固相萃取-超高效液相色谱-串联质谱法测定瓶装饮用水中双酚A、双酚S
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摘要
目的建立固相萃取(solid phase extraction,SPE)结合超高效液相色谱-串联质谱法(ultra performance liquid chromatography-tandem mass spectrometry,UPLC-MS/MS)测定瓶装饮用水中双酚A(bisphenol A,BPA)、双酚S(bisphenol S,BPS)的方法。方法利用BPA-D_4和BPS-~(13)C_(12)混合同位素内标,经Waters Oasis系列的HLB固相萃取柱富集样品,以甲醇-水为流动相,经Waters BEH C_(18)色谱柱分离,采用UPLC-MS/MS在负离子电离(electron spray ionization,ESI-)模式和多反应监控(multiple reaction monitoring,MRM)模式下检测。结果用该方法测定时,BPA在1~50μg/L范围内线性良好,BPS在0.2~10μg/L范围内线性良好,相关系数r均为0.9999,BPA的平均回收率为99.5%~100.7%,相对标准偏差为0.8%~4.6%;BPS的平均回收率为95.9%~102.1%,相对标准偏差为1.3%~2.5%,BPA的最低检出浓度为20 ng/L,BPS的最低检出浓度为5 ng/L。结论此方法操作简单、灵敏度高、重现性好,适用于瓶装饮用水中双酚A、双酚S的检测。
Objective To establish an ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) with solid phase extraction(SPE) method for the determination of bisphenol A(BPA) and bisphenol S(BPS) in bottled drinking water. Methods With BPA-D_4 and BPS-~(13)C_(12) isotope as mixed internal standards, the BPA and BPS were enriched by Waters Oasis HLB column. The samples were separated by Waters BEH C_(18) chromatographic column with methanol-water as mobile phase, and then detected by UPLC-MS/MS under the multiple reactions monitoring(MRM) mode with the negative-ion mode and quantified by an internal standard method. Results Using the established method, BPA and BPS had good linearities in the ranges of 1-50 μg/L and 0.2-10 μg/L for BPA and BPS, respectively(r>0.999). The average recoveries of BPA were 99.5%-100.7% and the relative standard deviations were 0.8%-4.6%. The average recoveries of BPS were 95.9%-102.1% and the relative standard deviations were 1.3%-2.5%. The least determination limits were 20 ng/L and 5 ng/L for BPA and BPS, respectively. Conclusion The established method is simple, sensitive and has good repeatability, which is suitable for the determination of BPA and BPS in bottled drinking water.
Objective To establish an ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) with solid phase extraction(SPE) method for the determination of bisphenol A(BPA) and bisphenol S(BPS) in bottled drinking water. Methods With BPA-D_4 and BPS-~(13)C_(12) isotope as mixed internal standards, the BPA and BPS were enriched by Waters Oasis HLB column. The samples were separated by Waters BEH C_(18) chromatographic column with methanol-water as mobile phase, and then detected by UPLC-MS/MS under the multiple reactions monitoring(MRM) mode with the negative-ion mode and quantified by an internal standard method. Results Using the established method, BPA and BPS had good linearities in the ranges of 1-50 μg/L and 0.2-10 μg/L for BPA and BPS, respectively(r>0.999). The average recoveries of BPA were 99.5%-100.7% and the relative standard deviations were 0.8%-4.6%. The average recoveries of BPS were 95.9%-102.1% and the relative standard deviations were 1.3%-2.5%. The least determination limits were 20 ng/L and 5 ng/L for BPA and BPS, respectively. Conclusion The established method is simple, sensitive and has good repeatability, which is suitable for the determination of BPA and BPS in bottled drinking water.
引文
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[2]陈波,肖锋,赵琼辉,等.液相色谱-串联质谱法测定乳制品中双酚A及其环氧衍生物[J].中国卫生检验杂志,2013,23(3):584-594.Chen B,Xiao F,Zhao QH,et al.Determination of bisphenol A and its epoxy derivatives in dairy products by high performance liquid chromatography tandem mass spectrometry[J].Chin J Health Lab Technol,2013,23(3):584-594.
[3]张建莹,杨修斌,罗耀,等.超高效液相色谱-串联质谱法检测牛奶中双酚A[J].食品安全质量检测学报,2014,11(5):3437-3443.Zhang JY,Yang XB,Luo Y,et al.Determination of bisphenol A residues in milk by ultra performance liquid chromatography-tandem mass spectrometry[J].J Food Saf Qual,2014,11(5):3437-3443.
[4]Pouokam GB,Ajaezi GC,Mantovani A,et al.Use of Bisphenol A-containing baby bottles in Cameroon and Nigeria and possible risk management and mitigation measures:community as milestone for prevention[J].Sci Total Environ,2014,481(2):296-302.
[5]任东升,周志俊.双酚A生殖与发育毒性研究现状[J].环境与职业医学,2012,29(11):722-726.Ren DS,Zhou ZJ.A review of studies on reproductive and developmental toxicities of bisphenol A[J].J Environ Occup Med,2012,29(11):722-726.
[6]杨蕴嘉,尹杰,邵兵.双酚A替代物-双酚S的研究进展[J].首都公共卫生,2016,10(5):222-225.Yang YJ,Yin J,Shao B.Researchprogress of bisphenol S:A substitute for bisphenol A[J].Capit J Public Health,2016,10(5):222-225.
[7]Kinch CD,Ibhazehiebo K,Jeong JH,et al.Low-dose exposure to bisphenol A and replacement bisphenol S induces precocious hypothalamic neurogenesis in embryonic zebrafish[J].Proc Natl Acad Sci USA,2015,112(5):1475-1480.
[8]Ullah H,Jahan S,Ain QU,et al.Effect of bisphenol S exposure on male reproductive system of rats:A histological and biochemical study[J].Chemosphere,2016,152(2):383-391.
[9]薛鸣,张虹.食品及包装材料中双酚A及其环氧衍生物残留分析的研究进展[J].食品研究与开发,2009,30(7):169-173.Xue M,Zhang H.The residue analytical development of bisphenol A and its epoxy derivatives in food and packing materials[J].Food Res Dev,2009,30(7):169-173.
[10]毛丽莎,刘桂华,姜杰,等.固相萃取-LC-MS/MS测定水中双酚A类物质[J].实用预防医学,2016,23(10):1260-1263.Mao LS,Liu GH,Jiang J,et al.Determination of bisphenol A analogs in water sample by liquid chromatography-tandem mass spectrometry with solid phase extraction[J].Pract Prev Med,2016,23(10):1260-1263.
[11]郝鹏鹏.液相色谱-质谱法检测包装饮用水中双酚A[J].食品科技,2013,38(9):282-286.Hao PP.Determination of bisphenol A in packaged drinking water by liquid chromatography-mass spectrometry[J].Food Sci Technol,2013,38(9):282-286.
[12]田宏哲,徐静.高效液相色谱法测定牛奶中双酚A[J].食品科技,2012,37(8):286-289.Tian HZ,Xu J.Quantitative analysis of bisphenol A in milk samples by HPLC[J].Food Sci Technol,2012,37(8):286-289.
[13]王延翠,张立衡,杨肖,等.在线固相萃取-高效液相色谱同时检测水中双酚A和双酚S[J].分析试验室,2017,36(8):971-974.Wang YC,Zhang LH,Yang Xiao,et al.On-line solid phase extraction-high performance liquid chromatography for simultaneous determination of bisphenol A and bisphenol S in environmental water[J].Chin J Anal Lab,2017,36(8):971-974.
[14]张圣虎,张易曦,吉贵祥,等.高效液相色谱-串联质谱法测定儿童和成人尿液中双酚A、四溴双酚A和辛基酚[J].分析化学,2016,44(1):19-24.Zhang SH,Zhang YX,Ji GX,et al.Determination of bisphenol A,tetrabromobisphenol A and 4-tertoctylphenol in child and adult urine samples using high performance liquid chromatography-tandem mass spectrometry[J].Chin J Anal Chem,2016,44(1):19-24.
[15]王春民,张秋萍,李建.液相色谱/串联质谱法测定生活饮用水中的双酚A方法验证[J].中国卫生检验杂志,2013,23(3):582-591.Wang CM,Zhang QP,Li J.Method validation on determination of BPA in drinking water by liquid chromatography-triple quadrupole mass spectrometer[J].Chin J Health Lab Technol,2013,23(3):582-591.
[16]李帮锐,冯家力,曾栋,等.在线捕集消除本底技术应用于饮用水中双酚A和壬基酚的测定[J].中国卫生检验杂志,2015,25(11):1713-1715.Li BR,Feng JL,Zeng D,et al.Application of on-line capture and elimination technique for the determination of bisphenol A and nonylphenol in drinking water[J].Chin J Health Lab Technol,2015,25(11):1713-1715.
[17]章勇,张蓓蓓,穆肃,等.液质联用法测定水中六溴环十二烷和四溴双酚A[J].环境科学与技术,2014,37(4):107-112.Zhang Y,Zang BB,Mu S,et al.Determination of hexabromocyclododecane and tetrabromobisphenol a in water by ultra performance liquid chromatography-tandem mass spectrometry[J].Environ Sci Technol,2014,37(4):107-112.
[18]GB 5749-2006生活饮用水卫生标准[S].GB5749-2006 Standards for drinking water quality[S].
[2]陈波,肖锋,赵琼辉,等.液相色谱-串联质谱法测定乳制品中双酚A及其环氧衍生物[J].中国卫生检验杂志,2013,23(3):584-594.Chen B,Xiao F,Zhao QH,et al.Determination of bisphenol A and its epoxy derivatives in dairy products by high performance liquid chromatography tandem mass spectrometry[J].Chin J Health Lab Technol,2013,23(3):584-594.
[3]张建莹,杨修斌,罗耀,等.超高效液相色谱-串联质谱法检测牛奶中双酚A[J].食品安全质量检测学报,2014,11(5):3437-3443.Zhang JY,Yang XB,Luo Y,et al.Determination of bisphenol A residues in milk by ultra performance liquid chromatography-tandem mass spectrometry[J].J Food Saf Qual,2014,11(5):3437-3443.
[4]Pouokam GB,Ajaezi GC,Mantovani A,et al.Use of Bisphenol A-containing baby bottles in Cameroon and Nigeria and possible risk management and mitigation measures:community as milestone for prevention[J].Sci Total Environ,2014,481(2):296-302.
[5]任东升,周志俊.双酚A生殖与发育毒性研究现状[J].环境与职业医学,2012,29(11):722-726.Ren DS,Zhou ZJ.A review of studies on reproductive and developmental toxicities of bisphenol A[J].J Environ Occup Med,2012,29(11):722-726.
[6]杨蕴嘉,尹杰,邵兵.双酚A替代物-双酚S的研究进展[J].首都公共卫生,2016,10(5):222-225.Yang YJ,Yin J,Shao B.Researchprogress of bisphenol S:A substitute for bisphenol A[J].Capit J Public Health,2016,10(5):222-225.
[7]Kinch CD,Ibhazehiebo K,Jeong JH,et al.Low-dose exposure to bisphenol A and replacement bisphenol S induces precocious hypothalamic neurogenesis in embryonic zebrafish[J].Proc Natl Acad Sci USA,2015,112(5):1475-1480.
[8]Ullah H,Jahan S,Ain QU,et al.Effect of bisphenol S exposure on male reproductive system of rats:A histological and biochemical study[J].Chemosphere,2016,152(2):383-391.
[9]薛鸣,张虹.食品及包装材料中双酚A及其环氧衍生物残留分析的研究进展[J].食品研究与开发,2009,30(7):169-173.Xue M,Zhang H.The residue analytical development of bisphenol A and its epoxy derivatives in food and packing materials[J].Food Res Dev,2009,30(7):169-173.
[10]毛丽莎,刘桂华,姜杰,等.固相萃取-LC-MS/MS测定水中双酚A类物质[J].实用预防医学,2016,23(10):1260-1263.Mao LS,Liu GH,Jiang J,et al.Determination of bisphenol A analogs in water sample by liquid chromatography-tandem mass spectrometry with solid phase extraction[J].Pract Prev Med,2016,23(10):1260-1263.
[11]郝鹏鹏.液相色谱-质谱法检测包装饮用水中双酚A[J].食品科技,2013,38(9):282-286.Hao PP.Determination of bisphenol A in packaged drinking water by liquid chromatography-mass spectrometry[J].Food Sci Technol,2013,38(9):282-286.
[12]田宏哲,徐静.高效液相色谱法测定牛奶中双酚A[J].食品科技,2012,37(8):286-289.Tian HZ,Xu J.Quantitative analysis of bisphenol A in milk samples by HPLC[J].Food Sci Technol,2012,37(8):286-289.
[13]王延翠,张立衡,杨肖,等.在线固相萃取-高效液相色谱同时检测水中双酚A和双酚S[J].分析试验室,2017,36(8):971-974.Wang YC,Zhang LH,Yang Xiao,et al.On-line solid phase extraction-high performance liquid chromatography for simultaneous determination of bisphenol A and bisphenol S in environmental water[J].Chin J Anal Lab,2017,36(8):971-974.
[14]张圣虎,张易曦,吉贵祥,等.高效液相色谱-串联质谱法测定儿童和成人尿液中双酚A、四溴双酚A和辛基酚[J].分析化学,2016,44(1):19-24.Zhang SH,Zhang YX,Ji GX,et al.Determination of bisphenol A,tetrabromobisphenol A and 4-tertoctylphenol in child and adult urine samples using high performance liquid chromatography-tandem mass spectrometry[J].Chin J Anal Chem,2016,44(1):19-24.
[15]王春民,张秋萍,李建.液相色谱/串联质谱法测定生活饮用水中的双酚A方法验证[J].中国卫生检验杂志,2013,23(3):582-591.Wang CM,Zhang QP,Li J.Method validation on determination of BPA in drinking water by liquid chromatography-triple quadrupole mass spectrometer[J].Chin J Health Lab Technol,2013,23(3):582-591.
[16]李帮锐,冯家力,曾栋,等.在线捕集消除本底技术应用于饮用水中双酚A和壬基酚的测定[J].中国卫生检验杂志,2015,25(11):1713-1715.Li BR,Feng JL,Zeng D,et al.Application of on-line capture and elimination technique for the determination of bisphenol A and nonylphenol in drinking water[J].Chin J Health Lab Technol,2015,25(11):1713-1715.
[17]章勇,张蓓蓓,穆肃,等.液质联用法测定水中六溴环十二烷和四溴双酚A[J].环境科学与技术,2014,37(4):107-112.Zhang Y,Zang BB,Mu S,et al.Determination of hexabromocyclododecane and tetrabromobisphenol a in water by ultra performance liquid chromatography-tandem mass spectrometry[J].Environ Sci Technol,2014,37(4):107-112.
[18]GB 5749-2006生活饮用水卫生标准[S].GB5749-2006 Standards for drinking water quality[S].