 7.01 to 196 ng/g lipid wt) and ∑BDEs was 41.4 ng/g lipid wt (range, 17.2 to 462 ng/g lipid wt). PBDE concentrations found in paired abdominal and breast adipose tissue samples were similar and statistically correlated. The study group also included samples with malignant tumor conditions (n=12), ductal carcinomas in situ (DCIS) (n=3) and benign tumor conditions (n=8). Concentrations of the ∑BDEs and specific congeners were not related to the disease status of malignancies (malignant or DCIS) of the individuals. However, ∑BDE concentrations were correlated negatively with age. In a study from California, Petreas et al. (68) measured only BDE-47 concentrations in adipose tissue samples from women (n=32) collected between 1996 and 1998. BDE-47 was detected in all samples with a median concentration of 16.5 ng/g lipid wt (range, 5.2 – 196 ng/g lipid wt). The limit of detection reported for BDE-47 (LOD, < 0.5 ng/g lipid wt) in adipose fat was < 20 times lower than the limit of detection reported for the same congener in serum (LOD, 10 ng/g lipid wt). PBDE concentrations from a set of 23 samples reported by She et al. (23) showed a negative correlation with age (Spearman, R = -0.413, P 183 > 99 > 100. These congeners collectively constituted 96% of the ∑PBDE concentrations. In Tarragona, BDE-183 as a marker of octa-BDE mixture, was not detected. Tan et al. (74) investigated BDE concentrations in 88 maternal adipose tissues from Singapore. BDE-153 was the most common congener detected but PBDE-47 was the most abundant congener in the samples. BDE-47 accounted for 37% with a median of 1.84 ng/g lipid wt, followed by BDE-153, accounting for 28%, with a median of 1.39 ng/g lipid wt. Choi et al. (75) investigated the levels of PBDEs in women of ages 40-50 years from Tokyo, Japan. Adipose tissue samples were collected in 1970 and in 2000. The median concentration in samples from 2000 (1.3 ng/g lipid wt.) was more than 40 times greater than the median concentration in samples from 1970 (0.03 ng/g lipid wt). BDE-47 was the predominant congener in the samples accounting for > 56% of the total PBDE concentration in 1970 and 35.6 % in 2000. Changes in the PBDE product usage during the past 30 years (1970-2000) were reflected in the variation in PBDE profiles in tissues. Reported concentrations of PBDEs in samples of adipose tissue (23, 68), serum (76), and milk (77) were obtained from archived specimen banks in the U.S. and demographic information was limited for those samples. The rising levels of PBDEs in the world and the higher levels detected in the U.S. highlighted the importance of conducting systematic biomonitoring studies to assess the risks associated with such exposures. Studies that measure PBDE concentrations along with several biological variables can help in understanding the factors that influence the accumulation of PBDEs in individuals. Breast milk and adipose tissue samples collected, along with several demographic variables such as gender, age, race, and occupation, were used to investigate PBDE concentrations (25, 78, 79).

31 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

32

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Table 3. Median concentrations of PBDEs (ng/g lipid weight) in human samples from selected countries, published in peer-reviewed journals. Geometric mean (GM), CA = California; IL =Illinois; IN = Indiana; New York = NY; MA= Massachusetts; Meryland = MD; MS= Mississippi; Montana = MO, Oregon=OR, Tennessee = TN; TX = Texas; Washington =WA. British Columbia, Canada = BC Country / Region

Sample

n

Year collection

PBDE congeners

Range

∑PBDEs

References

Australian Melbourne

milk

2003-2003

pool

47, 99, 100, 154, 183, 196

9 - 12.4

11.2

(103)

Sydney

milk

2004-2003

pool

47, 99, 100, 154, 183, 196

8.5 - 11

9.75

(103)

adipose tissues

2000

20

28, 47, 99, 100, 153

2.23 - 11.7

3.9

(70)

adipose tissues

2001-2003

53

28, 47, 99, 100,153, 154, 183

1.23 - 57.2

5.32

(71)

adipose tissues

2004-2005

25

17, 28, 47, 71, 85, 99, 100, 138, 153, 154, 183

0.19132

1.51

(110)

milk

1992

10

28, 47, 99, 100,153, 154, 183

0.79 - 28.5

3.14

(111)

Belgium Antwerp

Brazil Porto Alegre Canada Ontario/Quebec China

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

33

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Country / Region

Sample

n

Year collection

PBDE congeners

Range

∑PBDEs

References

Guangzhou

cord serum

2005

21

28, 47, 99, 100,153, 154, 183

1.5 - 12

3.9

(84)

Guangzhou

milk

2005

27

28, 47, 99, 100,153, 154, 183

1.7 - 7.2

3.5

(84)

Guangzhou

serum

2005

21

28, 47, 99, 100,153, 154, 183

1.6 - 17

4.4

(84)

Guangzhou

serum

2005

15

28, 47, 99, 100,153, 154, 183, 196,197, 203,206, 207, 208, 209

6.2 - 578

35.1

(88)

Guangzhou

serum

2005

20

28, 47, 99, 100,153, 154, 183,197, 207, 208, 209

1.3 - 95.6

10.1

(88)

milk

2003

103

28, 47,49, 66, 99, 100,153, 154, 183

0.16 - 13.3

2.2

(100)

Copenhagen

milk

1997 - 2001

36

28, 47, 66,85, 99, 100,153

1.1 – 9.1

3.3

(102)

Copenhagen

placenta

1998 - 2001

129

28, 47, 99, , 100,153, 154, 183

0.6-3.3

1.3

(102)

Tórshavn

milk

1999

9

47, 99, 100,153, 209

4.7 - 13

5.8

(101)

Tórshavn

serum

1994 -1995

57

47, 99, 100,153, 209

0.4 – 50.1

3.9

(81)

Czech Republic Olomouc Denmark

Faroe Island

Continued on next page.

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Table 3. (Continued). Median concentrations of PBDEs (ng/g lipid weight) in human samples from selected countries, published in peer-reviewed journals. Geometric mean (GM), CA = California; IL =Illinois; IN = Indiana; New York = NY; MA= Massachusetts; Meryland = MD; MS= Mississippi; Montana = MO, Oregon=OR, Tennessee = TN; TX = Texas; Washington =WA. British Columbia, Canada = BC Country / Region

Sample

n

Year collection

PBDE congeners

Range

∑PBDEs

References

Finland Turku

milk

1997 - 2001

32

28, 47, 66, 99, 100,153, 154, 183

1.04 - 29.5

3.1

(102)

Turku

placenta

1998 - 2001

56

28, 47, 66,99, , 100,153

0.35 9.9

1.2

(102)

Venice

milk

2000 - 2001

pool

17, 28, 47,66, 85, 99, 100,153, 154, 183

1.6 - 2.8

2.5

(96)

Rome

milk

1998 - 2000

pool

17, 28, 47,66, 85, 99,100,153, 154, 183

4.1

(96)

Tokyo

adipose tissues

1970

10

28, 47, 99, 100

0.007 – 0.08

0.029

(28)

Tokyo

adipose tissues

2000

10

28, 47, 99, 100, 153, 154, 183

0.47 - 2.8

1.29

(28)

Kyoto

milk

2004

30

28, 47, 99, 153, 154,

1.39 (GM)

(106)

Shimane

milk

2004

20

28, 47, 99, 100, 153, 154, 183

0.83 (GM)

(106)

Italy

Japan

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Sample

n

Year collection

PBDE congeners

Range

∑PBDEs

References

Hokkaido

milk

2005

20

15, 28, 47, 99, 100,153, 154, 183, 196,197,206, 207, 209

1.02 - 4.55

2.23 (GM)

(83)

Miyagi

milk

2005

40

15, 28, 47, 99, 100,153, 154, 183, 196, 197, 206, 207, 209

0.49 - 3.41

1.42 (GM

(83)

Gifu

milk

2005

20

15, 28, 47, 99, 100,153, 154, 183, 196,197,206, 207, 209

0.66 - 2.38

1.45 (GM)

(83)

Hyogo

milk

2005

9

15, 28, 47, 99, 100,153, 154, 183, 196,206, 207, 209

0.49 - 4.55

1.3 (GM)

(83)

Kanagawa

milk

1999

10

28,37, 47, 66,99, 100,153, 154, 183

0.56 - 2.91

1.47

(83)

Hokkaido

serum

2005

20

15, 28, 47, 99,100, 154, 183, 196, 197, 203, 207,209

1.04 - 5.43

2.75 (GM)

(83)

Miyagi

serum

2005

40

15, 28, 47, 99,100, 154, 183, 196, 197, 203, 206,207,209

1.33 - 21.2

3.64 (GM)

(83)

Gifu

serum

2005

20

15, 28, 47, 99,100, 154, 183, 196, 197, 203, 207,209

0.74 - 4.5

2.06 (GM)

(83)

35

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Country / Region

Continued on next page.

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Table 3. (Continued). Median concentrations of PBDEs (ng/g lipid weight) in human samples from selected countries, published in peer-reviewed journals. Geometric mean (GM), CA = California; IL =Illinois; IN = Indiana; New York = NY; MA= Massachusetts; Meryland = MD; MS= Mississippi; Montana = MO, Oregon=OR, Tennessee = TN; TX = Texas; Washington =WA. British Columbia, Canada = BC Country / Region

Sample

n

Year collection

PBDE congeners

Range

∑PBDEs

References

0.76 - 5.38

2.52 (GM)

(83)

serum

2005

9

15, 28, 47, 99,100, 154, 183, 196, 203, 206, 207,209

Ciudad Juarez

serum

2006

43

47, 99,100, 153, 154,209

4.8 (GM)

(112)

San Luis Potosi

serum

2006

16

47, 99,100, 153, 154,209

7.3 (GM)

(112)

Milpillas

serum

2006

52

47, 99,100, 153, 154,209

8.6 (GM)

(112)

El refugio

serum

2006

15

47, 99,100, 153, 154,209

15.7 (GM)

(112)

San Juan Tilapa

serum

2006

20

47, 99,100, 153, 154,209

3.7 (GM)

(112)

Chihuahua

serum

2006

27

47, 99,100, 153, 154,209

2.7 (GM)

(112)

milk

2006

22

47, 99, 100, 154

2

(97)

Murmansk

milk

2000

14

47, 99,100, 154,183

1.09

(99)

Arkhangelsk

milk

2000

23

28, 47, 99,154, 183,209

1.13

(99)

Hyogo Mexico

Poland Wielkopolska

0.8 - 8.4

Russia

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Country / Region

Sample

n

Year collection

PBDE congeners

Range

∑PBDEs

References

37

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Sweden Stockholm

adipose tissues

1994

5

28, 47, 85, 99, 100, 154, 183

3.8 - 7.7

5.2

(69)

Stockholm

plasma

2000 - 2001

15

28, 47, 66, 99, 100, 154, 183, 196

6.53 - 57.9

2.07

(80)

Stockholm

cord plasma

2000 - 2001

15

28, 47, 66, 99, 100, 154, 196

1.1 - 9.42

1.69

(80)

Stockholm

liver

1994

5

28, 47, 85, 99,100, 154,183

4.5 - 18.4

5.8

(69)

Stockholm

milk

1972

pool

47, 154

0.07

Stockholm

milk

1976

pool

28, 47, 66, 99, 100, 154,183

0.35

Stockholm

milk

1980

pool

28, 47, 99, 100, 154,183

0.48

Stockholm

milk

1984/1985

pool

28, 47, 99, 100, 154,183

0.73

Stockholm

milk

1990

pool

28, 47, 66, 99, 100, 154,183

1.21

Stockholm

milk

1994

pool

28, 47, 66, 99, 100, 154,183

2.17

Stockholm

milk

1996

pool

28, 47, 66, 85, 99, 100, 154,183

3.11 Continued on next page.

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

38

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Table 3. (Continued). Median concentrations of PBDEs (ng/g lipid weight) in human samples from selected countries, published in peer-reviewed journals. Geometric mean (GM), CA = California; IL =Illinois; IN = Indiana; New York = NY; MA= Massachusetts; Meryland = MD; MS= Mississippi; Montana = MO, Oregon=OR, Tennessee = TN; TX = Texas; Washington =WA. British Columbia, Canada = BC Country / Region

Sample

n

Year collection

PBDE congeners

Range

∑PBDEs

References

Stockholm

milk

1997

pool

28, 47, 66, 85, 99, 100, 154,183

Uppsala

milk

1996-1999

93

47, 99, 100, 154,183

0.91 - 28.2

3.15

(95)

Stockholm

milk

2000 - 2001

15

28, 47, 66, 85, 99, 100, 154,183, 196

0.56 - 7.72

2.14

(80)

adipose tissues

2006

88

47, 99,100, 154,183, 196

4.93

(74)

Tarragona

adipose tissues

1997

13

47, 99, 100, 154

1.02 -11.9

3.1

(72)

Granada

adipose tissues

2003

20

28, 47, 66, 85, 99, 100,154, 183, 196, 197, 203, 209

1.4 - 10.6

2.94

(73)

Madrid

serum

2003 -2004

61

47, 66, 85, 99, 100,154, 183, 196, 203, 207

9.6

(108)

Madrid

cord serum

2005 -2004

44

47, 66, 99, 100, 154, 183, 196, 197, 203, 207

14.9

(108)

4.02

Singapore Singapore Spain

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

39

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Country / Region

Sample

n

Year collection

PBDE congeners

Range

∑PBDEs

References

Madrid

milk

2006 -2004

22

28, 47, 85, 99, 100, 154, 183, 196, 197, 207

5.6

(108)

Madrid

placenta

2007 -2004

30

28, 47, 66, 99, 100, 154, 183, 196, 197, 207

1.8

(108)

milk

1998

103

28, 47, 99,100, 154, 196

3.34

(98)

milk

2003

37

47, 99

1.4 - 0.4

0.23

(113)

London

milk

2001-2003

27

28, 47, 99, 100, 153,154

3.1 - 6.9

7.8

(104)

Lancaster

milk

2001-2003

27

28, 47, 99, 100, 153,154

0.3-34

4.6

(104)

CA

adipose tissues

1996 - 1999

23

47, 99, 153, 154

17.2 - 462

41.4

(23)

NY

adipose tissues

2003-2004

52

28, 30, 47, 85, 99, 100, 153, 154

17 - 9630

75

(24)

IN

cord serum

2001

12

47, 99, 100, 153, 154

14 - 460

39

(107)

MD

cord serum

2004 - 2005

297

28, 47, 85, 99, 100, 153, 154,183

26.9

(114)

IL

serum

1988

12

47, 99, 100, 153, 154

7.06

(76)

The Netherlands

Turkey Kahramanmaras United Kindom

United States

0.5 - 134

Continued on next page.

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Country / Region

Sample

n

Year collection

PBDE congeners

Range

∑PBDEs

References

TN

serum

1985 -1989

pool

47, 100, 153

4.6 - 74

9.6

(115)

TN

serum

1990 -1994

pool

47, 85, 99

7.5 - 86

48

(115)

TN, WA

serum

1995 -1999

pool

47, 85, 99, 100, 153, 154

42 - 120

71

(115)

TN, WA

serum

2000 -2002

pool

47, 85, 99, 100, 153, 154

47 - 160

61

(115)

MS

whole blood

2003

29

17, 28, 47, 66, 85, 99, 100, 138, 153, 154, 183

4.7 - 362

30.8

(17)

NY

whole blood

2003

10

28, 47, 99, 100, 138, 153, 154, 183

4.6 - 135

25

(116)

MO, OR,WA,BC

milk

2003

40

28, 32, 47, 66, 85, 99, 100, 153, 154, 183

6.34 - 321

50.4

(92)

TX

milk

2001 - 2004

47

17, 28, 47, 66, 85, 99, 100, 138, 153, 154, 183

6.2 - 418

34

(77)

MA

milk

2004 - 2005

46

28, 47, 66, 85, 99, 100, 138, 153, 154, 183

4.3 - 264

30.2

(78)

MA

milk

2005

38

28, 47, 66, 77, 85, 99, 100, 118, 138, 153, 154, 183, 203, 209

0.06 -1910

19.8

(49)

40

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Table 3. (Continued). Median concentrations of PBDEs (ng/g lipid weight) in human samples from selected countries, published in peer-reviewed journals. Geometric mean (GM), CA = California; IL =Illinois; IN = Indiana; New York = NY; MA= Massachusetts; Meryland = MD; MS= Mississippi; Montana = MO, Oregon=OR, Tennessee = TN; TX = Texas; Washington =WA. British Columbia, Canada = BC

Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries I ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1243.ch002

Blood Blood is the most common type of specimen used in human biomonitoring studies for PBDEs and chlorinated contaminants. Blood samples have been used as whole blood, serum, or plasma. Plasma is obtained by centrifugation of the whole blood sample with an appropriate anti-coagulant such as EDTA or heparin, while serum is produced from whole blood by centrifugation without any added anticoagulant. There were identified seversal types of blood samples used in various studies. Although blood samples are relatively easy to collect and the levels of contaminants in blood represent the most recent exposures, contaminant analysis in this matrix has some limitations. The most significant limitation is the need for a large volume of sample (10 – 20 ml) to quantify PCBs and PBDEs due to the low lipid content present in this matrix (1 - 3%). Nevertheless, recent state of the art analytical methods based on solid phase extraction (SPE) and high resolution mass spectrometry (HRMS) require less than 2 ml of blood. Other limitations of monitoring using a blood matrix include the need for expensive GC coupled to HRMS and the low limits of detection when low volumes of samples are used. Concentrations of PBDEs (tri – hexa-BDEs) in serum samples from the U.S. and Canada were compared with those from European countries (80–82), Japan (83), and China (84–87). Concentrations of PBDEs were one to two orders of magnitude higher in North American samples than in European or Asian samples. In samples from the U.S., BDE-17, 28, 31, 47, 66, 72, 77, 138, 153, 154, 183, and 209 were detected. BDE-47, 153, and 99 were the predominant congeners, accounting for 43 - 64%, 3.3 – 14%, and 0.5 – 6.7%, respectively, of the total PBDE concentrations. Only a few studies have reported concentrations of BDE-209 in blood. However, low median concentrations of BDE-209, ranging from < LOD to 1.5 ng/g lipid wt, in the U.S.,