The Handbook of Environmental Chemistry Editors-in-Chief: O.Hutzinger·D.Barceló·A.Kostianoy Volume2 ReactionsandProcesses PartP AdvisoryBoard: D.Barceló·P.Fabian·H.Fiedler·H.Frank·J.P.Giesy·R.A.Hites M.A.K.Khalil·D.Mackay·A.H.Neilson·J.Paasivirta·H.Parlar S.H.Safe·P.J.Wangersky TheHandbookofEnvironmentalChemistry RecentlyPublishedandForthcoming Volumes Polymers:ChancesandRisks EmergingContaminantsfromIndustrialand VolumeEditors:P.Eyerer,M.Weller MunicipalWaste andC.Hübner RemovalTechnologies 2010 VolumeEditors:D.BarcelóandM.Petrovic Vol.5/S/2,2008 AlpineWaters VolumeEditor:U.Bundi EmergingContaminantsfromIndustrialand Vol.6,2010 MunicipalWaste Occurrence,AnalysisandEffects TheAralSeaEnvironment VolumeEditors:D.BarcelóandM.Petrovic VolumeEditors:A.G.Kostianoyand Vol.5/S/1,2008 A.N.Kosarev 2010 FuelOxygenates VolumeEditor:D.Barceló TransformationProductsofSynthetic Vol.5/R,2007 ChemicalsintheEnvironment VolumeEditor:A.B.A.Boxall TheRhine Vol.2/P,2009 VolumeEditor:T.P.Knepper Vol.5/L,2006 ContaminatedSediments VolumeEditors:T.A.KassimandD.Barceló PersistentOrganicPollutants Vol.5/T,2009 intheGreatLakes VolumeEditor:R.A.Hites BiosensorsfortheEnvironmentalMonitoringof Vol.5/N,2006 AquaticSystems BioanalyticalandChemicalMethodsfor AntifoulingPaintBiocides EndocrineDisruptors VolumeEditor:I.Konstantinou VolumeEditors:D.BarcelóandP.-D.Hansen Vol.5/O,2006 Vol.5/J,2009 Estuaries EnvironmentalConsequencesofWarand VolumeEditor:P.J.Wangersky Aftermath Vol.5/H,2006 VolumeEditors:T.A.KassimandD.Barceló Vol.3/U,2009 TheCaspianSeaEnvironment VolumeEditors:A.KostianoyandA.Kosarev TheBlackSeaEnvironment Vol.5/P,2005 VolumeEditors:A.KostianoyandA.Kosarev Vol.5/Q,2008 MarineOrganicMatter:Biomarkers, IsotopesandDNA VolumeEditor:J.K.Volkman Vol.2/N,2005 TransformationProducts of Synthetic Chemicals in the Environment Volume Editor: AlistairB. A. Boxall Withcontributionsby C.D.Adams·D.Barceló·W.A.Battaglin·R.Baumgartner A.B.A.Boxall·J.Coats·K.E.Conn·L.B.M.Ellis B.I.Escher·K.Fenner·E.T.Furlong·S.T.Glassmeyer K.Henderson·P.H.Howard·D.Hu·S.J.Kalkhoff·D.W.Kolpin J.Lienert·M.T.Meyer·S.Pérez·M.Petrovic·U.Schenker M.Scheringer·D.J.Schnoebelen·C.J.Sinclair·L.P.Wackett 123 Environmentalchemistryisaratheryoungandinterdisciplinaryfieldofscience.Itsaimisacomplete descriptionoftheenvironmentandoftransformationsoccurringonalocalorglobalscale.Environ- mentalchemistryalsogivesanaccountoftheimpactofman’sactivitiesonthenaturalenvironmentby describingobservedchanges. TheHandbookofEnvironmentalChemistryprovidesthecompilationoftoday’sknowledge.Contribu- tionsarewrittenbyleadingexpertswithpracticalexperienceintheirfields.TheHandbookwillgrow withtheincreaseinourscientificunderstandingandshouldprovideavaluablesourcenotonlyfor scientists,butalsoforenvironmentalmanagersanddecision-makers. TheHandbookofEnvironmentalChemistryispublishedinaseriesoffivevolumes: Volume1:TheNaturalEnvironmentandtheBiogeochemicalCycles Volume2:ReactionsandProcesses Volume3:AnthropogenicCompounds Volume4:AirPollution Volume5:WaterPollution TheseriesVolume1TheNaturalEnvironmentandtheBiogeochemicalCyclesdescribesthenatural environmentandgivesanaccountoftheglobalcyclesforelementsandclassesofnaturalcompounds. TheseriesVolume2ReactionsandProcessesisanaccountofphysicaltransport,andchemicaland biologicaltransformationsofchemicalsintheenvironment. The series Volume 3 Anthropogenic Compounds describes synthetic compounds, and compound classesaswellaselementsandnaturallyoccurringchemicalentitieswhicharemobilizedbyman’s activities. TheseriesVolume4AirPollutionandVolume5WaterPollutiondealwiththedescriptionofcivilization’s effectsontheatmosphereandhydrosphere. Withintheindividualseriesarticlesdonotappearinapredeterminedsequence.Instead,weinvite contributorsasourknowledgematuresenoughtowarrantahandbookarticle. SuggestionsfornewtopicsfromthescientificcommunitytomembersoftheAdvisoryBoardortothe Publisherareverywelcome. TheHandbookofEnvironmentalChemistry,Subseries2 ISSN1433-6839 ISBN978-3-540-88272-5 e-ISBN978-3-540-88273-2 DOI10.1007/978-3-540-88273-2 SpringerDordrechtHeidelbergLondonNewYork LibraryofCongressControlNumber:2008939070 (cid:1)c Springer-VerlagBerlinHeidelberg2009 Thisworkissubjecttocopyright.Allrightsarereserved,whetherthewholeorpartofthematerial isconcerned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation,broad- casting,reproductiononmicrofilmorinanyotherway,andstorageindatabanks.Duplicationof thispublicationorpartsthereofispermittedonlyundertheprovisionsoftheGermanCopyrightLaw ofSeptember9,1965,initscurrentversion,andpermissionforusemustalwaysbeobtainedfrom Springer.ViolationsareliabletoprosecutionundertheGermanCopyrightLaw. 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Coverdesign:WMXDesignGmbH,Heidelberg TypesettingandProduction:le-texpublishingservicesGmbH,Leipzig Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Editors-in-Chief Prof.em.Dr.OttoHutzinger Prof.AndreyKostianoy UniversitätBayreuth P.P.ShirshovInstituteofOceanology c/oBadIschlOffice RussianAcademyofSciences Grenzweg22 36,NakhimovskyPr. 5351Aigen-Vogelhub,Austria 117997Moscow,Russia [email protected] [email protected] Prof.Dr.DamiàBarceló DepartmentofEnvironmentalChemistry IDAEA-CSIC,C/JordiGirona18–26, 08034Barcelona,Spain,andCatalan InstituteforWaterResearch(ICRA), ParcCientíficiTecnològicdela UniversitatdeGirona, EdificiJaumeCasademont,15 E-17003Girona,Spain [email protected] VolumeEditor Dr.AlistairB.A.Boxall EnvironmentDepartment UniversityofYork Heslington,York,YO105DD UnitedKingdom [email protected] AdvisoryBoard Prof.Dr.D.Barceló Dr.H.Fiedler DepartmentofEnvironmentalChemistry ScientificAffairsOffice IDAEA-CSIC,C/JordiGirona18–26, UNEPChemicals 08034Barcelona,Spain,andCatalan 11–13,chemindesAnémones InstituteforWaterResearch(ICRA), 1219Châteleine(GE),Switzerland ParcCientíficiTecnològicdela hfi[email protected] UniversitatdeGirona, EdificiJaumeCasademont,15 Prof.Dr.H.Frank E-17003Girona,Spain LehrstuhlfürUmwelttechnik [email protected] undÖkotoxikologie Prof.Dr.P.Fabian UniversitätBayreuth Postfach101251 LehrstuhlfürBioklimatologie 95440Bayreuth,Germany undImmissionsforschung derUniversitätMünchen Hohenbachernstraße22 85354Freising-Weihenstephan,Germany VI Prof.Dr.J.P.Giesy Prof.Dr.J.Paasivirta DepartmentofZoology DepartmentofChemistry MichiganStateUniversity UniversityofJyväskylä EastLansing,MI48824-1115,USA Survontie9 [email protected] P.O.Box35 40351Jyväskylä,Finland Prof.Dr.R.A.Hites Prof.Dr.Dr.H.Parlar IndianaUniversity SchoolofPublic InstitutfürLebensmitteltechnologie andEnvironmentalAffairs undAnalytischeChemie Bloomington,IN47405,USA TechnischeUniversitätMünchen [email protected] 85350Freising-Weihenstephan,Germany Prof.Dr.M.A.K.Khalil Prof.Dr.S.H.Safe DepartmentofPhysics DepartmentofVeterinary PortlandStateUniversity PhysiologyandPharmacology ScienceBuildingII,Room410 CollegeofVeterinaryMedicine P.O.Box751 TexasA&MUniversity Portland,OR97207-0751,USA CollegeStation,TX77843-4466,USA [email protected] [email protected] Prof.Dr.D.Mackay Prof.P.J.Wangersky DepartmentofChemicalEngineering UniversityofVictoria andAppliedChemistry CentreforEarthandOceanResearch UniversityofToronto P.O.Box1700 Toronto,ON,M5S1A4,Canada Victoria,BC,V8W3P6,Canada [email protected] Prof.Dr.A.H.Neilson SwedishEnvironmentalResearchInstitute P.O.Box21060 10031Stockholm,Sweden [email protected] TheHandbookofEnvironmentalChemistry AlsoAvailableElectronically ForallcustomerswhohaveastandingordertoTheHandbookofEnvironmen- talChemistry,weoffertheelectronicversionviaSpringerLinkfreeofcharge. Pleasecontactyourlibrarianwhocanreceiveapasswordorfreeaccesstothe fullarticlesbyregisteringat: springerlink.com Ifyoudonothaveasubscription,youcanstillviewthetablesofcontentsofthe volumesandtheabstractofeacharticlebygoingtotheSpringerLinkHome- page,clickingon“BrowsebyOnlineLibraries”,then“ChemicalSciences”,and finallychooseTheHandbookofEnvironmentalChemistry. Youwillfindinformationaboutthe – EditorialBoard – AimsandScope – InstructionsforAuthors – SampleContribution atspringer.comusingthesearchfunction. Color figures are published in full color within the electronic version on SpringerLink. Preface Followingrelease to the environment, synthetic chemicals may be degraded by biotic and abiotic processes. The degradation of the chemical can follow a plethora of pathways and a range of other substances can be formed via thesedifferentpathways(e.g.[1]).Anumberoftermshavebeenusedforthese substancesincluding metabolites,degradatesandtransformationproducts– inthisbookweusethetermtransformationproducts.While weoftenknow a lot about the environmental properties and effects of the parent synthetic chemical,weknowmuchlessaboutthetransformationproducts. Transformationproductscanbehaveverydifferentlyfromtheparentcom- pound (e.g. [2]). For example, selected transformation products are much more persistent than their associated parent compound in soils, waters and sedimentsandsomemaybetransportedaroundthelocal,regionalandglobal environmentstoadifferentextentthantheparentcompound.Transformation products can also have very different toxicities than the parent compound (e.g.[3])andinsomecasestransformationproductscanbeordersofmagni- tudemoretoxicthantheir parent compound; althoughthissituationisrare. The environmental risks of transformation products can therefore be very differentthantherisksoftheparentcompound. Thepotentialenvironmentalimpactsoftransformationproductsarerecog- nisedbymanyregulatoryassessmentschemes.Forexample,intheEU,pesti- cideproducersarenotonlyrequiredtoassessthefateandeffectsoftheparent pesticidebutarealsorequiredtoassessthepotentialadverseeffectsofmajor metabolitesandminormetabolitesthataredeemedtobeofconcern[4].Sim- ilar requirements also exist for new human and veterinary pharmaceuticals and biocides (e.g. [5]). However, for many older substances and many other substanceclasses(e.g.industrialchemicals),dataontheenvironmentalrisks oftransformationproductscanbelimitedornon-existent. Theassessmentoftheenvironmentalrisksoftransformationproductscan howeverbechallenging.Perhapsthebiggestchallengeisthatthereareavast number of synthetic chemicals in use today which can each degrade into anumber oftransformationproducts;wedon’thavetheresourcestotestthe fate and environmental effects of the parent compounds let alone the trans- formationproducts.Theidentificationandcharacterisationoftransformation productsarisingfromaparticularparentsubstanceinaparticularsystemcan X Preface also be extremely difficult due to problems of extraction, detection at envi- ronmentally relevant levels, and quantification in the absence of standards; althoughthearrivalofnewanalyticalmethodologies(e.g.time-of-flightmass spectrometry)andtheavailabilityofexpertsystemsforpredictingtransforma- tionpathwaysisnowmakingthistasklessdaunting.Themodellingoftrans- formationproductexposureandeffectscanalsobechallengingaswearefaced withadynamicsysteminvolvingacomplexmixtureofsubstanceswherepar- entcompoundsarebeingdegradedtotransformationproductswhicharethen degradedtoothertransformationproducts.Finally,whiletreatmentmethod- ologiesthatareused tocontrolhuman andenvironmentalexposure areable toremovetransformationproducts,theycanalsoactasamechanismoftrans- formationproductformationandselectedtreatmentprocesses(e.g.advanced oxidationprocessesfordrinkingwatertreatment)mayevenproducetransfor- mationproductsmorehazardousthanthesubstancethathasbeentreated. While,thereareanumberofscientificchallengesandlargeknowledgegaps, asignificantamountofinformationisavailableontheroutesofformation,de- tection,exposure,effectsandmodellingapproachesfortransformationprod- uctsofsomeclassesofsubstances.Ifwecanbringthisinformationtogether,we shouldbeabletoassesstransformationproductsinamuchmorepragmatic way. This will allow resources to be focused on transformation products of mostconcernwhilemaintainingthehealthofthenaturalenvironment. Thereforeinthisbook,wehavebroughttogethercontributionsfromlead- ing experts in thisfield to provide an overview ofthe current knowledge on the formation, detection, occurrence, effects and treatability of transforma- tionproductsintheenvironment.Manyofthechaptersintroducemethodsfor assessingthedifferentcomponentsrequiredtodeterminetherisksoftransfor- mationproductstonaturalsystems.InthechapterMechanismsofdegradation ofsyntheticchemicals,Wackettetal.(thisvolume)discussthemechanismsby which transformation products are formed and describe how this informa- tioncanbeusedtopredictthestructuresoftransformationproducts.Howard discussesawiderrangeofmethodsforpredictingdegradationratesanddegra- dationpathwaysinthechapterPredictingthepersistenceoforganiccompounds. ThechapterAnalysingtransformationproductsofsyntheticchemicalsbyPerez etal.describesthechallengesforanalysingtransformationproductsanddis- cussestheapplicationofsomeofthenewanalyticalmethodsforidentification and quantification of transformation products in environmental systems. In OccurrenceofTransformationProductsintheEnvironment, Kolpindescribes the results of a series of monitoring studies into the occurrence of selected transformationinUSwaterbodies.Huetal.(FateofTransformationProducts ofSyntheticChemicals)discussexperimentaldataonthepersistenceandmo- bilityoftransformationproductsinenvironmentalsystemsandinthechapter Modelingenvironmentalexposuretotransformationproductsoforganicchem- icals,Fenneretal.describemodellingapproachesforassessingexposurelevels fortransformationproductsinarangeofenvironmentalsystems.Thechapters Preface XI EcotoxicityofTransformationProducts(SinclairandBoxall)andPredictingthe EcotoxicologicalEffectsofTransformationProducts(Escheretal.)describethe ecotoxicological effects of transformation products and discuss approaches that could be employed for estimating ecotoxicity based on transformation productstructureandinformationontheassociatedparentchemicals.Finally, inTreatment ofTransformationProducts,Adams et al. discuss howtransfor- mationproductscanberemovedintreatmentprocessesbutalsodiscusshow treatmentprocessescanactasroutesoftransformationproductformation. It is clear fromeach of the chapters that while we are now well placed to betterassesstransformationproductrisk,thereisstillmuchthatneedstobe done.Areaswhereweneedfurtherdevelopmentinclude: – Expert systems for predicting the nature of transformation products – Work should focus on the development of methods to identify the most probable transformation pathway in a particular environmental system. The approaches need to be evaluated against high-quality experimental dataondegradationpathwaysindifferentmedia.Newexpertsystemsneed tobedevelopedforsystemswheretheyarenotyetavailable,e.g.drinking watertreatmentprocesses. – Analyticalmethods–Weneedtodevelophigh-qualitymethodsthatareable toextractandidentifyalltransformationproductsofpotentialconcernin arangeofenvironmentalsystems.Weshouldexplorehowwecanquantify (or semi-quantify) transformation product concentrations in the absence ofstandards. – Monitoringstudiesfortransformationproducts–Anumberofmonitoring studieshaveexploredtheoccurrenceoftransformationproductsintheen- vironment.Thesestudieshavetendedtofocusontransformationproducts arisingfromtheuseofonlyafewpesticideactiveingredients.Itwouldbe usefultoprioritisetransformationproductsintermsoftheirpotentialrisk to a particular system (e.g. using approaches similar to that described by Sinclair et al. [6]) and extend these monitoring studies to a much wider range of substances. Where possible, monitoring studies should not just lookatoccurrencebutshouldalsoaimtounderstandtheunderlyingmech- anisms determining thetransport oftransformationproductsaroundthe environment. – Exposuremodels–Modelsareavailableforestimating exposureoftrans- formationproductsatarangeofscales.Thesemodelsneedevaluationand mayneedfurtherdevelopmentasourknowledgeexpands. – Ecotoxicologicaleffects – Most experimental data is on the acute toxicity of transformation products to aquatic organisms so it would be valuable to generate an understanding of the potential chronic effects as well as an understanding of the impacts on terrestrial organisms. Predictive ap- proaches for estimating the ecotoxicity of transformation products show somepromise,howevertheseneedfurtherdevelopment andvalidation.It