Environmental Forensics for Persistent Organic Pollutants PDF
Preview Environmental Forensics for Persistent Organic Pollutants
Environmental Forensics for Persistent Organic Pollutants Environmental Forensics for Persistent Organic Pollutants Edited by Gwen O’Sullivan MountRoyal University Court Sandau Chemistry MattersInc. AMSTERDAM(cid:129)BOSTON(cid:129)HEIDELBERG(cid:129)LONDON NEWYORK(cid:129)OXFORD(cid:129)PARIS(cid:129)SANDIEGO SANFRANCISCO(cid:129)SINGAPORE(cid:129)SYDNEY(cid:129)TOKYO Elsevier Radarweg 29, PO Box 211, 1000AE Amsterdam, The Netherlands The Boulevard, Langford Lane, Kidlington, Oxford, OX51GB, UK 225 WymanStreet, Waltham, MA 02451, USA Copyright r 2014 ElsevierB.V. All rights reserved. No partof thispublication may be reproduced, stored inaretrieval system ortransmitted inany formor by anymeanselectronic, mechanical, photocopying, recording orotherwise without the prior written permission of the publisherPermissions may be sought directly fromElsevier’s Science &Technology Rights Department inOxford,UK: phone (144)(0) 1865 843830; fax (144) (0) 1865 853333; email: [email protected]. 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British Library Cataloguing-in-Publication Data Acatalogue record for thisbookis available from the BritishLibrary Library ofCongress Cataloging-in-Publication Data Acatalog record for this bookis available from the Library ofCongress ISBN:978-0-444-59424-2 ForinformationonallElsevierpublications visit ourweb site at store.elsevier.com Printed andboundin Italy 14 15 16 17 18 10 9 8 7 6 5 4 3 2 1 Foreword Environmental Forensics for Persistent Organic Pollutants was conceived as a treatise with the objective of providing a comprehensive examination of persistent organic pollutants (POPs). Environmental Forensics for Persistent Organic Pollutants exceedsthis goal inan exceptional manner. EnvironmentalForensicsforPersistentOrganicPollutantsisthefirstenvi- ronmentalforensicstextdevotedexclusivelytoPOPsandintroducesthereader toamultitudeofchemicalsandforensictechniques.Thetopicselection,organi- zation, incorporation of scientific information, and extensive references result inacomprehensivebuteasytousetreatise.Thebookfollowsalogicalpresen- tationofthekeyfacetsassociatedwithPOPs,beginningwithanintroductionto POPs, including their general physiochemical properties (Chapter 1) followed byahistoricalsummary,whichincludestheidentificationofrelevantlitigation, key treaties, statutes, regulations, and case law pertaining to the control of POPsintheUnitedStatesandCanada(Chapter2).Thepropercollection,man- agement,and analysisofsamples for POPs described inChapters 3 and 4 pro- vide a complete template for developing an investigative program for POPs. The discussion of the analysis of POPs in Chapter 3 describes methods to ensurethattargetanalytesareidentifiedandquantifiedwithoutbias,giventhat POPs are present in a variety of chemical forms (i.e., polycyclic aromatic hydrocarbons, polychlorinated biphenyls, polybrominated/fluorinated com- pounds, and polychlorinated dibenzo-p-dioxins and dibenzofurans), environ- mentalmatrices,andcommercialproducts. Thistreatiseisuniqueintheenvironmentalforensicliteraturewithitsinclu- sionofachapterdevotedtohumanbiomonitoring.Chapter5includesinforma- tionontoxicokinetics—absorption,thedistribution/metabolismandelimination of POPs in humans, the development of reference values and biomonitoring equivalents and environmental exposure pathwaysin food, soil, dust, clay, and beef. While biomonitoring of POPs is a mature scientific discipline in human health research, its consideration to environmental forensic investigations is in its infancy. The addition of human biomonitoring provides the environmental forensiccommunitywithanotherresourceforconsiderationwhendesigningan environmentalforensicinvestigation. Chapters 6(cid:1)8 follow a logical organization withthe presentation ofPOPs in the atmospheric, terrestrial, and aquatic environments. Chapter 6 describes the transport of POPs from primary and secondary sources through the xiii xiv Foreword atmosphere and techniques used for source identification, for evaluating the fate, transport, and timing of a POP release, and the potential allocation of residual contamination with a particular source. Noteworthy in this chapter, as in others, are polyaromatic hydrocarbon, polychlorinated biphenyl, poly- brominated/fluorinated compound, and dioxins/furan case studies. In concert with the literature review, the case studies provide the means to contemplate the design and implementation of an environmental forensics investigation that involvingPOPs inthe atmosphere. Chapter 7 examines POPs in the terrestrial environment and integrates information from preceding chapters via two POP case studies. The first POP case study describes the collection and analysis of environmental sam- ples,including liver,tissue,andbloodsamplesofwildlifenearafluorochem- ical plant near Antwerp. The second case study describes the investigation of dioxin/furan sources, which include the collection and analysis of dioxins and furans in duck and chicken eggs, soil sampling and congener analysis of environmental samples and principal component analysis as an exploratory statistical technique. Chapter 8 includes a similar format of POPs as in Chapters 5 and 7, but in the aquatic environment and includes novel forensic opportunities using pharmaceutical and nanomaterials (1(cid:1)100nm) as poten- tial diagnostic indicators. The presentation of the use of polyaromatic hydro- carbon to examine coal tar and oil sands is especially relevant, given the role of oilsands inour global energy demands. EnvironmentalForensicsforPersistentOrganicPollutantsprovidesaclear and concisepresentationofPOPs and includesnumerousnovel approachesfor considerationinforensicinvestigations.Theinformationinthiswell-referenced treatiserepresentsasignificantadvancementintheforensicsciencesandwhile specific to POPs, is applicable to the forensic investigation of many contami- nantsofconcern. Robert Morrison July 31, 2013 List of Contributors SungwooAhn,Exponent,Bellevue,WA,USA LesaL.Aylward,SummitToxicology,LLP,FallsChurch,VA,USA StevenBaicker-McKee,Babst-Calland,TwoGatewayCenter,Pittsburgh,PA,USA; DuquesneUniversitySchoolofLaw,Pittsburgh,PA,USA KaitCarey,BennetteJonesLLP,BankersHallEast,Calgary,AB,Canada AdrianCovaci,ToxicologicalCenter,UniversityofAntwerpUniversiteitsplein1, Wilrijk,Belgium FrankL.Dorman,PennStateUniversity,BiochemistryandMolecularBiology, ForensicScienceProgram,UniversityPark,PA,USA Jean-Franc¸oisFocant,UniversityofLie`geOrganicandBiologicalAnalytical Chemistry,Lie`ge,Belgium AlfredFranzblau,UniversityofMichigan,SchoolofPublicHealth,AnnArbor,MI BradGilmour,BennetteJonesLLP,BankersHallEast,Calgary,AB,Canada VeerleJaspers,DepartmentofBiology,NorwegianUniversityofScienceand Technology(NTNU),Trondheim,Norway;DepartmentofBiology,Universityof Antwerp,Wilrijk(Antwerp),Belgium KarlJ.Jobst,EnvironmentCanada,Burlington,ON,Canada;OntarioMinistryof theEnvironment,LaboratoryServicesBranch,Toronto,ON,Canada LindaMartello,ENVIRON,Emeryville,CA,USA DavidMegson,UniversityofPlymouth,SchoolofGeographyEarthand EnvironmentalScience,DrakeCircus,Plymouth,UK GwenO’Sullivan,MountRoyalUniversity,DepartmentofEnvironmentalScience, Calgary,AB,Canada DonaldG.PattersonJr.,Exponent,4921BillCheekRoad,Auburn,GA30011 JaanaPietari,Exponent,Maynard,MA,USA EricJ.Reiner,OntarioMinistryoftheEnvironment,LaboratoryServicesBranch, Toronto,ON,Canada;UniversityofToronto,DepartmentofChemistry,Toronto, ON,Canada PhilRichards,ChemistryMattersInc.,Calgary,Alberta,Canada KristinRobrock,Exponent,Oakland,CA,USA LaurelRoyer,Exponent,Maynard,MA,USA xv xvi ListofContributors CourtSandau,ChemistryMattersInc.,Calgary,Alberta,Canada;Departmentof CivilEngineering,SchulichSchoolofEngineering,UniversityofCalgary, Calgary,Alberta,Canada WalterJ.Shields,Exponent,Bellevue,WA,USA RichardJ.Wenning,ENVIRON,Emeryville,CA,USA TimothyC.Wolfson,Babst-Calland,TwoGatewayCenter,Pittsburgh,PA,USA EdwardP.Yim,Babst-Calland,TwoGatewayCenter,Pittsburgh,PA,USA Chapter 1 Brief Overview: Discovery, Regulation, Properties, and Fate of POPs GwenO’Sullivanaand David Megsonb aMountRoyalUniversity,DepartmentofEnvironmentalScience,Calgary,AB,Canada, bUniversityofPlymouth,SchoolofGeographyEarthandEnvironmentalScience,DrakeCircus, Plymouth,UK 1.1 INTRODUCTION The field of environmental forensics emerged in the 1980s as a consequence of legislative frameworks enacted to enable parties, either states or indivi- duals, to seek compensation with regard to contamination or injury due to damage to the environment [1]. Environmental laws, including CERCLA (“Superfund”) [2] in the United States and Environmental Liability Directive [3] in the European Union (EU), are based on the polluter pays and precau- tionary principles and require the parties responsible for the release of haz- ardous substance to report the release, investigate the nature and extent of the release and to then remediate it to some objective cleanup standard [4]. Morrison and Murphy [5] define environmental forensics as a “...systematic and scientific evaluation of physical, chemical, and historical information for the purpose of developing defensible scientific and legal conclusions regard- ing the source orage ofa contaminant released intothe environment”. Globally there are many 100,000 existing chemicals on the market [6] and they are an integral part of our modern life. Since the 1960s, following the publication of Rachel Carson’s book Silent Spring [7], mounting scien- tific evidence has suggested that certain chemicals pose a significant risk to the environment and human health. The United Nations Environmental Programme (UNEP) has identified a number of these chemicals as substance of very high concern (SVHC) andcategorizes them aspersistent, bioaccumu- lative, and toxic (PBT). Chemicals categorized as PBT do not break down easily in the environment, accumulate in the tissues of organisms, and are toxic. Persistent organic pollutants (POPs) are a subset of the PBT category, EnvironmentalForensicsforPersistentOrganicPollutants. ©2014ElsevierB.V.Allrightsreserved. 1 2 EnvironmentalForensicsforPersistentOrganicPollutants others include trace metals and organo-metal compounds. As the name sug- gests POPs are compounds which are organic (natural or anthropogenic) in nature and resist biological, chemical, and photolytic degradation [8]. The UNEP defines POPs as “...chemical substances that persist in the environ- ment, bioaccumulate through the food web, and pose a risk of causing adverseeffectstohuman health and the environment” [9]. There are thousands of chemicals which may be classified as POPs including whole families of chemicals, for example polychlorinated biphe- nyls (PCBs), polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo- furans (PCDD/PCDF), polybrominated diphenyl ethers (PBDEs), and organochlorinated pesticides (e.g., dichlorodiphenyltrichloroethane, DDT). Sources of POPs may be broadly classified as agrochemical (pesticides), industrial (synthesized for industrial use), or unintentional by-products (pro- ductsof combustionorindustrial synthesis ofotherchemicals). The following subsections will provide a brief overview of the history of POPs, introduce some of the key chemical and physical characteristics which help to define POPs, and outline the environmental fate and behavior of POPs. Thepurposeofthischapter isnottoprovideacomprehensivedescrip- tion of what POPs are but to provide you with a basic familiarity to assist you when readingthe subsequent chapters. 1.2 BRIEF HISTORY POPs have been used for more than a 100 years, with some of the infa- mous POPs discovered as early as the late 1800s (Table 1.1). A chronol- ogy for POPs, including when certain POPs were first discovered to be harmful, development of key analytical techniques and legislative mile- stones, may be found in Figure 1.1. In the early 1960s, advancements in analytical techniques, including elec- tron capture detectors, allowed for the detection of compounds such as DDT, Dichlorodiphenyldichloroethylene(DDE),dieldrin,andPCBsinenvironmen- talandbiologicalsamplesatlowlevels[6].Inadditionanumberofkeypub- lications (e.g., Silent Spring by Rachel Carson [7]), scientific discoveries (e.g., Soeren Jensen finding PCBs in Baltic fish [44]), and human exposure incidents (the fatal poisoning in Turkey of 500 people with hexachloroben- zene (HCB)-treated seeds [45], poisoning of 1800 people in Japan with rice oil contaminated with Kanechlor 400 [46]) laid the foundations for discus- sions regarding the control of POPs. Initially action focused on individual specificindustrialchemicals: (cid:1) DDT: The US EPA (United States Environmental Protection Agency) issueda cancellation order based onadverseeffect ofits use (1972) [13]. (cid:1) Mirex: The US EPA issued regulations authorize restricted use by permit only(1972) [22]. Chapter | 1 BriefOverview 3 TABLE1.1 TheDiscoveryandBanningofDirtyDozenPOPs Compound/ Use DateBanned Class Aldrin Firstsynthesizedin1940s 1970:USDepartmentofAgriculturecanceled andusedasinsecticidein alluses 1948[10] 1971:EPAinitiatescancelationprocedures 1972:FederalInsecticide,Fungicide,and RodenticideActbansuseinallbutthree specialistapplications.Thelastofthese(termite control)wasvoluntarilycanceledin1987[10] Chlordane Firstsynthesizedin1940s, 1978:EPAinitiatescancelationprocedures describedasaninsecticide 1988:AllusesbannedintheUnitedStates in1945andcommercially [11] synthesizedin1947[11] DDT Firstsynthesizedin1874 1973:AllusesbannedintheUnitedStates Firstdescribedasan [13] insecticidein1939 Firstcommercially synthesizedin1945[12] Dieldrin Firstsynthesizedin1940s 1970:USDepartmentofAgriculturecanceled andusedasinsecticidein alluses 1948 1971:EPAinitiatescancelationprocedures 1972:FederalInsecticide,Fungicide,and RodenticideActbansuseinallbutthree specialistapplications.Thelastofthese (termitecontrol)wascanceledin1989[10] Endrin Developedformanufacture 1986:Majorityofuseswerevoluntarilycanceled in1950[14]andfirstused bythemanufacturers asinsecticidein1951[15] 1991:Lastregistrationasapesticide voluntarilycanceledintheUnitedStates[15] Heptachlor Firstisolatedin1946 1974:EPAinitiatescancelationprocedures Firstcommercially 1988:AllusesbannedintheUnitedStates[17] synthesizedin1952[16] HCB Firstusedasapesticidein 1984:Lastregistrationasapesticidevoluntarily 1945[18] canceledintheUnitedStates[19] (Althoughitisstillbeinggenerated inadvertentlyasaby-productand/orimpurity inseveralchemicalprocesses[20]) Mirex Firstsynthesizedin1946 1971:EPAcancelsalluseofmirex Firstusedasapesticidein 1972:EPAauthorizedtherestricteduseof 1955(1959intheUnited mirexbypermitonly States)[21] 1978:AllusesbannedintheUnitedStates[22] PCBs Firstdiscoveredinlate 1976:UseofPCBswerefirstregulatedbythe 1800s EPAthroughtheTSCA Firstcommercially 1979:EPArulesgraduallyendedmany synthesizedin1929[22] industrialusesofPCBsovera5-yearperiod, butallowedtheircontinueduseinexisting enclosedelectricalequipmentundercarefully controlledconditions[23] (Continued)
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