Studies On Levels Of Estrogens In Licun River-Jiaozhou Bay Water Area

Estrogens such as estril (E3),estradiol (E2) and estrone (El)which are excretedby humans and animals or synthetic compounds such as 17β-ethinyl estradiol (EE2)are a group of hormone steroids.These compounds could affect wildlife and humanhealth by disrupting their normal endocrine systems.With number of populations andanimals increasing,amount of these steroids hormones will be discharged toenvironment and cause potential threat to the ecological balance.Therefore,thestudies on estrogens in environment is very important.For Investigation on whether waters in Qingdao are polluted by estrogens,in thispaper,levels of four hormone steroids in aquatic environment in Licun river -Jiaozhou Bay in Qingdao in China were determined by Gas chromatography Massspectrum (GC-MS) method .According to the levels of estrogens in water,sedimentand shellfish meat tissue from the waters,pollution of estrogens in the aquaticenvironment will be evaluated.Moreover,estrogens in water from Haipo river watersamples and Shilaoren and Zhanqiao seawater sample were studiedIn this work,an off-line solid-phase extraction procedure,using a modifiedpolymeric sorbent,in combination with GC-MS detection was proposed for theanalysis of estrogens in waters,sediment and shellfish samples.All steps comprisedin the analytical procedure were systematically studied.In the first,three natural (E1,E2,E3)and synthetic estrogens (EE2) werederivatized with N-methyl-N-(trimethylsilyl)trifluoroacetamide(MSTFA) ortrifluoroacetyl anhydride (TFA) and determined by GC.Derivatization conditions inthe yield of the process was systematically investigated.Under optimal conditions,quantification limits between 6.9 and 21.9ng/L were achieved for trifluoroacetylestrogens by injection way of samples condensed on needle and these of estrogens silylated were 1.3 and 9.8 ng/L by GC-FID mode.The results showed that recoveriesof estrogens spiked in real samples can be accurately detected by the GC-FID mode.Estrogens in real samples were detected by GC-MS mode and the detected limits areE1=1.98ng/L,E2=1.91ng/L,EE2=6.98ng/L,E3=2.15ng/L or ( solid ng/g) byGC-MS mode,respectively.Qualitative analysis of the targets in real samples aretaken by diagnostic ion of mass spectrum,the concentration are calculated usingmethod of internal standard or internal standard calibration curve.Correlationcoefficients of these curves are between 0.98 and 0.99.The relative standard deviationreached 3～15%.The second,considered estrogens in real samples are extracted by C-18 solidphase extraction (SPE) (or) liquid-solid extraction method.Properties of the C-18silica particles that sorbs estrogens,influence of parameters such as breakthroughvolumes ,PH of water samples,nature of the samples and soon in the recoveries ofthe solid-phase extraction step and in the cleanliness of obtained extracts wereexamined and optimized.Furthermore,according to conditions of real samples,C-18sorbent were modified and recoveries of estrogens spiked in pollution samplesreached 88-120% by using 400mg of the silica particles.The recoveries ofestrogens in the water,sediment and meat samples were 70～120% by extraction andanalysis (GC-FID mode) on the performance of the whole analytical procedure.Finally,the developed method was applied to the determination of estrogens ineffluent sewage water samples,sediment and shellfish tissue such as oysters andcalms from Licun river-Jiaozhou gulf for 3～6 month in 2005～2007 years.The resultsshowed that estrogens such as mainly E1,E2 and E3 were found in every sample butEE2 exited in several samples.Levels of estrogens in water samples were nd( notdetected)～306.0 ng/L,nd～42.0 ng/g dry soil in sediment and nd～29.7ng/g wet weighin shellfish tissue.Moreover,estrogens from water in Haipo river were between 31.0and 97.0 ng/L,nd～13.3ng/L and nd～10.0ng/L in sea water from Shilaoren orZhanqiao,respectively.Estrogens concentration were nd～5.9ng/g dry soil in activesludge from Licun wastewater treatment plant.Compared to some determining valuefrom China,our results are similar with ,but estrogens levels in three kinds of samples are similarly with reported value or higher than these from other countries.The distribution of estrogens in water and sediment are as follow:First,estrogenslevels in water and sediment were affected by water quality of fiver or sea water,forexample estrogens contents in different location not only exited significant difference(such as the levels in fiver was higher than that in sea) but it did in different time inthe same sampling side.Second,concentrations of E1 in most samples were higherthan these of E3.Third,in most sampling sites,proportions of E1 in sediment andwater ranged from 28～444 L/kg,these of E3 were 20～140L/kg.Forth,estrogenslevels in oysters tissue on rocks in beach were higher than these in blue seawater andmore estrogens in clams in the sediment in estuary were found than these in market.Finally,persistence of these hormone steroids in water or sediment in the zone wasclear for 3 and 5 month and levels of estrogens in shellfish tissue were higher thanthat from sediment in clam habitat。According to the survey,Licun River mainly came from the discharging ofindustry and agriculture,domestic sewage effluents and disposal of animal waste.This results show that estrogens have entered the aquatic environment in Licunriver and Jiaozhou Bay,estrogens levels in the water might affect endocrine system ofsensitive wild animals in the zone.However,further investigations are necessary tounderstand whether or not the estrogens pollutions caused harm to ecosystem in thewater.