State Environmental Protection Key Laboratory of Environmental Pollution Health Risk Assessment, South China Institute of Environmental Sciences, Ministry of Ecology and Environment, Guangzhou, 510655, PR China.
State Environmental Protection Key Laboratory of Environmental Pollution Health Risk Assessment, South China Institute of Environmental Sciences, Ministry of Ecology and Environment, Guangzhou, 510655, PR China; School of Public Health, Key Laboratory of Environmental Pollution and Disease Monitoring of Ministry of Education, Guizhou Medical University, Guiyang, 550000, PR China.
Chemosphere. 2021 Jan;262:127807. doi: 10.1016/j.chemosphere.2020.127807. Epub 2020 Jul 30.
Human hair has been identified as a non-invasive alternative matrix for assessing the human exposure to specific organic contaminants. In the present study, a solvent-saving analytical method for the simultaneous determination of 8 polybrominated diphenyl ethers (PBDEs), 3 hexabromocyclododecanes (HBCDDs), 12 phosphorus flame retardants (PFRs), and 4 emerging PFRs (ePFRs) has been developed and validated for the first time. Hair sample preparation protocols include precleaning with Milli-Q water, digestion with HNO/HO (1:1, v/v), liquid-liquid extraction with hexane:dichloromethane (4:1, v/v), and fractionation and cleanup on a Florisil cartridge. The method was validated by using two levels of spiked hair samples of 3 replicates for each spiking group. Limits of quantification (LOQs) were 0.12-22.4 ng/g for all analytes, average values of accuracies were ranging between 88 and 115%, 82-117%, 81-128%, and 81-95% for PBDEs, HBCDDs, PFRs, and ePFRs, respectively; and precision was also acceptable (RSD < 20%) for all analytes. Eventually, this method was applied to measure the levels of the targeted analytes in hair samples of e-waste dismantling workers (n = 14) from Qingyuan, South China. Median values ranged between 3.00 and 18.1 ng/g for PBDEs, 0.84-4.04 ng/g for HBCDDs, 2.13-131 ng/g PFRs, and 1.49-29.4 ng/g for ePFRs, respectively. PFRs/ePFRs constitute the major compounds in human hair samples, implying the wide use of PFRs/ePFRs as replacements of PBDEs and HBCDDs, as well the potential high human exposure risks of PFRs/ePFRs. Overall, this work will allow to a comprehensive assessment of human exposure to multiple groups of FRs using hair as a non-invasive bioindicator.
人类头发已被确定为一种非侵入性的替代基质，可用于评估人体对特定有机污染物的暴露情况。在本研究中，首次开发并验证了一种用于同时测定 8 种多溴二苯醚（PBDEs）、3 种六溴环十二烷（HBCDDs）、12 种磷系阻燃剂（PFRs）和 4 种新兴 PFRs（ePFRs）的溶剂节约型分析方法。头发样品制备方案包括先用 Milli-Q 水预清洗，然后用 HNO3/H2O（1:1，v/v）消解，用正己烷/二氯甲烷（4:1，v/v）液液萃取，最后用 Florisil 柱进行分离和净化。该方法通过使用 3 个重复的 2 个浓度水平的加标头发样品进行验证。所有分析物的定量限（LOQs）均为 0.12-22.4ng/g，平均准确度值在 88-115%、82-117%、81-128%和 81-95%之间，分别为 PBDEs、HBCDDs、PFRs 和 ePFRs；所有分析物的精密度也可接受（RSD<20%）。最终，该方法应用于测量来自中国南方清远市电子废物拆解工人头发样本中目标分析物的水平（n=14）。PBDEs 的中位数范围在 3.00-18.1ng/g 之间，HBCDDs 的中位数范围在 0.84-4.04ng/g 之间，PFRs 的中位数范围在 2.13-131ng/g 之间，ePFRs 的中位数范围在 1.49-29.4ng/g 之间。PFRs/ePFRs 构成了人类头发样本中的主要化合物，这意味着 PFRs/ePFRs 作为 PBDEs 和 HBCDDs 的替代品被广泛使用，以及 PFRs/ePFRs 对人体暴露的潜在高风险。总的来说，这项工作将允许使用头发作为非侵入性生物标志物，对人类接触多组 FRs 进行全面评估。
