Organohalogen Contaminants In Wildlife From . - DiVA Portal
Organohalogen contaminants in wildlife fromthe Yangtze River DeltaDevelopment of methods and assessments of legacy and emergingpersistent organic pollutantsGe Yin
Organohalogen contaminants inwildlife from the Yangtze River DeltaDevelopment of methods and assessments of legacy andemerging persistent organic pollutantsGe Yin
Ge Yin, Stockholm University 2016ISBN 978-91-7649-477-6Printed in Sweden by E-print AB, Stockholm 2016Distributor: Department of Environmental Scienceand Analytical Chemistry, Stockholm University
To Yihui, my parents, and aunt.
Cover page: A fictitious football match between organohalogen contaminants andwildlife held in the Yangtze River Delta (Designed by Yihui Zhou and Ziye Zheng)Team in left side: Organohalogen contaminantsGoalkeeper: chlorinated paraffinDefender: BDE-47, CB-153, 4,4’-dicofol, 2’-OH-CDE-206Midfield: HCB, HCH, PCPForward: OCDD, 4,4’-DDE, HBCDDTeam in right side: WildlifeGoalkeeper: codDefender: clam, snail, musselMidfield: toad, eel, snake, frogForward: heron, falcon, tern
List of publicationsThe thesis is based on the following articles and manuscripts, referred to inthe text by their roman numerals (I-VI). Published articles are reprinted withthe permission from the publisher.Paper I. Chlorinated and brominated organic pollutants in shellfish fromthe Yellow Sea and East China SeaYin, G.; Asplund, L.; Qiu, Y.L.; Zhou, Y.H.; Wang, H.; Yao, Z.L.; Jiang, J.B.;Bergman, Å. Environmental Science and Pollution Research. 22 (2015), pp.1713–1722Paper II. A refined method for analysis of 4,4’-dicofol and4,4’-dichlorobenzophenoneYin, G.; Athanassiadis, I.; Bergman, Å.; Zhou, Y.H.; Qiu, Y.L.; Asplund, L.ManuscriptPaper III. Extensive organohalogen contamination in wildlife from a sitein the Yangtze River DeltaZhou, Y.H.; Asplund, L.; Yin, G.; Athanassiadis, I.; Wideqvist, U.; Bignert,A.; Qiu, Y.L.; Zhu, Z.L.; Zhao, J.F.; Bergman, Å. Science of the TotalEnvironment. 554-555 (2016), pp. 320-328Paper IV. A novel pollution pattern: Highly chlorinated biphenylsretained in Black-crowned night heron (Nycticorax nycticorax) andWhiskered tern (Chlidonias hybrida) from the Yangtze River DeltaZhou, Y.H.; Yin, G.; Asplund, L.; Qiu, Y.L.; Bignert, A.; Zhu, Z.L.; Zhao,J.F.; Bergman, Å. Chemosphere. 150 (2016), pp. 491-498Paper V. High concentrations of OCDD and related chemicals in heronand tern eggs from Yangtze River Delta indicating PCP originZhou, Y.H.; Yin, G.; Asplund, L.; Stewart, K.; Ruokojärvi, P.; Bignert, A.;Rantakokko, P.; Kiviranta, H.; Qiu, Y.L.; Bergman, Å. Submitted manuscripti
Paper VI. Sampling designs for contaminant temporal trend analysesusing sedentary species exemplified by the snails Bellamya aeruginosa andViviparus viviparusYin, G.; Danielsson, S.; Dahlberg, A-K.; Zhou, Y.H.; Qiu, Y.L.; Nyberg, E.;Bignert, A. ManuscriptContribution to Paper I-VIPaper I and II: I participated in the design of the study. I was responsible forall the experimental work, data evaluation and I took the lead in writing themanuscript and finalizing the publication.Paper III: I assisted the experiment, data evaluation and participated in writing.Paper IV and V: I assisted the experiment, date evaluation and took the leadin writing.Paper VI: I participated in the design of the study and sampling. I wasresponsible for the experimental work, assisted data evaluation andparticipated in writing.Publication/Manuscripts not included in the thesisSpatial distribution and Bioaccumulation of polychlorinated biphenyls(PCBs) and polybrominated diphenyl ethers (PBDEs) in snails (Bellamyaaeruginosa) and sediments from Taihu lake area, ChinaYin, G.; Zhou, Y.H.; Strid, A.; Zheng, Z.Y.; Asplund, L.; Bignert, A.; Ma,T.W.; Qiu, Y.L.; Athanassiadis, I.; Bergman, Å. Manuscriptii
ContentsList of publications . iContents . iiiAbbreviations. v1. Background . 11.1 Aim of thesis . 52. Introduction . 72.1 Yangtze River Delta . 72.2 Legacy POPs . 92.2.1 Chemicals intentionally produced and distributed to theenvironment . 102.2.2 Chemicals intentionally produced and unintentionallydistributed to the environment . 132.2.3 Unintentionally produced POPs. 152.3 Emerging environmental contaminants . 172.4 Wildlife assessed . 223. Methodology . 243.1 Samples and sampling information . 243.2 Sample pretreatment . 273.2.1 Extraction and lipid determination . 273.2.2 Lipid removal . 283.2.3 Separation of substances groups . 283.3 Instrumental analysis . 313.4 Quality assurance and quality control . 343.5 Statistical analysis . 354. Results and discussion . 39iii
4.1 Environmental exposure. 394.1.1 Chlorinated paraffins . 394.1.2 Polychlorinated diphenyl ethers, hydroxylated polychlorinateddiphenyl ethers and methoxylated polychlorinated diphenylethers. 414.1.3 Polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans. 424.1.4 Highly chlorinated biphenyls . 424.1.5 Legacy POPs . 424.2 Potential sources. 444.2.1 PCDD/Fs, PCDEs and OH-/MeO-PCDEs . 444.2.2 Highly chlorinated biphenyls . 464.2.3 DDT and dicofol. 474.3 Environmental monitoring consideration . 474.3.1 Spatial and temporal trend monitoring efforts . 484.3.2 Wildlife exposure vs. Human risk . 494.3.3 Sampling strategy (Paper VI) . 505. Concluding remarks . 51Svensk sammanfattning . 53中文概要 . 55Acknowledgement . 57Appendix . 60References . 64iv
sPCAPCBsbrominated flame retardantschlorinated ethyl sulfoxideelectron capture detectorelectron capture negative ionizationelectron impact ionizationgas chromatographygel permeation enehexachlorocyclohexaneshigh resolution mass spectrometryliquid chromatographylong chain chlorinated paraffinslimit of detectionlimit of quantificationlow resolution mass spectrometrymedium chain chlorinated paraffinsmethoxylated polychlorinated diphenyl etherssodium chlorine pesticidesorganohalogen contaminantshydroxylated polychlorinated diphenyl ethershighly chlorinated biphenyls (i.e. PCBs with 8-10chlorine substituents, octaCBs, nonaCBs &decaCB)polybrominated diphenyl ethers (individual PBDEsare presented as “BDE-#”)principal component analysispolychlorinated biphenyls (individual PCBs arepresented as “CB-#”)v
PCPpentachlorophenolPCDDsPCDEspolychlorinated dibenzo-p-dioxinspolychlorinated diphenyl ethers (individual PCDEsare presented as “CDE-#”)polychlorinated dibenzofuransperfluorooctane sulfonatepersistent organic pollutantsStockholm Conventionshort chain chlorinated paraffinsselected ion ze River DeltaPCDFsPFOSPOPsSCSCCPsSIMTCDDYRDvi
1. BackgroundThe development of human civilization is in part related to innovations indevelopment and applications of man-made chemicals. In China, peopleare proud of the four great innovations: Paper making, Printing,Gunpowder and the Compass. In three of these, chemistry and use ofchemicals play a key role. In particular, papermaking and printingtechnique not only have an invaluable influence to the world, but also makeit possible for you to read my thesis from the printed book. However, eachcoin has two sides. Paper making is the cause of some severeenvironmental contamination, particularly when chlorine gas came into usefor paper pulp bleaching.1 This type of bleaching led to discharges of alarge number of organochlorine contaminants, including poly-chlorinateddibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs).2 However, alarge number of other sources have emerged over the years as the origin oforganohalogen contaminants (OHCs). First to be discovered were thoseintentionally distributed in the environment, pesticides; soon followed byintentionally produced but unintentionally distributed in the environmentsuch as the polychlorinated biphenyls (PCBs).One of the most well-known OHCs is dichlorodiphenyltrichloroethane(DDT). It was first synthesized in 1874 by Othmar Zeidler.3 However, itwas not until the 1930’s as Paul Hermann Müller discovered DDT’sinsecticidal properties that it really became a very important innovation.DDT was applied in a lot of applications and deliberately used for insertcontrol. DDT was even applied in soldiers helmets to protect them fromvector transferred diseases during the Second World War.4 Müller wasawarded the Nobel Prize in Physiology or Medicine in 1948 but already atthis time a warning had been raised for use of DDT.5 The successfulapplication of DDT inspired the development of new organic pesticidesand other man-made chemicals. In 1962, Rachel Carson published the book“Silent Spring”, elaborating how pesticides are related to adverse effectsin the ecosystems.6 This book caught enormous attention both fromscientific and public side and has been considered as one of the mostinfluential book on environmental pollution in the last century.1
From the mid 1960’s, more research on environmental pollution wasinitiated and details of the ingredients in DDT were discovered. It wasshown that the main ingredient in DDT was 1,1-bis(4-chlorophenyl)-2,2,2trichloroethane (4,4’-DDT), which is metabolized to 1,1-bis(4chlorophenyl)-2,2-dichloroethene (4,4’-DDE), but also a full range ofother metabolites.7 DDT, and its main metabolites DDE, showed negativeeffects such as eggshell thinning in birds of prey.8 DDT is still today oneof the major environmental pollutants threatening both wildlife and humanhealth.4Severe contamination in wildlife9, 10 and an accident in Japan11 led to theidentification of PCBs as an environmental contaminant and a class ofchemicals of great concern in relation to health. The important discoverieswere the identification of PCB in white-tailed sea eagle in Sweden 196612and the contamination of rice oil from a factory in Southern Japan,resulting in thousands people being poisoned.11Another astonishing example of environmental pollution is the discoveryof 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) exposure coming fromimpurities in Agent Orange which was used as a defoliant during the warin Vietnam.13 This is only one example of how unintentional byproducts ina chemical process are unintentionally distributed in the environment. Theclass of PCDD/Fs, commonly referred to as “dioxins” led to intensiveresearch from the latter part of the 1970’s due to their toxicity and commonformation from numerous industrial processes.14-16Other technically produced chemicals, such as polybrominated diphenylethers (PBDEs) and per- and polyfluorinatred substances, in particularrepresented by perfluoroctane sulfonate (PFOS) came into focus during1980’s/1990’s and in the beginning of the new century, respectively.Although the usage and sources are different, these chemicals mentionedabove (DDTs, PCBs, PCDD/Fs, PBDEs and PFOS) have been consideredto share overall similar properties. Their structures make them all persistentin the environment; their lipophilic properties make the first fourbioaccumulative, while the proteinophilic character of PFOS make thiscompound accumulate in blood and liver; their semi-volatility make themundergo long range environmental transportation and finally their toxicitycause wide attention. In 2001, the Stockholm Convention (SC) onPersistent Organic Pollutants (POPs) was signed and has been ratified by172 countries in the world since 2004.17 This is an international treaty toprotect human health and the environment from POPs. It can be achievedby elimination, restriction and/or controlling the production process or2
finding the substitution method. Initially there were 12 groups of chemicalslisted in the SC and today the number has expanded to 26 (Table 1.1).17However, it must not be overlooked that other OHCs, not currently listedas POPs according to the SC, the so called “legacy POPs”, have a potentialto fulfill the requirements as new POPs. In this thesis these chemicals aredivided into three categories. The first category includes impurities andbyproducts from the POPs and OHCs in general (e.g. polychlorinateddiphenyl ethers (PCDEs), hydroxylated polychlorinated diphenyl ethers(OH-PCDEs)). The second category is chemicals which are produced forsubstitution of POPs, such as chlorinated paraffins (CPs) and dicofol. Thethird category is the novel pattern and profile of POPs (e.g. highlychlorinated biphenyls, the octa-, nona- and decaCBs (OND-PCBs)) as wellas novel OHCs. Due to the limited study of these categories compared withPOPs, they are considered as emerging environmental contaminants in thisthesis. It means that these contaminants have been documented regardingproduction and use and/or have been shown to occur in wildlife andhumans.China, with a population of 1.4 billion, is the biggest developing countryin the world. Studies on environmental exposure of OHCs are highlynecessary due to, but not limited to, the following reasons: (1) Agricultureis considered as the lifeline to afford such a large population. Therefore,organochlorine pesticides (OCPs) and antimicrobial agent are widely usedto protect crops from pests and farmed animal; (2) OCPs have been usedfor disease prevention (e.g. malaria, schistosomasis); (3) the rapidindustrialization and urbanization has been taken place during the past 40years. Chemicals are produced not only for domestic use but also for export;(4) certain hotspots of electron waste recycling have been reportedregarding legacy POPs, resulting in extremely high level of contaminationlevels of PBDEs calling for concern on public health and food safety issueto local residents.18, 19To date, numerous studies have been conducted on OHCs level in theenvironment in China, as exemplified with a few references.19-25 However,the studies which focus on emerging environmental contaminants are lessfrequent than those on POPs. The studies pursued are not geographicallyevenly distributed, as much work has been carried out in South China(Pearl River Delta) and North China, whereas information onenvironmental exposure level on OHCs in the Yangtze River Delta (YRD)are more limited. In terms of environmentally relevant studies performedin the YRD, most of them have been conducted in abiotic matrices.3
Table 1.1. Basic information on legacy POPs under the Stockholm Convention,17with those included in this thesis are marked with an al octa-bromodiphenyl ethers*Commercial penta-bromodiphenyl strial ial esticideIndustrial chemicalIndustrial strial 009200920012009A2015PFOSPFOS-FIndustrial ol and itssalts and esters*Perfluorooctane sulfonicacid, its salts andperfluorooctane sulfonylfluoridePolychlorinated nated phenePCNsa. Annex A: Elimination; Annex B: restriction; Annex C: unintentional production4
1.1 Aim of thesisThis thesis includes both chemical exposure assessments and methoddevelopment. Paper I, III, IV and V aimed to increase the collectiveknowledge on OHCs in several wildlife species to improve the knowledgeof the pollution burden of OHCs in the Yangtze River Delta. To reach thisgoal, both quantitative and qualitative analyses have been applied. Paper IIis about methodological development for a specific compound, dicofol,which has been listed as a candidate under the SC. Paper VI is to designsampling strategy by taking advantage of power analysis. The aims of theindividual papers I - VI are summarized as follows:Paper I: The aim was to determine residual concentrations of OCPs, PCBs,brominated flame retardants (BFRs) in shellfish from a few locations alongthe eastern coastline of China. In addition, the paper described a generalcontamination situation in YRD by using shellfish as a bioindicator.Paper II: Extremely high level of 4,4’-DDE found in Paper I arose ourinterests to focus on DDT related compounds. DDT was banned foragricultural use from 1983 and ha
GC gas chromatography GPC gel permeation chromatography HBCDD hexabromocyclododecane HCB hexachlorobenzene HCHs hexachlorocyclohexanes HRMS high resolution mass spectrometry LC liquid chromatography LCCPs long chain chlorinated paraffins LOD limit of detection LOQ limit of quantification .
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