氯消毒对乙炔基雌醇的去除及雌激素活性消毒副产物的生成
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摘要
乙炔基雌醇(EE2)是最强的合成雌激素之一,在水环境中广泛存在,为探究水处理中氯消毒工艺对EE2的去除效果,并研究雌激素活性消毒副产物的生成,采用二级出水和自配水进行了模拟氯消毒实验,并运用酵母雌激素报告基因法和雌激素受体蛋白亲和层析法进行了检测。结果表明:对于自配水中的EE2,氯消毒在[Cl]/[EE2]质量浓度比达到20后,能够将雌激素活性的去除率稳定在96%～98%。在pH=6-9区间内,pH=8是最为适宜的pH值,pH值通过影响EE2与次氯酸在水溶液中的离子化状态,进而EE2氯消毒去除效率。二级出水中的氨氮使EE2的去除率降低到58.1%,而DOC对于消毒速率有所影响,但对总体去除率影响不大,氨氮与自由氯结合形成氯胺阻碍了氯消毒对EE2的去除。EE2在氯消毒后,即使EE2本身几乎被完全去除,仍旧残留雌激素活性。由雌激素受体蛋白亲和分离的结果证实,在EE2的消毒副产物中,产生了新的具有雌激素活性的物质。
Ethynylestradiol(EE2) is one of the strongest synthetic estrogens, which is widely found in water environment. To explore the removal of EE2 by chlorine disinfection in water treatment, and to study the estrogen activity of the disinfection by-products of EE2, the simulated chlorination experiments were carried out on the secondary effluent and the synthetic water. The yeast estrogen screening(YES) assay and the estrogen receptor protein affinity chromatography method were used to determine the estrogen activity in the study. The results showed that for EE2 in synthetic water, the removal rate of estrogen activity by chlorine disinfection is 96 %～98 % with the [Cl]/[EE2] mass concentration ratio larger than 20. In the pH range from 6 to 9, pH=8 is the most suitable pH condition,indicating that the pH value affects the ionization state of EE2 and HClO in aqueous solution, and therefore affects the EE2 chlorine disinfection removal efficiency.The ammonia nitrogen in the secondary effluent reduced the removal rate of EE2 to 58.1 %, while DOC had an effect on the disinfection rate, but little effect on the overall removal rate. The result proved that the formation of chloramine reduces the free chlorine level and hence reduces the removal of EE2. After chlorination process, even if EE2 itself is almost completely removed, estrogen activity remains. The results of affinity chromatography confirmed that new estrogenic DBPs were generated by chlorination of EE2.
Ethynylestradiol(EE2) is one of the strongest synthetic estrogens, which is widely found in water environment. To explore the removal of EE2 by chlorine disinfection in water treatment, and to study the estrogen activity of the disinfection by-products of EE2, the simulated chlorination experiments were carried out on the secondary effluent and the synthetic water. The yeast estrogen screening(YES) assay and the estrogen receptor protein affinity chromatography method were used to determine the estrogen activity in the study. The results showed that for EE2 in synthetic water, the removal rate of estrogen activity by chlorine disinfection is 96 %～98 % with the [Cl]/[EE2] mass concentration ratio larger than 20. In the pH range from 6 to 9, pH=8 is the most suitable pH condition,indicating that the pH value affects the ionization state of EE2 and HClO in aqueous solution, and therefore affects the EE2 chlorine disinfection removal efficiency.The ammonia nitrogen in the secondary effluent reduced the removal rate of EE2 to 58.1 %, while DOC had an effect on the disinfection rate, but little effect on the overall removal rate. The result proved that the formation of chloramine reduces the free chlorine level and hence reduces the removal of EE2. After chlorination process, even if EE2 itself is almost completely removed, estrogen activity remains. The results of affinity chromatography confirmed that new estrogenic DBPs were generated by chlorination of EE2.
引文
[1]SUMPTER J P,JOBLING S.Vitellogenesis as a Biomarker for Estrogenic Contamination of the Aquatic Environment[J].Environ Health Persp,1995,103:173-8.
[2]DESBROW C,ROUTLEDGE E J,BRIGHTY G C,et al.Identification of estrogenic chemicals in STW effluent.1.Chemical fractionation and in vitro biological screening[J].Environmental Science&Technology,1998,32(11):1549-58.
[3]PAL A,GIN K Y H,LIN A Y C,et al.Impacts of emerging organic contaminants on freshwater resources:Review of recent occurrences,sources,fate and effects[J].Science of the Total Environment,2010,408(24):6062-9.
[4]JACKSON L M,FELGENHAUER B E,KLERKS P L.Feminization,altered gonadal development,and liver damage in least killifish(Heterandria formosa)exposed to sublethal concentrations of 17alpha-ethinylestradiol[J].Ecotoxicol Environ Saf,2019,170:331-7.
[5]ADEEL M,SONG X,WANG Y,et al.Environmental impact of estrogens on human,animal and plant life:A critical review[J].Environ Int,2017,99:107-19.
[6]孙艳,黄璜,胡洪营,等.污水处理厂出水中雌激素活性物质浓度与生态风险水平[J].环境科学研究,2010,23(12):1488-93.
[7]THORPE K L,CUMMINGS R I,HUTCHINSON T H,et al.Relative potencies and combination effects of steroidal estrogens in fish[J].Environmental Science&Technology,2003,37(6):1142-9.
[8]CALDWELL D J,MASTROCCO F,ANDERSON P D,et al.Predicted-no-effect concentrations for the steroid estrogens estrone,17beta-estradiol,estriol,and 17alpha-ethinylestradiol[J].Environ Toxicol Chem,2012,31(6):1396-406.
[9]FENET H,GOMEZ E,PILLON A,et al.Estrogenic activity in water and sediments of a French river:contribution of alkylphenols[J].Arch Environ Contam Toxicol,2003,44(1):1-6.
[10]HASHIMOTO S,HORIUCHI A,YOSHIMOTO T,et al.Horizontal and vertical distribution of estrogenic activities in sediments and waters from Tokyo Bay,Japan[J].Arch Environ Contam Toxicol,2005,48(2):209-16.
[11]SUN J,JI X W,ZHANG R,et al.Endocrine disrupting compounds reduction and water quality improvement in reclaimed municipal wastewater:A field-scale study along Jialu River in North China[J].Chemosphere,2016,157:232-40.
[12]UENO H,MOTO T,SAYATO Y,et al.Disinfection by-products in the chlorination of organic nitrogen compounds:By-products from kynurenine[J].Chemosphere,1996,33(8):1425-33.
[13]STACKELBERG P E,GIBS J,FURLONG E T,et al.Efficiency of conventional drinking-water-treatment processes in removal of pharmaceuticals and other organic compounds[J].Science of the Total Environment,2007,377(2-3):255-72.
[14]ACERO J L,BENITEZ F J,REAL F J,et al.Chlorination of organophosphorus pesticides in natural waters[J].Journal of Hazardous Materials,2008,153(1-2):320-8.
[15]MORIYAMA K,MATSUFUJI H,CHINO M,et al.Identification and behavior of reaction products formed by chlorination of ethynylestradiol[J].Chemosphere,2004,55(6):839-47.
[16]HU J Y,AIZAWA T,OOKUBO S.Products of aqueous chlorination of bisphenol A and their estrogenic activity[J].Environmental Science&Technology,2002,21(10):1980-7.
[17]QUINTANA J B,RODIL R,LóPEZ-MAHíA P,et al.Investigating the chlorination of acidic pharmaceuticals and by-product formation aided by an experimental design methodology[J].Water Research,2010,44(1):243-55.
[18]HU J Y,CHENG S J,AIZAWA T,et al.Products of aqueous chlorination of 17 beta-estradiol and their estrogenic activities[J].Environmental Science&Technology,2003,37(24):5665-70.
[19]SHANG G,XUE J,LI M,et al.Estrogen receptor affinity chromatography:a new method for characterization of novel estrogenic disinfection by-products[J].Chemosphere,2014,104(251-7.
[20]LI M,XU B,LIUNGAI Z,et al.The removal of estrogenic activity with UV/chlorine technology and identification of novel estrogenic disinfection by-products[J].J Hazard Mater,2016,307(119-26.
[21]XU B,LI K,QIAO J,et al.UV photoconversion of environmental oestrogen diethylstilbestrol and its persistence in surface water under sunlight[J].Water Res,2017,127:77-85.
[22]NISHIKAWA J,SAITO K,GOTO J,et al.New screening methods for chemicals with hormonal activities using interaction of nuclear hormone receptor with coactivator[J].Toxicol Appl Pharm,1999,154(1):76-83.
[23]SUN W,LI S,MAI J,et al.Initial photocatalytic degradation intermediates/pathways of 17alpha-ethynylestradiol:effect of pH and methanol[J].Chemosphere,2010,81(1):92-9.
[24]ZHAO T T,LI C,YU T C.Chlorination Degradation of Estriol under Various pH Values in Aqueous Solution[J].Applied Mechanics and Materials,2014,535(713-7.
[25]王斌楠,刘国强,孔德洋,等.炔雌醇氯化反应的动力学和机制研究[J].环境科学,2013,34(6):2225-31.
[26]HE G,LI C,DONG F,et al.Chloramines in a pilot-scale water distribution system:Transformation of 17beta-estradiol and formation of disinfection byproducts[J].Water Res,2016,106(41-50.
[27]GERVAIS G,BICHON E,ANTIGNAC J P,et al.Differential global profiling as a new analytical strategy for revealing micropollutant treatment by-products:application to ethinylestradiol and chlorination water treatment[J].Chemosphere,2011,83(11):1553-9.
[28]MORIYAMA K,MATSUFUJI H,CHINO M,et al.Identification and behavior of reaction products formed by chlorination of ethynylestradiol[J].Chemosphere,2004,55(6):839-47.
[29]LI C,DONG F,CRITTENDEN J C,et al.Kinetics and mechanism of17beta-estradiol chlorination in a pilot-scale water distribution systems[J].Chemosphere,2017,178:73-9.
[2]DESBROW C,ROUTLEDGE E J,BRIGHTY G C,et al.Identification of estrogenic chemicals in STW effluent.1.Chemical fractionation and in vitro biological screening[J].Environmental Science&Technology,1998,32(11):1549-58.
[3]PAL A,GIN K Y H,LIN A Y C,et al.Impacts of emerging organic contaminants on freshwater resources:Review of recent occurrences,sources,fate and effects[J].Science of the Total Environment,2010,408(24):6062-9.
[4]JACKSON L M,FELGENHAUER B E,KLERKS P L.Feminization,altered gonadal development,and liver damage in least killifish(Heterandria formosa)exposed to sublethal concentrations of 17alpha-ethinylestradiol[J].Ecotoxicol Environ Saf,2019,170:331-7.
[5]ADEEL M,SONG X,WANG Y,et al.Environmental impact of estrogens on human,animal and plant life:A critical review[J].Environ Int,2017,99:107-19.
[6]孙艳,黄璜,胡洪营,等.污水处理厂出水中雌激素活性物质浓度与生态风险水平[J].环境科学研究,2010,23(12):1488-93.
[7]THORPE K L,CUMMINGS R I,HUTCHINSON T H,et al.Relative potencies and combination effects of steroidal estrogens in fish[J].Environmental Science&Technology,2003,37(6):1142-9.
[8]CALDWELL D J,MASTROCCO F,ANDERSON P D,et al.Predicted-no-effect concentrations for the steroid estrogens estrone,17beta-estradiol,estriol,and 17alpha-ethinylestradiol[J].Environ Toxicol Chem,2012,31(6):1396-406.
[9]FENET H,GOMEZ E,PILLON A,et al.Estrogenic activity in water and sediments of a French river:contribution of alkylphenols[J].Arch Environ Contam Toxicol,2003,44(1):1-6.
[10]HASHIMOTO S,HORIUCHI A,YOSHIMOTO T,et al.Horizontal and vertical distribution of estrogenic activities in sediments and waters from Tokyo Bay,Japan[J].Arch Environ Contam Toxicol,2005,48(2):209-16.
[11]SUN J,JI X W,ZHANG R,et al.Endocrine disrupting compounds reduction and water quality improvement in reclaimed municipal wastewater:A field-scale study along Jialu River in North China[J].Chemosphere,2016,157:232-40.
[12]UENO H,MOTO T,SAYATO Y,et al.Disinfection by-products in the chlorination of organic nitrogen compounds:By-products from kynurenine[J].Chemosphere,1996,33(8):1425-33.
[13]STACKELBERG P E,GIBS J,FURLONG E T,et al.Efficiency of conventional drinking-water-treatment processes in removal of pharmaceuticals and other organic compounds[J].Science of the Total Environment,2007,377(2-3):255-72.
[14]ACERO J L,BENITEZ F J,REAL F J,et al.Chlorination of organophosphorus pesticides in natural waters[J].Journal of Hazardous Materials,2008,153(1-2):320-8.
[15]MORIYAMA K,MATSUFUJI H,CHINO M,et al.Identification and behavior of reaction products formed by chlorination of ethynylestradiol[J].Chemosphere,2004,55(6):839-47.
[16]HU J Y,AIZAWA T,OOKUBO S.Products of aqueous chlorination of bisphenol A and their estrogenic activity[J].Environmental Science&Technology,2002,21(10):1980-7.
[17]QUINTANA J B,RODIL R,LóPEZ-MAHíA P,et al.Investigating the chlorination of acidic pharmaceuticals and by-product formation aided by an experimental design methodology[J].Water Research,2010,44(1):243-55.
[18]HU J Y,CHENG S J,AIZAWA T,et al.Products of aqueous chlorination of 17 beta-estradiol and their estrogenic activities[J].Environmental Science&Technology,2003,37(24):5665-70.
[19]SHANG G,XUE J,LI M,et al.Estrogen receptor affinity chromatography:a new method for characterization of novel estrogenic disinfection by-products[J].Chemosphere,2014,104(251-7.
[20]LI M,XU B,LIUNGAI Z,et al.The removal of estrogenic activity with UV/chlorine technology and identification of novel estrogenic disinfection by-products[J].J Hazard Mater,2016,307(119-26.
[21]XU B,LI K,QIAO J,et al.UV photoconversion of environmental oestrogen diethylstilbestrol and its persistence in surface water under sunlight[J].Water Res,2017,127:77-85.
[22]NISHIKAWA J,SAITO K,GOTO J,et al.New screening methods for chemicals with hormonal activities using interaction of nuclear hormone receptor with coactivator[J].Toxicol Appl Pharm,1999,154(1):76-83.
[23]SUN W,LI S,MAI J,et al.Initial photocatalytic degradation intermediates/pathways of 17alpha-ethynylestradiol:effect of pH and methanol[J].Chemosphere,2010,81(1):92-9.
[24]ZHAO T T,LI C,YU T C.Chlorination Degradation of Estriol under Various pH Values in Aqueous Solution[J].Applied Mechanics and Materials,2014,535(713-7.
[25]王斌楠,刘国强,孔德洋,等.炔雌醇氯化反应的动力学和机制研究[J].环境科学,2013,34(6):2225-31.
[26]HE G,LI C,DONG F,et al.Chloramines in a pilot-scale water distribution system:Transformation of 17beta-estradiol and formation of disinfection byproducts[J].Water Res,2016,106(41-50.
[27]GERVAIS G,BICHON E,ANTIGNAC J P,et al.Differential global profiling as a new analytical strategy for revealing micropollutant treatment by-products:application to ethinylestradiol and chlorination water treatment[J].Chemosphere,2011,83(11):1553-9.
[28]MORIYAMA K,MATSUFUJI H,CHINO M,et al.Identification and behavior of reaction products formed by chlorination of ethynylestradiol[J].Chemosphere,2004,55(6):839-47.
[29]LI C,DONG F,CRITTENDEN J C,et al.Kinetics and mechanism of17beta-estradiol chlorination in a pilot-scale water distribution systems[J].Chemosphere,2017,178:73-9.