超高效液相色谱-四极杆串联飞行时间质谱法筛查上海市生活饮用水和地表水中的雌激素水平  

Screening estrogens in drinking water and surface water of Shanghai city using ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry

作　　者：王和兴[1] 周颖[1] 王霞[1] 屈卫东[1] 姜庆五[1] 

机构地区：[1]复旦大学公共卫生学院公共卫生安全教育部重点实验室,上海200032

出　　处：《复旦学报（医学版）》2011年第5期396-401,406,共7页Fudan University Journal of Medical Sciences

基　　金：国家"十一五"科技支撑计划(2006BAI19B02);复旦大学09年青年基金项目(EYF201023)

摘　　要：目的建立应用超高效液相色谱-四级杆串联飞行时间质谱法快速筛查上海市生活饮用水和地表水中天然或人工合成的雌激素的方法。方法分别采集上海市不同地点生活饮用水、黄浦江与苏州河不同河段地表水水样各1L,每点设2个平行,取500mL水样经Oasis HLB固相萃取柱(500mg,Waters)萃取,70%甲醇淋洗,10mL体积分数为10%的甲醇乙酸乙酯溶液洗脱待测物,用Waters ACQUITYUPLC HSS T3色谱柱(100mm×2.1mm,1.8μm)分离,在MS和MS/MS模式下,采用负离子模式电喷雾离子源对常见雌激素进行Q-TOFMS分析。结果 5种常见雌激素(雌三醇、β-雌二醇、17α-乙炔雌二醇、雌酮、己烯雌酚)在0.001～0.1μg/mL范围内线性关系良好,检出限(S/N=3)为0.11～0.25 ng/L,定量限(S/N=10)为0.38～0.84 ng/L,在添加水平分别为5、50 ng/L时,平均回收率为58%～115%,RSD为1.4%～13.9%,5种雌激素测定其相对分子质量(Mr)与理论值的误差在(-1.7～2.8)×10-3之间。生活饮用水中未检出上述5种雌激素,而黄浦江和苏州河的各个河段的水样中均检测出雌三醇(0.8～10.5 ng/L)和雌酮(1.6～5.6 ng/L)。结论本方法灵敏度高、定性准确,适用于生活饮用水和地表水中雌激素的筛查。流经上海市不同河段的黄浦江和苏州河水样中均检测出ng/L级的雌三醇和雌酮,应当在今后的监测中引起重视。Objective To develop a screening method for natural or synthetic estrogens in drinking water and surface water in Shanghai using ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry（UPLC-Q-TOF MS）.Methods Duplicate 1 L drinking water and surface water samples were obtained from different sites in Shanghai city,Suzhou River and Huangpu River,respectively.The compounds in 500 mL water sample were extracted by Oasis HLB column（500 mg,Waters）,washed by 70% methanol,eluted by the mixture containing 10% methanol in ethyl acetate（volume percentage）,and then separated on a Waters ACQUITYUPLC HSS T3 column（100 mm×2.1 mm,1.8 μm） and analyzed qualitatively and quantitatively by UPLC-Q-TOF in MS and MS/MS model.Results Five frequent estrogens including estriol,β-estradiol,17α-ethinylestradiol,estrone and diethylstilbestrol had good linearity between 0.001-0.1 μg/mL with the limits of detection（LODs） ranging from 0.11 to 0.25 ng/L and the limits of quatitation（LOQs） from 0.38 to 0.84 ng/L.The mass errors between theoretical and experimental masses obtained for deprotonated molecules of five estrogens,internal standard（β-estradiol-d3） and their daughter ions were between（-1.7-2.8）×10-3（Mr）.At the spiked levels of 5,50 ng/L,the average recoveries ranged from 58% to 115% with the relative standard deviations between 1.4% and 13.9%.No target estrogens were found in drinking water,but estriol（0.8-10.5 ng/L） and estrone（1.6-5.6 ng/L） were all detected in surfacewater samples from Suzhou River and Huangpu River.Conclusions The proposed method was sensitive,accurate and suitable for screening estrogens in drinking water and surface water.Estriol and estrone at ng/L level exist in Suzhou River and Huangpu River,which should be paid more attention in further surveillance.

关 键 词：雌激素 生活饮用水 地表水 超高效液相色谱-四极杆串联飞行时间质谱法 

分 类 号：Q657.63[生物学—生物物理学]