Lin Xiao, Bao Dejun, Sun Qi, Zhang Xu, Feng Zhuangzhuang, Zhu Ying
China CDC Key Laboratory of Environment and Population Health, National Institute of Environmental Health, Chinese Center for Disease Control and Prevention, Beijing 100021, PR China.
China CDC Key Laboratory of Environment and Population Health, National Institute of Environmental Health, Chinese Center for Disease Control and Prevention, Beijing 100021, PR China.
J Chromatogr A. 2025 Sep 27;1759:466234. doi: 10.1016/j.chroma.2025.466234. Epub 2025 Jul 18.
An efficient technique for quantitative analysis of BPA, BPF, BPS, and 11 emerging bisphenol analogues in human urine has been developed, which combined solid phase extraction (SPE) with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Stable isotope internal standards were added to 1.0 mL of urine, which was hydrolyzed by β-glucuronidase overnight, and the target analytes were enriched and purified using an HLB 96-well plate, concentrated to dryness by nitrogen blowdown and reconstituted in 0.5 mL of 20 % aqueous methanol solution. Separation of the 14 analytes was achieved using Acquity BEH C (100 mm × 2.1 mm, 1.7 μm) as the analytical column and gradient elution with water and methanol as the mobile phase. Qualitative and quantitative analyses were performed in multiple reaction monitoring (MRM) mode with parallel positive and negative ion detection. Fourteen analytes showed good linearity in the concentration range of 0.1-50 ng/mL with correlation coefficients (r) greater than 0.999. The method detection limits (MDLs) range from 0.01 to 0.07 ng/mL and the method quantification limits (MQLs) were between 0.02 and 0.23 ng/mL. Recoveries across three spike levels were within the range of 72 % to 127 %. Intra-day precision and inter-day precision were below 12.7 % and 15.1 %, respectively. The proposed method successfully determined bisphenol analogues in 187 urine samples from young people in Beijing, revealing high prevalence rates for BPA (98.9 %) and BPS (80.2 %), with median concentrations of 6.44 μg/L and 0.17 μg/L, respectively. No significant differences in BPA and BPS levels were observed between genders, suggesting similar exposure patterns in males and females. Notably, the detection rate of the new alternative DBSP reached 32.6 %, indicating its significant exposure in the population. This study highlights the ongoing public health concerns regarding exposure to bisphenol analogues, encompassing both traditional compounds (such as BPA and BPS) and emerging alternatives.
已开发出一种高效的技术，用于定量分析人尿中的双酚A（BPA）、双酚F（BPF）、双酚S（BPS）以及11种新兴双酚类似物，该技术将固相萃取（SPE）与超高效液相色谱 - 串联质谱（UHPLC - MS/MS）相结合。向1.0 mL尿液中加入稳定同位素内标，用β - 葡萄糖醛酸酶水解过夜，目标分析物用HLB 96孔板进行富集和纯化，通过氮气吹干浓缩至干，再用0.5 mL 20%的甲醇水溶液复溶。使用Acquity BEH C（100 mm×2.1 mm，1.7μm）作为分析柱，以水和甲醇为流动相进行梯度洗脱，实现了14种分析物的分离。在多反应监测（MRM）模式下进行定性和定量分析，采用平行正离子和负离子检测。14种分析物在0.1 - 50 ng/mL的浓度范围内呈现良好的线性，相关系数（r）大于0.999。方法检测限（MDLs）范围为0.01至0.07 ng/mL，方法定量限（MQLs）在0.02至0.23 ng/mL之间。三个加标水平的回收率在72%至127%范围内。日内精密度和日间精密度分别低于12.7%和15.1%。所提出的方法成功测定了北京年轻人的187份尿液样本中的双酚类似物，结果显示BPA（98.9%）和BPS（80.2%）的检出率很高，中位数浓度分别为6.44μg/L和0.17μg/L。未观察到BPA和BPS水平在性别之间存在显著差异，表明男性和女性的暴露模式相似。值得注意的是，新型替代物双（2 - 苯氧基苯基）砜（DBSP）的检出率达到32.6%，表明其在人群中的暴露情况较为显著。这项研究突出了当前公众对双酚类似物暴露的健康担忧，包括传统化合物（如BPA和BPS）以及新兴替代物。
