School of Public Health and Beijing Key Laboratory of Environmental Toxicology, Capital Medical University, Beijing, 100069, China.
Beijing Center for Disease Prevention and Control, Beijing Research Center for Preventive Medicine, Beijing, 100013, China.
Anal Bioanal Chem. 2022 Jun;414(14):4255-4265. doi: 10.1007/s00216-022-04079-3. Epub 2022 Apr 21.
Organophosphate esters (OPEs) and their diester metabolites have been frequently found in various environmental matrices and regarded as emerging environmental pollutants, whereas data on their occurrence in foods and human matrices are still limited. In this study, a novel and simple procedure was developed to simultaneously determine 14 OPEs and 6 diester metabolites in dairy products and human milk. After enzymatic hydrolysis by β-glucuronidase/arylsulfatase, a freeze-dried milk sample was extracted with acetonitrile and purified by solid-phase extraction. Subsequently, all target compounds were determined by HPLC-ESI-MS/MS. Linearity, limits of detection (LODs), recovery, precision, and matrix effects of the proposed methodology were validated, and the parameters of HPLC-ESI-MS/MS were optimized. LODs for OPEs and their diester metabolites were from 0.001 to 0.02 ng/mL, and limits of quantification (LOQs) were 0.01-0.3 ng/mL. Average recoveries at two spiked levels ranged between 67.3 and 121%, with relative standard deviation lower than 20.7%. A test for matrix effects showed that most analytes presented signal suppression, and isotopically labeled ISs were essential for compensating for the matrix effects. Finally, OPEs and their metabolites both showed high detecting frequencies in real samples, which indicated that these emerging pollutants were ubiquitous in foods and the human body, and the impact of the diester metabolites on population exposure must be included in exposure assessment.
有机磷酸酯 (OPEs) 及其二酯代谢物已在各种环境基质中频繁检出，被视为新兴环境污染物，然而其在食品和人体基质中的数据仍然有限。在本研究中，开发了一种新颖且简单的方法来同时测定乳制品和人乳中的 14 种 OPEs 和 6 种二酯代谢物。经 β-葡萄糖醛酸酶/芳基硫酸酯酶酶解后，冷冻干燥的奶样用乙腈提取并用固相萃取法纯化。随后，采用高效液相色谱-电喷雾串联质谱法（HPLC-ESI-MS/MS）测定所有目标化合物。对所提议方法的线性、检出限 (LOD)、回收率、精密度和基质效应进行了验证，并优化了 HPLC-ESI-MS/MS 的参数。OPEs 及其二酯代谢物的 LOD 为 0.001-0.02ng/mL，定量限 (LOQ) 为 0.01-0.3ng/mL。两个加标水平的平均回收率在 67.3%至 121%之间，相对标准偏差低于 20.7%。基质效应试验表明，大多数分析物表现出信号抑制，且使用同位素标记的内标对于补偿基质效应至关重要。最后，在实际样品中均高度检测到 OPEs 及其代谢物，这表明这些新兴污染物在食品和人体中普遍存在，在进行暴露评估时必须考虑二酯代谢物对人群暴露的影响。
