State Key Laboratory of Organic Geochemistry, Guangzhou Institute of geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China; University of Chinese Academy of Sciences, Beijing, 100049, China.
South China Institute of Environmental Sciences, Ministry of Environmental Protection, Guangzhou, 510655, China.
J Chromatogr A. 2018 May 25;1551:29-40. doi: 10.1016/j.chroma.2018.04.003. Epub 2018 Apr 5.
Personal care products (PCPs) are ubiquitous in aquatic environments owing to the continuous discharge of domestic wastewater from highly urbanized regions. These PCPs can be adsorbed by fish and thereafter usually enter the bile of the fish through biliary excretion. In this study, a sensitive method based on a combination of hybrid solvent precipitation and dispersive solid phase extraction (d-SPE) purification was developed to simultaneously extract and detect 24 PCPs, namely, 16 biocides, 4 synthetic musks, and 4 benzotriazoles, from fish bile. Hybrid precipitation on solid phase extraction (SPE) tubes was applied to remove phospholipids and proteins, and a d-SPE procedure was used for further purification. The extraction solvents for the hybrid precipitation/SPE tubes and d-SPE materials were optimized. The method performance for bile samples both with and without enzyme hydrolysis using β-glucuronidase/aryl-sulfatase were validated. The 24 PCPs in fish bile were spiked with standard concentrations of 10 ng/mL, 20 ng/mL, 100 ng/mL, and 200 ng/mL to evaluate recoveries, which ranged from 70 to 120% for 16, 16, 22, and 21 analytes with hydrolysis, respectively, and 70-120% for 14, 15, 23, and 23 analytes without hydrolysis, respectively. The quantification limits for target PCPs were in the range 0.26-7.38 ng/mL [excluding musk xylene (MX) and musk ketone (MK)] and 0.20-9.48 ng/mL (excluding MX and MK) for bile samples with and without enzyme hydrolysis, respectively. After enzyme hydrolysis, 12 PCPs were detected in bile from fish collected from the Yangtze River, with a maximum detected concentration of 460 ng/mL, for triclosan (TCS). The hydrolysis reaction indicated that high percentages of glucuronide and sulfate metabolites for some PCPs, i.e. four parabens and TCS, existed in the bile.
个人护理产品（PCPs）由于高度城市化地区的生活污水不断排放，在水生环境中无处不在。这些 PCPs 可以被鱼类吸附，然后通常通过胆汁排泄进入鱼类的胆汁中。在本研究中，开发了一种基于混合溶剂沉淀和分散固相萃取（d-SPE）净化相结合的灵敏方法，用于同时从鱼胆汁中提取和检测 24 种 PCPs，即 16 种杀菌剂、4 种合成麝香和 4 种苯并三唑。在固相萃取（SPE）管上进行混合沉淀以去除磷脂和蛋白质，并用 d-SPE 程序进一步纯化。优化了混合沉淀/SPE 管和 d-SPE 材料的萃取溶剂。使用 β-葡萄糖醛酸酶/芳基硫酸酯酶对胆汁样品进行酶水解，并验证了方法性能。将 24 种 PCPs 以 10ng/mL、20ng/mL、100ng/mL 和 200ng/mL 的标准浓度加入到鱼胆汁中进行加标，水解后 16、16、22 和 21 种分析物的回收率分别在 70-120%之间，而不水解时 14、15、23 和 23 种分析物的回收率分别在 70-120%之间。目标 PCPs 的定量限在 0.26-7.38ng/mL[不包括麝香二甲苯（MX）和麝香酮（MK）]和 0.20-9.48ng/mL（不包括 MX 和 MK）之间，用于酶水解和不酶水解的胆汁样品。经酶水解后，从长江采集的鱼类胆汁中检测到 12 种 PCPs，其中三氯生（TCS）的检出浓度最高，为 460ng/mL。水解反应表明，胆汁中某些 PCPs 的葡萄糖醛酸和硫酸盐代谢物比例较高，即四种对羟基苯甲酸酯和 TCS。
