典型规模化养猪场废水中兽用抗生素污染特征与去除效率研究陈永山

3011201011ActaScientiaeCircumstantiaeVol．30No．11Nov．2010No．2008ZX07101-006-052008ZX07101-006-06No．40930739“、”SupportedbytheWaterSpecialProjectNo．2008ZX07101-006-052008ZX07101-006-06theKeyProjectofNationalNaturalScienceFoundationofChinaNo．40930739andtheInitialFundingforOutstandingDoctoralDissertationorPresidentialAwardofChineseAcademyofSciences1980—[e-mail]*[e-mail]1980—[e-mail]*[e-mail]currenceanddissipationofantibioticsinswinewastewaterJ．ActaScientiaeCircumstantiae30112205－221212112*33121．2100082．1000493．2100362010-03-172010-04-152010-06-28/．、、413．65×103ng·L－1．、3675．4ng·L－1．．．10ng·L－1．、．0253-2468201011-2205-08X592AApreliminarystudyontheoccurrenceanddissipationofantibioticsinswinewastewaterCHENYongshan12ZHANGHaibo1LUOYongming12*HUGuanjiu3ZHAOYonggang3SONGJing121．KeyLaboratoryofSoilEnvironmentandPollutionRemediationInstituteofSoilScienceChineseAcademyofSciencesNanjing2100082．GraduateSchooloftheChineseAcademyofSciencesBeijing1000493．EnvironmentalMonitoringCenterofJiangsuProvinceNanjing210036Received17March2010receivedinrevisedform15April2010accepted28June2010AbstractTheoccurrenceanddissipationofthefollowing11selectedantibioticswerestudiedinswinewastewateratonelargeanimalfeedingoperationAFOusingHPLC/MS/MStetracyclineTCoxytetracyclineOTCchlortetracyclineCTCdoxycyclineDXCsulfadiazineSDsulfamethoxazoleSMTsulfamethazineSMXnorfloxacinNFCofloxacinOFCerythromycin-H2OETM-H2OandroxithromycinRTM．ThewastewatersampleswereunavoidablycontaminatedwithantibioticsandthemaincontaminantswereTCOTCCTCandDXCwithmaximumconcentrationsofindividualcontaminantsreaching13．65×103ng·L－1．ThesulfonamidesSDSMXandSMTwerealsopresentinmeasurableconcentrationswithamaximumvalueof675．4ng·L－1forSMT．OFCETM-H2OandRTMwereobservedintherawwastewateronly．Anaerobicdigestiontechnologycansignificantlydegradethecontaminantsbutshowedlowefficienciesofdissipationofotheranalytesatlowerlevelsofcontamination．OnthebasisoftheEuropeanUniontriggervalue10ng·L－1effluentwaterfromthiswastewatertreatmentsystemmayposeriskstotheaquaticenvironmentinthevicinityoftheswinefarmbecauseoftheantibioticspresentathigherconcentrations．Itisimportanttocomparetheactualconcentrationsofveterinaryantibioticsinwastewaterproducedbythisfarmandthepredictedconcentrationscalculatedonthebasisofdetectionintheanimalfeedsused．GreaterattentionmustbegiventothepatternofuseofmedicinesonthefarmincludingenvironmentalriskassessmentandresearchonthemitigationofDOI:10.13671/j.hjkxxb.2010.11.00730antibioticcontaminants．Keywordsswine-feedingoperationswastewatercontaminationveterinaryantibiotics1Introduction、、、．30%～90%Sarmahetal．2006．mg·kg－1μg·L－1BoundandVoulvoulis2004Huetal．2008Benetal．2008Venglovskyetal．2009Morleyetal．2009．6000tZhaoetal．201030%～90%1800～5400t．200743989.520082．5m3GB18596－2001．COD、BOD、Benetal．2009．．．2Materialsandmethods2．1＞98%MerckMerckKGaADarmstadtGermany、Milliport．、、、、、7DrDr．EhrenstorferGmbHGermany1．1ESI-MS/MSTable1AnalyzedantibioticcompoundsandoptimizedESI-MS/MSparametersforthetargetantibioticsm/zm/z/V/VTetracyclineTC444．4596．0%445．3154303541020354271030OxytetracyclineOTC460．4497．0%461．3381304042620404431040ChlortetracyclineCTC478．8992．0%479．1154303544420354621535DoxycyclineDXC444．4598．5%445．1154303541020354281535SulfadiazineSD250．2899．5%251．191．93030155．91530SMX253．2899．0%254．292．23030Sulfamethoxazole107．920306022111m/zm/z/V/VSMT278．3399．0%279．191．93035Sulfamethazine155．920351862035NorfloxacinNFC319．3499．6%320．05276．42040302．22040OfloxacinOFC361．3899．0%36230220402612040Enythromycin-H2OETM-H2O733．9593．5%734．51583535576．32035RoxithromycinRTM837．0794．1%837．61583935679．42035EDTA-McIlvaine12．9g27．5g37．2g1LpH≈4．0．/WatersAquity/TQDMasslynx4．0BEHC18100×2.0mm1.7μmBCHILabortechnikAGSwitzerlandCNWTechnologiesGmbHGermanyLC-SAX3mL·500mg－1SupelcoofSigma-AldrichIncUSAHLB6mL·500mg－1WatersCorp．USA0．22μm．2．21．4①、②、③④、、2～3m．20m2．0m．2d120．→→→1Fig．1Wastewatertreatmentprocess2．3Xu20070．45μm500mL0．5gEDTA-Na25%v/vpH3．0LC-SAXHLB10mL、10mL3．0mL·min－1．10mLLC-SAXHLB20min6．0mL·min－110mL0．1%v/v1．0mL·min－12mL1．0mL13C-1．0mg·L－110μL0．1%v/v1．0mL0．22μmHPLC-MS/MS．20082．000g80mL/EDTA-Mcllvainev/v=1∶120mL30min．30min230mL．2．4HPLC-MS/MSAB0．1%v/v．10%B0～10min100%BAB10min．30℃0．3mL·min－15μL．ESI-MS/MSESI-702230MS/MS1．ESI-MS/MS+4000V290℃SourceCID10VCID1．0mTorr．2．513C-1．0、2．0、5．0、10．0、20．0、50．080．0μg·L－17R20．99．2．2Table2RecoveryrateandmethoddetectionlimitMDLforsurfacewateranddrinkingwater1LOQ/ng·L－1TC84．4%±7．7%87．4%±8．7%0．1OTC75．5%±6．3%73．3%±7．4%1．0CTC77．2%±10．4%77．2%±12．2%1．0DXC69．7%±8．9%62．5%±7．8%0．1SD88．9%±23．2%74．2%±7．4%0．1SMX84．1%±17．7%74．2%±10．1%0．1SMT80．7%±0．4%77．5%±3．7%0．01NFC79．9%±6．7%82．9%±2．2%0．1OFC90．7%±43．1%77．0%±12．0%0．1ETM-H2O74．9%±6．0%84．0%±1．9%0．01RTM71．4%±9．8%68．0%±10．8%0．0117LOQLOQ=S×tn－10．99S7n－10．9999%LOQ．3Results3．13．TC、OTC、CTCDXC4967.6、12.07×103、13．65×1033．635×103ng·L－1．TC、OTCDXC31．05×103、60．50×103100．75×103ng·L－1CTCCTC2008TC、OTCCTC1．14×103～