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 HNO₃/H₂O₂ (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.

人发已被鉴定为评估人类暴露于特定有机污染物的非侵入性替代基质。在本研究中，开发并验证了一种同时测定8种多溴二苯醚（PBDEs），3种六溴环十二烷（HBCDDs），12种磷阻燃剂（PFRs）和4种新兴PFRs（ePFRs）的节省溶剂的分析方法。首次。毛发样品制备方案包括用Milli-Q水预清洗，用HNO ₃ / H ₂ O ₂消解（1：1，v / v），用己烷：二氯甲烷（4：1，v / v）进行液-液萃取，并在Florisil柱上进行分馏和净化。对于每个加标组，通过使用两个水平的加标毛发样品（重复3次）来验证该方法。所有分析物的定量限（LOQs）为0.12–22.4 ng / g，PBDEs，HBCDDs，PFRs的平均准确度范围为88％至115％，82–117％，81–128％和81–95％和ePFR，分别；所有分析物的精密度（RSD <20％）也是可以接受的。最终，该方法用于测量来自华南清远的电子废物拆解工人（n = 14）的头发样本中目标分析物的水平。PBDEs的中位数值在3.00至18.1 ng / g之间，HBCDDs的中位数值在0.84–4.04 ng / g之间，ePFRs的中位数值分别在2.13–131 ng / g和1.49–29.4 ng / g之间。PFRs / ePFRs是人发样品中的主要化合物，这意味着PFRs / ePFRs可以作为PBDEs和HBCDDs的替代品而广泛使用，以及PFRs / ePFRs潜在的高人体暴露风险。总体而言，这项工作将允许使用头发作为非侵入性生物指示剂来全面评估人类对多组FR的暴露程度。