给水工程英文文献翻译.docx

附录己外文文献及其译文外文文献：RemovalofPharmaceuticalsduringDrinkingWaterTreatmentTheeliminationofselectedpharmaceuticals(bezafibrate,clofibricacid,carbamazepine,diclofenac)duringdrinkingwatertreatmentprocesseswasinvestigatedatlabandpilotscaleandinrealwaterworks.Nosignificantremovalofpharmaceuticalswasobservedinbatchexperimentswithsandundernaturalaerobicandanoxicconditions,thusindicatinglowsorptionpropertiesandhighpersistencewithnonadaptedmicroorganisms.TheseresultswereunderscoredbythepresenceofcarbamazepineinbankfiItratedwaterwithanaerobicconditionsinawaterworksarea.Flocculationusingiron(lll)chlorideinlab-scaleexperiments(Jartest)andinvestigationsinwaterworksexhibitednosignificanteliminationoftheselectedtargetpharmaceuticals.However,ozonationwasinsomecasesveryeffectiveineliminatingthesepolarcompounds.Inlabscaleexperiments,0.5mg/Lozonewasshowntoreducetheconcentrationsofdiclofenacandcarbamazepinebymorethan90%,whilebezafibratewaseliminatedby50%witha1.5mg/Lozonedose.Clofibricacidwasstableevenat3mg/Lozone.Underwaterworksconditions,similarremovalefficiencieswereobserved.Inadditiontoozonation,filtrationwithgranularactivatedcarbon(GAC)wasveryeffectiveinremovingpharmaceuticals.Exceptforclofibricacid,GACinpilot-scaleexperimentsandwaterworksprovidedamajoreliminationofthepharmaceuticalsunderinvestigation.IntroductionInGermany,somepharmaceuticalsareusedinquantitiesofmorethan100t/yr(1).Pharmacokineticstudiesexhibitthatanappreciableproportionoftheadministeredpharmaceuticalsareexcretedviafecesandurine(2)andthusarepresentinthedomesticwastewater.Afurthersourceforthecontaminationofwastewaterisassumedtobethedisposalof(expired)medicineviatoilets.However,thisportionisverydifficulttoestimatebecausereliabledataarenotavailable.Afterpassingthroughsewagetreatmentplants(STPs),pharmaceuticalresiduesenterreceivingwaters.Pointdischargesfrompharmaceuticalmanufacturerscanalsocontributetocontaminationofriversandcreeks(3).Firstresultsconcerningenvironmentaloccurrenceofpharma-ceuticalsarereportedbyGarrisonetal.(4)andHigniteandAzarnoff(5),whodetectedclofibricacidinthelowermicrogramsperliterrangeintreatedsewageintheUnitedStates.Furtherstudiesin1981inGreatBritainrevealedthatpharmaceuticalsarepresentinriversupto1ig/L(6).OnIonaIsland(Vancouver,Canada)Rogersetal.(7)identifiedthetwoantiphlogisticsibuprofenandnaproxeninwaste-water.Recentinvestigationsshowedtheexposureofawiderangeofpharmaceuticalsfrommanymedicinalclasses(e.g,betablockers,Sympathomimetics,antiphlogistics,lipidregulators,antiepileptics,antibiotics,vasodilators)toriversandcreeks.ReviewsfromHalling-SOrensenetal.(8),DaughtonandTemes(9),andJOrgensenetal.(10)summarizemostoftheliteratureinthisnewemergingfieldabouttheenviron-mentalrelevanceofpharmaceuticals.Furthermore,Mohleetal.(11),Alderetal.(12),Temesetal.(3),andZuccatoetal.(13)havereportedtheidentificationofpharmaceuticalsintheaquaticenvironment.Contaminationisinfluencedbytherelativeportionsofrawandtreatedwastewater(14)suchthatevensmallriversandcreekscanbehighlycontaminated.Groundwateriscontaminatedwithpharmaceuticalsprimarilybyinfiltrationofsurfacewatercontainingpharmaceuticalresiduesaswellasbyleaksinlandfillsitesandsewerdrains.Becauseofthewidespreadoccurrenceofpharmaceuticalsintheaquaticenvironmentandsometimesalsointherawwaterofwaterworks,afewcasessurfacedwherepharmaceuticalsweredetectedindrinkingwaterinthelowernanogramsperliterrange(15,16).Althoughuptonownoadversehealtheffectscanbeattributedtotheconsumptionofpharmaceuticalsattheselowconcentrationlevels,basedonprecautionaryprinciples,drinkingwatershouldbefreeofsuchanthro-pogeniccontaminants.Currently,fewpapershavebeenpublisheddealingwiththeremovalofpharmaceuticalsindrinkingwatertreatment.Ozonationandespeciallyadvancedoxidationprocessesseemtobeveryeffectiveinremovalofdiclofenac,whileclofibricacidandibuprofenwereoxidizedinlab-scaleexperimentsmainlybyozoneH2O2asshownbyZwienerandFrimmel(17).Hebereretal.(18)exhibitedthatreverseosmosisisappropriatetoremoveavarietyofdifferentpharmaceuticalsfromhighlycontaminatedsurfacewaters.Theobjectiveoftheworkpresentedherewastostudytheefficiencyofdifferenttreatmentstepstoremovetheanti-phlogisticdiclofenac,theantiepilepticcarbamazepine,andthelipidregulatorsclofibricacidandbezafibrateduringdrinkingwatertreatment.Therefore,theprimaryeliminationoftheselectedpharmaceuticalswasinvestigatedunderlaboratory,pilot,andrealwaterworksconditions.Inadditiontoprocessessuchasbankfiltrationandartificialgroundwaterrecharge,widelyusedtechniquesforsurfacewatertreatmentsuchasactivatedcarbonfiltration,ozonation,andfloccula-tionwereinvestigated.ThemonitoringresultsoftwoGermanwaterworksareextendedbylab-andpilot-scaleexperimentstoobtainmoregeneralizedresults.ExperimentalSectionSelectedpharmaceuticals.Foralllab-andpilot-scalespikingexperiments,fourrelevantpharmaceuticals(theantiphlo-gisticdiclofenac,theantiepilepticcarbamazepine,thelipidregulatorsclofibricacidandbezafibrate)havebeenselectedastargetcompounds.TheirmolecularstructuresareshowninTable1.ThesecompoundshavebeenchosenbecauseoftheirpredominantoccurrenceinGermanfeedingwatersforwaterworkssuchasrivers,bankfiltrates,andground-water(14,19).Additionally,theantiepilepticprimidonewasincludedinoxidationexperimentsandawaterworkssurvey.Primidone144-LI-6andepilepticTABLELSeIeCtedTargetPharmaCeUtiCaISNameCAS-numberChcmiculstructureAppJicationClofibrieacid4LS5M7-08睫-09-7crJJlipidr霏ImotITicLaboIiIcoflipidicgularorsclcfibrate.erofibme,theofibrateDkkfenacCarbamazepine15307-86525M5-4HODt.1rfaniipMogiMKantiepilepticAnalyticalMethods.Thedeterminationofthepharma-ceuticalswasperformedusingdifferentanalyticalmethods(seeTable2).Allmethodswerebasedonasolid-phaseextractionoftheanalytesontoRP-CisorLichroluteENmaterial.Aftersolid-phaseextraction(SPE)andanelutionstepwithmethanoloracetone,thecompoundswerederivatizedusingdifferentagents.Eitheramethylationwithdiazomethane(20)oraSilylationwithamixtureofN,O-bis(trimethylsilyl)acetamide(BSA)and5%trimethylchlo-rosilane(TMCS)(Fa.Fluka,Buchs,Schweiz)wereused(60minat120oC)(21).CarbamazepinewasdeterminedaftersilylationeitherbyamixtureofMSTFATMSIDTE(N-methyl-N-(trimethylsilyl)trifluoroacetamide/trimethylsilylim-idazol/dithioerytrit;1000iL/2yfZ2ig)(22)orbyamixtureofBSA/TMCS.Forprimidone,anacetylationbyacetanhy-drideandethanolaminewasused(22).Inallcases,GC-MSwasusedforthedetectionoftheanalytes.Furtherdetailsofthemethodsarereportedinrefs19-22.Allmethodsenabletheprecisedeterminationofthetargetpharmaceuticalsinriverwateranddrinkingwater.Aninterlaboratorycomparisonexercise(ICE)betweenthethreeparticipatinglaboratoriesatthebeginningandtheendofthestudyconfirmedthequalityoftheanalyticalmethods.Groundwaterandsurfacewatersampleswerespikedwiththeselectedpharmaceuticalsandanalyzedbyallthreelaboratoriestoconfirmtherecoveriesoftheanalytesintherespectivematrixes.Themeanrecoveryofthespikedconcentrationsalwaysexceeded70%throughdifferentspikingIeVelS:0.40-0.90ig/Linsurfacewaterand0.030-0.20ig/Lindrinkingwater.Therelativestandarddeviationsbetweenthethreeparticipatinglaboratorieswereingeneralbelow25%.Thus,itcouldbeshownthat(i)thedifferenceoffoundconcentrationswasminorbetweentheIhreelaboratoriesand(ii)thespikedconcentrationcouldbedetectedinthegroundwaterandsurfacewateraccuratel.1.imitsofQuantification(LOQ)andCalibration.TheLOQwascalculatedaccordingtotheGermanDIN32645(23)withaconfidenceintervalof99%usingthestandarddeviationofalinearregressioncurve.Calibrationrangesfrom0.005to0.050ig/Landfrom0.05to1ig/Lwereusedwithatleastsevenconcentrationlevelsbyspikinggroundwater.LOQisanothertermforlimitofdetermination(LOD)mentionedinDIN32645.SincethecalculatedLOQvalueswerealwaysbetweenthefirstandthesecondcalibrationpoints,theLOQusedwassetasthesecondlowestcalibrationpointofthelinearcorrelationtoensureaprecisequantification.Hence,theLOQwereatleast20ng/Lfordiclofenac,carbamazepine,primidone,andclofibricacidanddownto50ng/Lforbezafibrate.However,withafinalvolumeof100亿insteadof1mL,LOQdownto2ng/Lwereachievedforclofibricacid,primidone,diclofenac,andcarbamazepineanddownto10ng/Lforbezafibrate.Thecalibrationwasperformedoverthewholeprocedureafterspikinggroundwaterwiththestandardmixtureoftheselectedpharmaceuticals.Thecalculationoftheconcentrationsinnativesampleswascarriedoutusingsurrogatestandards(seeTable2)andalinear7-10pointcalibrationcurve.ReferenceStandards.Thereferencestandardsclofibricacid,bezafibrate,carbamazepine,diclofenac,andprimidoneaswellasthesurrogatestandardsmeclofenamicacidand2,3-dichlorophenoxyaceticacid(2,3-D)werepurchasedfromSigma,Germany;dihydrocarbamazepinewaspurchasedfromAlltech,Germany.Allstandardsweredissolvedinmethanol(1mgmL)anddilutedwithmethanoltothefinalstocksolutionof10igmL.TreatmentProcessesUsedinWaterworks.(a)StudyofBiodegradationinBatchExperimentswithNativeSurfaceWater,Groundwater,andDifferentFilterMaterials.Bio-degradationisoneofthecrucialfactorsthatdeterminetheeliminationoforganiccompoundsduringartificialground-waterrechargeandbankfiltration.Toassessthegeneralbiodegradabilityofpharmaceuticalsinaquaticenvironmentalmatrixes,batchexperimentswerecarriedoutaccordingtotheOECDguidelinesfortestingchemicals(24).Theinoc-culumusedconsistedof400mLofsurfacewaterand400mLofgroundwatermixedwith2LofMITIbasalmedium.TheMITIbasalmediumwaspreparedbymixing1Lofsteriledeionizedwaterwith3mLofsterilizedsolutionsA-D.SolutionAwasasolutionof21.75gofK2HPO4,8.5gofKH2PO4,44.6gofNa2HpO4A12H2O,and1.7gofNH4C1ini000mLofdeionizedwateratpH7.2.SolutionsB-Dweresolutionsof22.5gofMgSO4A7H2O,27.5gofCaC12,and0.25gofFeCh,respectively,in1000mLofdeionizedwater.ThegroundwaterwastakenfromaGermanwatercatchmentareawithartificialgroundwaterrechargeusingslowsandfiltrationandbankfiltration.Theindividualconcentrationsofbezafibrate,carbamazepine,clofibricacid,diclofenac,andibuprofenwereinthebatchexperimentsadjustedto0.1and100ig/L.Thebatchexperimentswereexposedtoeitherindividualoramixtureoftheselectedpharmaceuticals.Instocksolutionswithethanol,theconcentrationsofthetestedpharmaceuticalswere0.5mg/mLor0.5igmL,respectively.Afterbeingdiluted(480Lofstocksolutionin2.4Lofculturesolution),theconcentrationofethanolinbatchcultureswas0.02%(v:v).Thecultureswerealwaysincubatedinthedarkfor28dat14(insitutemperature).Foranoxicconditions,25mg/Lnitratewasaddedasanalternativeelectronacceptor.Thebottlesusedweregastight.Foraerobicsorptionexperi-ments,400gofsandor400gofgraveltakenfromtheundergroundofagroundwatercatchmentareawasusedasinocculumandmixedwith2LofMITIbasalmedium(solidphase/liquidphase)1:5).Sandthatisalsousedfortheslowsandfiltersofawaterworksconsistsofameangrainsizerangeof0.2-0.6mm.ThisfiltermaterialshowedamoderatepermeabilitywithaK/coefficientof4.3IO'4ms.Thegravel(naturalaquifersediment)wasveryheterogeneouswithapredominantfractionof2-10mmgrainsizeandaKjcoefficientof2.910'3ms.Sterilecontrols(sterilizationfor1h)werepreparedtodifferentiatebetweensorptionandmicrobialdegradation.Thesandcontains3.2mg/gironand0.056mg/gmanganese.Coatingswithironandmanganesehydroxidesweredetectedinthegravelbutwerenotquanti-fied.Esteraseactivitiesweremeasuredtocontrolthephysi-ologicalstatusofmicrobialcommunitiesduringtheincuba-tionofbatchcultures.Thehydrolysisoffluoresceindiacetate(FDA)byesteraseenzymeswasdeterminedaccordingtotheprocedureofSchnu"rerandRosswall(25).A20-iLvolumeofFDAsolution(20mg/10mLacetone,storedat-18)wasmixedwith3mLofsampleand0.5mLofHEPESbuffer(0.1MN-2-Hydroxyethylpiperazine-NC-2-ethansulfonicacidso-diumsaltindeionizedwater,adjustedtopH7.5;Merck).Afterbeingincubated(sterileconditions,90minat20oC,darkness),thefluoresceinformationwasimmediatelymea-suredwithaPerkin-ElmerfluorescencespectrometerLC(excitationat480nm,emissionat505nm).(b)Flocculation.ForflocculationexperimentsinIab-Scaleexperiments,anoncontinualprocedure,theso-called"Jartest1*,wasperformed.Spikingconcentrations,stirringvandreactiontimeswereselectedaccordingtoparametersofthetwowaterworksmonitoredinparallel.Thelabdeviceusedconsistsofglassbeakers(v)2L)withstator,astirrerwithstandardizedstirrergeometry,anddefinedsubmergedstirringdepths.Thestirringvelocitywasadjustedaccordingtothemeanvelocitygradient(Gvalue),whichisproportionaltotheintroducedenergyandthustotheaggregationofcolloids(26).Understirring(rpm:400min'1),0.1mLofiron(l11)chloridesolution(40%)wasaddedto1.8Lofrawwater(spikedwith1ig/Lpharmaceuticals).Afterastirringtimeof1min,pH7.5wasattainedbyaddingCa(OH)2(lmolL).Then,theaggregationtomicroflocswasachievedbystirringslowlyfor20minunder30minl.Aftersedimentationfor20min,asamplewastakenfromunderthewatersurface,andtheturbiditywasmeasured.Thesemeasurementsshowedthattheturbiditywasalwaysbelow1.5turbidityunitsofIbrmazine(TU/F).TABLE工AnalyticalMethodsUsedIcrDetenninationoftheTargetPharmaceuticalsmethodASCidmpotids"MhodBcarbamazepinemeUhudCacid8moLndSAcarbamazepinenwthDdDprimidonesamplevol(IL)1111filtrationglassfibers(=1tm)gldssfibers(<1glassfibers(<1rm)glassfibers(<1rmpH2.07.5io7.5SPEmalcrhlCL5gofRP-Ce(ilsolut)1gofRP-iSeC(Baker)1gofRPC18(IS0.5gofEN(Merck)elulon3mLofmehanol1AmLofmethanol4mLofAiCeIOnewaporatlon4mLofmrelhano'l,evaporationIodryness,additionot1mLofMhexaneevaporationIodrynesstodrynessWaporatlofitodrynessCierivatlzabofiaddHlonOfdiaZOmelhane50,trLofSllylationmixtureA?(fj也口mlnat1204OIDOjLofsllyhUonrnlxlijfeB-(fui&0mlrtat1120aC)16O.hLacetk:anhydrt×Je/Emity怕m21：1Sunogalcstandardmeclofenamkcacidd1hydrocarDamaztpine2r3-dlchIorophenoxyacelic3cW(5.3-D)dIhydrocaftama2cpl<ncGC.MSHP6890GCHP5970MSDHP6S90GCHP5(7)MSDGCQ(FinniganMAT)GC8000MD耽(Fbsons)GClumXTfl-560mx0.25mmX0.2=DBS130mx0.25mmKDB35(30m×CL2SmmxXTI-5(30mM0.55mmKRe-Slek)0.25lm,j4W)0.25/em.J&W)0J5pm.Rostek)injection2MLSM/spHllessat箱0,5LcoldinjectionGfirmiany)2jjLspi11/SPlItfSSat276空SuLsplivspHtisssat.加空tempprogram606C1.5ml50bC(1mln)5日(1mlr)20AmInto20ACftnInto120交6Io200P9dCmJnIo2My(10mln)MiCAninlOlTOACaXfrnlnto300,C(6min)U-CmltoISOaC5Gzminto300cC(3mln)1604ACAlninto280'C20阖mintt>30CrlC10mln)scanmode*51MSIMHullscan(rangemfiBO-400)-SIMliterature20222722(C)ActivatedcarbonAdsorption.AdsorptionIsothermsTorthedeterminationoftheadsorptionisotherms,thefollowingparametershavebeenused:(i)200mLofdeionizedwalerorgroundwaterspikedwithinitialconcentrationsof100ig/Lofthepharmaceuticalsunderinvestigation,(ii)pulverizedgranularactivatedcarbonbasedoncoal,(iii)quantitiesofactivatedcarbonvariedtoachieveafinalconcentrationofthepharmaceuticalsinthesolutionthatisatleast2ordersofmagnitudessmallerthantheinitialone,(iv)smallportionsofactivatedcarbon(<0.2gL)addedassuspension,(v)batcheswithactivatedcarbontumbledin250-mLflasksfor24h,(vi)finallyallsampleswerefilteredwith0.45-iinpolycarbonatefilterandanalyzedaccordingtotheanalyticalmethoddescribedbefore.Evaluationoftheisothermswasperformedindoublelogarithmicscaleac-cordingtoFreundlich(27,28).Forasinglecompound,theFreundlichequationq)Kcndescribestherelationbetweentheloadingqoftheactiva