Determination of Free and Conjugated Forms of Bisphenol A in Human Urine and Serum by Liquid Chromatography-Tandem Mass Spectrometry
Determination of Free and Conjugated Forms of Bisphenol A in Human Urine and Serum by Liquid Chromatography-Tandem Mass Spectrometry
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DOI：
10.1021/es300115a
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发表时间：
2012-05-01
影响因子：
11.4
通讯作者：
Kannan, Kurunthachalam
中科院分区：
文献类型：
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作者：
Liao, Chunyang;Kannan, Kurunthachalam
人类暴露于双酚A（BPA），一种广泛使用的工业化学品，是众所周知的。在人类和动物中，BPA分子与葡糖苷酸或硫酸盐的结合被认为是一种解毒机制。然而，很少有研究直接测量游离的、缀合的（例如，葡萄糖醛酸化的），和取代的（例如，氯化）形式的BPA。在本研究中，使用固相萃取（SPE）和液相色谱串联质谱（LC-MS/MS）技术测定了人尿液和血清样本中的游离、结合（BPA葡糖苷酸或BPAG和BPA二硫酸盐或BPADS）和取代（氯化BPA;单[BPAMC]、双[BPADC]和双[BPATrC]）形式的BPA。每种目标化合物的仪器校准范围为0.01 - 100 ng/mL，并显示出良好的线性（r> 0.99）。游离BPA的定量限（LOQ）为0.01 ng/mL，结合和取代BPA的定量限为0.05 ng/mL。加标至水空白和样品基质（尿液和血清）中并通过整个分析方法的6种目标化合物的回收率分别为96 +/-14%和105 +/-18%（平均值+/-SD）（尿液样品）和87 +/-8%和80 +/-13%（血清样品）。分析方法中BPAG和BPADS的最佳回收率表明，在SPE方法中未发生解偶联。该方法被应用于测量尿液和血清样本中的六个目标化学品收集自奥尔巴尼，纽约的志愿者。尿液样本中发现BPA及其衍生物，浓度范围从<LOQ到几十ng/mL。在血清中，检测到游离和结合BPA的浓度低于ng/mL，而未检测到BPA氯化物。尿液和血清样品也进行了分析，酶解结合和液液萃取（LLE）测定总BPA，并与固相萃取法测定的结果进行了比较。据我们所知，这是第一份关于人血清中BPAG和BPADS的报告。
Exposure of humans to bisphenol A (BPA), a widely used industrial chemical, is well-known. In humans and animals, conjugation of BPA molecule with glucuronide or sulfate is considered as a mechanism for detoxification. Nevertheless, very few studies have directly measured free, conjugated (e.g., glucuronidated), and substituted (e.g., chlorinated) forms of BPA in human specimens. In this study, free, conjugated (BPA glucuronide or BPAG and BPA disulfate or BPADS), and substituted (chlorinated BPA; mono- [BPAMC], di-[BPADC], and trichloride [BPATrC]) forms of BPA were determined in human urine and serum samples, using solid-phase extraction (SPE) and liquid chromatography tandem mass spectrometry (LC-MS/MS) techniques. The instrumental calibration for each of the target compounds ranged from 0.01 to 100 ng/mL and showed excellent linearity (r > 0.99). The limits of quantification (LOQs) were 0.01 ng/mL for free BPA and 0.05 ng/mL for the conjugated and substituted BPA. Respective recoveries of the six target compounds spiked into water blanks and sample matrices (urine and serum), and passed through the entire analytical procedure, were 96 +/- 14% and 105 +/- 18% (mean +/- SD) for urine samples and 87 +/- 8% and 80 +/- 13% for serum samples. The optimal recoveries of BPAG and BPADS in the analytical procedure indicted that no deconjugation occurred during the SPE procedure. The method was applied to measure six target chemicals in urine and serum samples collected from volunteers in Albany, New York. BPA and its derivatives were found in urine samples at concentrations ranging from < LOQ to a few tens of ng/mL. In serum, free and conjugated BPA were detected at sub ng/mL concentrations, whereas BPA chlorides were not detected. The urine and serum samples were also analyzed by enzymatic deconjugation and liquid liquid extraction (LLE) for the determination of total BPA, and the results were compared with those measured by the SPE method. To our knowledge, this is the first report on the occurrence of BPAG and BPADS in human serum.