高效液相色谱串联质谱测定城镇污水处理厂水样中典型雌激素内分泌干扰物质
|
摘要
雌激素内分泌干扰物质对生物体的影响逐渐成为人们关注的焦点。作为重要的化工生产中间体,大量此类物质会随污水排放进入城市污水处理厂,未被去除而进入周边水环境,对人和动物产生潜在的危害。为了解城市污水处理厂中典型雌激素内分泌干扰物质的污染现状,建立了固相萃取结合超高效液相色谱-质谱联用的方法,同时测定了污水处理厂水样中雌酮(E1)、雌二醇(E2)、雌三醇(E3)、17α-炔雌醇(EE2)、双酚A(BisphenolA,BPA)及壬基酚(Nonylphenol,NP)。结果表明,以AcquityUPLCTM BEH C18柱(50 mm×2.1 mm,1.7μm)为分离柱,乙腈和5 mmol·L~(-1)乙酸铵溶液为流动相,质谱在选择ESI负离子模式的条件下,目标化合物于8 min内实现了分离。方法的检测限为4～30 ng·L~(-1),定量限为10～40 ng·L~(-1),6种目标化合物在0.5～200μg·L~(-1)范围内线性关系显著,具有良好的精密度和回收率。按照此方法,对H市4个典型生活污水处理厂的水样进行分析,总排水口水样中检测出雌酮(E1)、雌二醇(α-E2)、雌三醇(E3)、双酚A(BPA)及壬基酚(NP)5种目标化合物,浓度范围分别为0.002～0.41μg·L~(-1)、0.01μg·L~(-1)、0.11～3.73μg·L~(-1)、0.04～4.42μg·L~(-1)、0.15～1.30μg·L~(-1)。该方法简单快捷,灵敏准确,满足污水处理厂水样中雌激素内分泌干扰物质的检测要求。
At present, the influence of estrogenic endocrine disrupting chemicals on organisms has gradually become the focus of attention. As an important chemical production intermediate, a large amount of such substances will be discharged into the urban sewage treatment plant along with the sewage, and will not be removed and enter the surrounding water environment, posing potential harm to humans and animals. In order to study the pollution status of typical estrogenic endocrine disrupting chemicals in municipal wastewater treatment plants, the method of solid phase extraction(SPE) combined with ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)was established in this paper, and estrone(E1), estradiol(E2), estriol(E3), 17α-ethinylestradiol(EE2), bisphenol A(BPA) and nonylphenol(NP) in water samples from sewage treatment plants were determined. The results showed that the Acquity UPLCTM BEH C18 column(50 mm×2.1 mm, 1.7 μm) was used as the separation column, and the acetonitrile and 5 mmol·L~(-1) ammonium acetate solution were used as the mobile phase. The mass spectrometer was selected under multiple reaction monitoring(MRM) mode. The compounds were separated within 8 min. The detection limit of the method is 4-30 ng·L~(-1), the limit of quantification is 10-40 ng·L~(-1), and the linearity of the six target compounds in the range of 0.5-200 μg·L~(-1) is significant, with good precision and recovery. According to this method,the water samples of four typical domestic sewage treatment plants in H City were analyzed. Five target compounds were detected in the total drainage water samples: estrone(E1), estradiol(α-E2), estriol(E3), bisphenol A(BPA)and nonylphenol(NP). It is 0.002-0.41 μg·L~(-1), 0.01 μg·L~(-1), 0.11-3.73 μg·L~(-1), 0.04-4.42 μg·L~(-1), 0.15-1.30 μg·L~(-1).The results show that the method is simple, rapid, sensitive and accurate, and meets the requirements for detection of estrogenic endocrine disrupting chemicals in water samples from sewage treatment plants.
At present, the influence of estrogenic endocrine disrupting chemicals on organisms has gradually become the focus of attention. As an important chemical production intermediate, a large amount of such substances will be discharged into the urban sewage treatment plant along with the sewage, and will not be removed and enter the surrounding water environment, posing potential harm to humans and animals. In order to study the pollution status of typical estrogenic endocrine disrupting chemicals in municipal wastewater treatment plants, the method of solid phase extraction(SPE) combined with ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)was established in this paper, and estrone(E1), estradiol(E2), estriol(E3), 17α-ethinylestradiol(EE2), bisphenol A(BPA) and nonylphenol(NP) in water samples from sewage treatment plants were determined. The results showed that the Acquity UPLCTM BEH C18 column(50 mm×2.1 mm, 1.7 μm) was used as the separation column, and the acetonitrile and 5 mmol·L~(-1) ammonium acetate solution were used as the mobile phase. The mass spectrometer was selected under multiple reaction monitoring(MRM) mode. The compounds were separated within 8 min. The detection limit of the method is 4-30 ng·L~(-1), the limit of quantification is 10-40 ng·L~(-1), and the linearity of the six target compounds in the range of 0.5-200 μg·L~(-1) is significant, with good precision and recovery. According to this method,the water samples of four typical domestic sewage treatment plants in H City were analyzed. Five target compounds were detected in the total drainage water samples: estrone(E1), estradiol(α-E2), estriol(E3), bisphenol A(BPA)and nonylphenol(NP). It is 0.002-0.41 μg·L~(-1), 0.01 μg·L~(-1), 0.11-3.73 μg·L~(-1), 0.04-4.42 μg·L~(-1), 0.15-1.30 μg·L~(-1).The results show that the method is simple, rapid, sensitive and accurate, and meets the requirements for detection of estrogenic endocrine disrupting chemicals in water samples from sewage treatment plants.
引文
[1]杜磊,李勃,马瑜,等.环境内分泌干扰物危害及作用机制研究进展[J].国外医学(医学地理分册),2012,33(4):261-265.
[2]孟顺龙,宋超,范立民,等.水体中环境内分泌干扰物(EDCs)污染现状及其对鱼类的生殖危害[J].江苏农业学报,2013,29(1):202-208.
[3]杜娟,胡红娟,杨靖,等.徐州地区地下水中内分泌干扰物的监测与风险评估[J].环境监测管理与技术,2016,28(6):38-40.
[4]刘畅伶,张文强,单保庆.珠江口典型河段内分泌干扰物的空间分布及风险评价[J].环境科学学报,2018,38(1):115-124.
[5]周海东,黄霞,王晓琳,等.北京市城市污水雌激素活性的研究[J].环境科学,2009,30(12):3590-3595.
[6]聂亚峰,强志民,张鹤清,等.内分泌干扰物在城市污水处理厂中的行为和归趋:综述[J].环境科学学报,2011,31(7):1352-1362.
[7]程雪梅.色谱分析样品前处理技术:固相萃取法[J].热带农业工程,2002(1):14-16.
[8]廖涛,吴晓翠,王少华,等.固相萃取-气相色谱/质谱联用法同时检测水体中9种环境雌激素[J].分析化学,2013,41(3):422-426.
[9]MUZ M,SELCEN S?NMEZ M,KOMESLI O T,et al.Determination of selected natural hormones and endocrine disrupting compounds in domestic wastewater treatment plants by liquid chromatography electrospray ionization tandem mass spectrometry after solid phase extraction[J].Analyst,2012,137(4):884-889.
[10]ZHANG H C,YU X J,YANG W C,et al.MCX based solid phase extraction combined with liquid chromatography tandem mass spectrometry for the simultaneous determination of 31 endocrine-disrupting compounds in surface water of Shanghai[J].J Chromatogr B,2011,879(28):2998-3004.
[11]马晓雁,高乃云,李青松,等.固相萃取-高效液相色谱检测原水中微量内分泌干扰物[J].给水排水,2006,32(1):6-10.
[12]王晓东,赵新华,张新波,等.固相萃取-高效液相色谱-荧光检测法同时测定水中的壬基酚和双酚A[J].分析试验室,2006,25(9):27-29.
[13]周鸿,樊建军,王占生.水中痕量污染物雌激素的内分泌干扰活性评价[J].净水技术,2013,32(1):1-5.
[14]丁洁,张圣虎,刘济宁,等.液相色谱-串联质谱法测定污水处理厂水样中双酚A、四溴双酚A及烷基酚类化合物[J].色谱,2014,32(5):529-534.
[15]谭丽超,葛峰,单正军,等.超高效液相色谱-串联质谱法测定污水处理厂水样中的雌激素[J].生态与农村环境学报,2011,27(5):86-92.
[2]孟顺龙,宋超,范立民,等.水体中环境内分泌干扰物(EDCs)污染现状及其对鱼类的生殖危害[J].江苏农业学报,2013,29(1):202-208.
[3]杜娟,胡红娟,杨靖,等.徐州地区地下水中内分泌干扰物的监测与风险评估[J].环境监测管理与技术,2016,28(6):38-40.
[4]刘畅伶,张文强,单保庆.珠江口典型河段内分泌干扰物的空间分布及风险评价[J].环境科学学报,2018,38(1):115-124.
[5]周海东,黄霞,王晓琳,等.北京市城市污水雌激素活性的研究[J].环境科学,2009,30(12):3590-3595.
[6]聂亚峰,强志民,张鹤清,等.内分泌干扰物在城市污水处理厂中的行为和归趋:综述[J].环境科学学报,2011,31(7):1352-1362.
[7]程雪梅.色谱分析样品前处理技术:固相萃取法[J].热带农业工程,2002(1):14-16.
[8]廖涛,吴晓翠,王少华,等.固相萃取-气相色谱/质谱联用法同时检测水体中9种环境雌激素[J].分析化学,2013,41(3):422-426.
[9]MUZ M,SELCEN S?NMEZ M,KOMESLI O T,et al.Determination of selected natural hormones and endocrine disrupting compounds in domestic wastewater treatment plants by liquid chromatography electrospray ionization tandem mass spectrometry after solid phase extraction[J].Analyst,2012,137(4):884-889.
[10]ZHANG H C,YU X J,YANG W C,et al.MCX based solid phase extraction combined with liquid chromatography tandem mass spectrometry for the simultaneous determination of 31 endocrine-disrupting compounds in surface water of Shanghai[J].J Chromatogr B,2011,879(28):2998-3004.
[11]马晓雁,高乃云,李青松,等.固相萃取-高效液相色谱检测原水中微量内分泌干扰物[J].给水排水,2006,32(1):6-10.
[12]王晓东,赵新华,张新波,等.固相萃取-高效液相色谱-荧光检测法同时测定水中的壬基酚和双酚A[J].分析试验室,2006,25(9):27-29.
[13]周鸿,樊建军,王占生.水中痕量污染物雌激素的内分泌干扰活性评价[J].净水技术,2013,32(1):1-5.
[14]丁洁,张圣虎,刘济宁,等.液相色谱-串联质谱法测定污水处理厂水样中双酚A、四溴双酚A及烷基酚类化合物[J].色谱,2014,32(5):529-534.
[15]谭丽超,葛峰,单正军,等.超高效液相色谱-串联质谱法测定污水处理厂水样中的雌激素[J].生态与农村环境学报,2011,27(5):86-92.