Heffernan A L, Thompson K, Eaglesham G, Vijayasarathy S, Mueller J F, Sly P D, Gomez M J
National Research Centre for Environmental Toxicology, The University of Queensland, 39 Kessels Rd, Coopers Plains, Brisbane, QLD 4108, Australia.
Queensland Children's Medical Research Institute, and Children's Health and Environment Program, The University of Queensland, Centre for Children's Health Research, Level 7, 62 Graham St South, Brisbane, QLD, 4101, Australia.
Talanta. 2016 May 1;151:224-233. doi: 10.1016/j.talanta.2016.01.037. Epub 2016 Jan 18.
Phthalates and bisphenol A (BPA) have received special attention in recent years due to their frequent use in consumer products and potential for adverse effects on human health. BPA is being replaced with a number of alternatives, including bisphenol S, bisphenol B, bisphenol F and bisphenol AF. These bisphenol analogues have similar potential for adverse health effects, but studies on human exposure are limited. Accurate measurement of multiple contaminants is important for estimating exposure. This paper describes a sensitive and automated method for the simultaneous determination of 14 phthalate metabolites, BPA and four bisphenol analogues in urine using online solid phase extraction coupled with high-performance liquid chromatography/tandem mass spectrometry using a hybrid triple-quadrupole linear ion trap mass spectrometer (LC-QTRAP-MS/MS), requiring very little sample volume (50µL). Quantification was performed under selected reaction monitoring (SRM) mode with negative electrospray ionization. The use of SRM combined with an enhanced product ion scan within the same analysis was examined. Unequivocal identification was provided by the acquisition of three SRM transitions per compound and isotope dilution. The analytical performance of the method was evaluated in synthetic and human urine. Linearity of response over three orders of magnitude was demonstrated for all of the compounds (R(2)>0.99), with method detection limits of 0.01-0.5ng/mL and limits of reporting of 0.07-3.1ng/mL. Accuracy ranged from 93% to 113% and inter- and intra-day precision were <22%. Finally, the validated method has been successfully applied to a cohort of pregnant women to measure biomarker concentrations of phthalates and bisphenols, with median concentrations ranging from 0.3ng/mL (bisphenol S) to 18.5ng/mL (monoethyl phthalate).
近年来，邻苯二甲酸盐和双酚A（BPA）因其在消费品中的频繁使用以及对人体健康的潜在不利影响而受到特别关注。双酚A正被多种替代品取代，包括双酚S、双酚B、双酚F和双酚AF。这些双酚类似物具有类似的健康不良影响潜力，但关于人体暴露的研究有限。准确测量多种污染物对于估计暴露情况很重要。本文描述了一种灵敏且自动化的方法，使用在线固相萃取结合高效液相色谱/串联质谱法，采用混合三重四极杆线性离子阱质谱仪（LC-QTRAP-MS/MS），同时测定尿液中的14种邻苯二甲酸酯代谢物、双酚A和四种双酚类似物，所需样品体积非常少（50µL）。在选择反应监测（SRM）模式下，采用负电喷雾电离进行定量分析。研究了在同一分析中结合增强产物离子扫描使用SRM的情况。通过每个化合物获取三个SRM跃迁和同位素稀释进行明确鉴定。该方法的分析性能在合成尿液和人尿液中进行了评估。所有化合物在三个数量级上均显示出线性响应（R(2)>0.99），方法检测限为0.01 - 0.5ng/mL，报告限为0.07 - 3.1ng/mL。准确度范围为93%至113%，日内和日间精密度均<22%。最后，该经过验证的方法已成功应用于一组孕妇，以测量邻苯二甲酸盐和双酚的生物标志物浓度，中位数浓度范围为0.3ng/mL（双酚S）至18.5ng/mL（邻苯二甲酸单乙酯）。
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