雌酮17雌二醇与17乙炔基雌二醇在污水样中的稳定性研究阳春

　20820088ChemicalResearchandApplicationVol.20,No.8Aug.,2008　:2008-01-10;:2008-03-18:,(CSTC,2006AB7055):(1975-),,,。Email:[e-mail]:1004-1656(2008)08-0967-05、17β-17α-阳　春1＊,胡碧波1,郑怀礼1,AndrewWheatley2,JohnChurchley3(1.,,400045;2.,LE113TU;3.SevernTrent,B263PU):(E1)、(E2)(EE2)ng·L-1,。E1,E2EE2。:(A)4℃,,22%、34%4%;14%、26%2%。(B)4℃pH=2(),E1、E2EE228%、20%4%;4%、17%1%。(C)Cu(NO3)2250mg·L-1HClpH=310℃,E1、E2EE2153%。CE1、E2EE2。:;17β-;17α-;:X132　　:Ang·L-1[1,2]。[3]。(E1)、17β-(E2)17α-(EE2)[4-5],[1]。E1、E2EE21。E1、E2EE2、E1E2,。[4]、[6][7],;Baronti[6],。Baronti[6]Carbograph4,-18℃。602%,。(EA)“”,E1、E2EE2,,、。,。图1　雌酮、17β-雌二醇和17α-乙炔基雌二醇的化学结构Fig1　Thechemicalstructuresofoestrone,17β-oestradioland17α-ethinyloestradiol化学研究与应用第20卷1　1.1　E1、E2EE2。Sigma。1g·L-1,。。0.1%。、、、FisherChemicals(UK)。1.2　156.0L,E1、E2EE252.0L。52.0L3,14,1.0L,7。,,1.0mL10.0μg·L-1E1,E2EE2,10ng·L-1。E2EE2E1,1.0L。,。。A:4℃,pH;B:H2SO4,1.0LpH=2,4℃,EA;C:Cu(NO3)2HCl,1.0LpH=3、Cu(NO3)2250.0mg·L-1,10℃。A,0、1、2、3、4、710。BC,0、1、2、5、7、9、15。1.3　[8]。0.45μm(Whatman),。,,,。C18(AlltechSupercleanTM,600mg)。5.0mL10.0mL;,5.0mL1.0min,5.0mL。5.0mL,。40-50℃,,1.0mL。(AlltechSupercleanTM,300mg),5.0mL5.0mL。1.0mL,5.0mL,6.0mL。,2.5mL,1.0mLmin-1(PolymerLabsPlgel50A,30℃),13.5min,9.0-12.0min0.2mL∶1∶9。1.4　HPLC-MS(TOF)E1、E2EE2HPLC-MS(TOF)[8]。HPLC-MS(TOF)Agilent1100,。HPLC:LunaPhenylHexyl(2.0mm×150mm,3.6(m,60℃),0.3mLmin-1,100μL。A,B95%+5%。:0.0-0.5min,95%A+5%B;0.5-1.0min,80%A+20%B;1.0-12.0min,60%A+40%B;12.0-14.0min,20%A+80%B;14.0-14.5min,95%A+5%B。MS:APPI。40psig,100-800amu,0.2mLmin-1,EIC1269.15-269.16,E1=269.1547。2　E1、E2EE227。968第8期阳　春等:雌酮、17β-雌二醇与17α-乙炔基雌二醇在污水样中的稳定性研究图2　E1在污水厂进水样中浓度随保存时间的变化Fig.2　ThevariationofE1concentrationsinanSTWinfluentsample　图3　E1在污水厂尾水样中浓度随保存时间的变化Fig.3　ThevariationofE1concentrationsinanSTWeffluentsample图4　E2在污水厂进水样中浓度随保存时间的变化Fig.4　ThevariationofE2concentrationsinanSTWinfluentsample　图5　E2在污水厂尾水样中浓度随保存时间的变化Fig.5　ThevariationofE2concentrationsinanSTWeffluentsample图6　EE2在污水厂进水样中浓度随保存时间的变化Fig.6　ThevariationofEE2concentrationsinanSTWinfluentsample　图7　EE2在污水厂尾水样中浓度随保存时间的变化Fig.7　ThevariationofEE2concentrationsinanSTWeffluentsampleE165.4ng·L-1,4℃(A)71064%74%;pH=2(B),71513%42%;(C),pHB,2%4%。10ng·L-1E117.7ng·L-1。4℃(A),E178.7ng·L-1,51%;10,4.9ng·L-1,72%。pH=24℃(B),E1:7,14.2ng·L-1,20%;15,E111.2ng·L-137%。Cu(NO3)2HClpH=3(C),E11517.2ng·L-1,969化学研究与应用第20卷3%,AB。E2,4℃(A)E1,143.6ng·L-131.9ng·L-1,27%;11.3ng·L-18.3ng·L-1,26%;350%。pH24℃(B),E2,50%15。pHCu(NO3)2(C)E2,15E23%,E1。EE2,15,4-6%,3-5%。EE2。,E1E2,。EApH=24℃2E1E2。Cu(NO3)2250.0mg·L-1HClpH=310℃15E1E23%。,,。3　(1)pH=24℃E1E2。2,E1E24%17%。。(2)HCl+Cu(NO3)2(pH=3)10℃153%。,,,。(3)EE2,15,3-6%。:[1]ButwellAJ,GardnerMJ,Gordon-WalkerSJ,etal.ScopingstudyforanationaldemonstrationprogrammeonEDCremoval[M].UK:UKWIR,06/TX/04/11,2005.[2]JoblingSNolanM,TylerCR,etal.Widespreadsexualdisruptioninwildfish[J].Env.Sci.Tech.,1998,32(17):2498-2506.[3]DamstraT,BarlowS,BergmanA.etal.Globalassessmentofthestate-of-the-scienceofendocrinedisruptors[M].WHO.2002.[4]DesbrowC,RoutledgeEJ,BrightyGC,etal.IdentificationofoestrogenicchemicalsinSTWeffluent.1.Chemicalfractionationandinvitrobiologicalscreening[J].Env.Sci.Tech.,1998,32(11):1549-1558.[5]RoutledgeEJ,SheahanD,DesbrowC.etal.IdentificationofoestrogenicchemicalsinSTWeffluent.2.invivoresponsesintroutandroach[J].Env.Sci.Tech,1998,32(11):1559-1565.[6]BarontiC,CuriniR,DAscenzoG,etal.Monitoringnaturalandsyntheticestrogensatactivatedsludgesewagetreatmentplantsandinareceivingriverwater[J],Env.Sci.Tech.,2000,34(24):5059-5066.[7]LópezdeAlda,MJ,BacelóD.Determinationofsteroidsexhormonesandrelatedsyntheticcompoundsconsideredasendocrinedisruptersinwaterbyliquidchromatographydiodearraydetectionmassspectrometry.[J]JournalofChromatographyA,2000,892,391-406.[8]HuoC,HickleyP.(2006)Anglianwater'sapproachtotheEDCdemonstrationprogrammeasanearlystartcompany[A],CIWEMconferenceproceeding-endocrinedisruptingchemicalsinthewaterenvironment[C].Nottingham:2006.970第8期阳　春等:雌酮、17β-雌二醇与17α-乙炔基雌二醇在污水样中的稳定性研究Stabilitytestsofoestrone,17β-oestradioland17α-ethinyloestradiolinsewagesamplesYANGChun1＊,HUBi-bo1,ZHENGHuai-li1,AndrewWHEATLEY2,JohnCHURCHLEY3(1.KeyLaboratoryofEco-environmentsinThreeGorgesReservoirRegion(MinistryofEducation),ChongqingUniversity,Chongqing400045,China;2.LoughboroughUniversity,LeicestershireLE113TU,UK;3.SevernTrentWaterLtd.,BirminghamB263PU,UK)Abstract:Oestrone(E1),17β-oestradiol(E2)and17α-ethinyloestradiol(EE2)arethemostconcernedendocrinedisruptingchemicalstoberegulatedbyenvironmentalqualitystandardsintheUK.Theyarepresentinsewageatanng·L-1level.ConcentrationsofE1,E2andEE2insewagesamplespreservedinthreedifferentwaysareanalysedinatimespell.Onlypreservedinthedarkat4°C(MethodA),22%and34%lossareseenintheSTWinfluentsample,and14%and26%lossareobservedforE1andE2intheSTWeffluentsample.8%E1and20%E2intheSTWinfluentaswellas4%ofE1and17%ofE2intheSTWeffluentarelostin2dayswhenpreservedinthedarkat4°CwithpH=2(MethodB),whichisrecommendedfororganicanalytesbytheUKEnvironmentalAgency(EA)standardmethod.ThelossofEE2intheabovetwopreservingmethodswerelessthan2%in10days.Itisrecommendedtospikesamplesins