The accumulation of organic contaminants in hair with different biological characteristics.

Human hair has increasingly been used as a noninvasive biomonitoring matrix for assessment of human exposure to various organic contaminants (OCs). However, the accumulation processes of OCs in hair remains unclear thus far, which raised concerns on the reliability of hair analysis results for OCs. Herein, Chinese population was selected as the study subject, the effects of changes in hair biological characteristics, including length and color, on the accumulation of OCs in hair was investigated. With the growing of hair shaft and the increased distance from the scalp, a significant increasing trend was found for levels of polychlorinated biphenyls (PCBs) and organophosphate flame retardants (PFRs) along the hair shafts (p < 0.05). Source identification using Chemical Mass Balance model indicated that PCBs in hair were mainly from exogenous sources (air and dust). The accumulation rates of PCB and PFR individuals in the hair shaft decreased with increasing of log Kow values. Additionally, the levels of OCs in hair decreased with the change in color from black to white, probably because of the loss of melanin in white hair. The ratios (R) of Cblack/Cwhite were significantly correlated with the log Kow values for individual chemicals (p < 0.05), implying that OCs with high log Kow values tend to accumulate more readily in black hair. The results of this study demonstrated the growth and change in colors of hair, as well as the physicochemical properties of chemicals, play vital roles in the accumulation of OCs in hair. The present study provides fundamental basis for the precise assessment of human exposure to OCs using hair as a biomonitoring matrix in future studies.

Changes in human hair levels of organic contaminants reflecting China's regulations on electronic waste recycling.

To assess the impacts of regulations and laws enhancing the management of e-waste in China, hair samples of local residents and dismantling workers in a former e-waste area in 2016 and 2019, five and eight years after the implementation of legislation and regulations in this area since 2011, respectively. The temporal changes in levels of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organophosphorus flame retardants (OPFRs) in the hair samples were investigated. Besides, the levels of these organic contaminants in hair samples collected from the same area in 2009, 2011, and 2015 reported in previous studies were used as comparison. The highest median levels of Σ9PCBs (719 ng/g), Σ3Penta-BDEs (16.1 ng/g), and Σ3Octa-BDEs (8.46 ng/g) in hair were found in 2011, with a significant decrease trend was observed from 2011 to 2019 (p < 0.05). As for Deca-BDE, the levels reached the maximum in 2015 (133 ng/g), following by a significant decrease to 2016 (7.46 ng/g) and 2019 (2.61 ng/g) (p < 0.05). The median levels of Σ8OPFRs, also decreased significantly (p < 0.05) from 2015 (357 ng/g) to 2016 (264 ng/g) and 2019 (112 ng/g). Moreover, a significantly increasing trend was observed for the ratios of triphenyl phosphate (TPHP) and tris(2-chloropropyl) phosphate (TCIPP), two predominant OPFRs, to Deca-BDE from 2015 to 2019 (p < 0.01), suggesting a shift of "legacy" to "emerging" contaminants released from e-waste recycling in this area. The temporal changes in hair levels of typical organic contaminants in residents and dismantling workers indicated the effectiveness of the regulations on informal e-waste recycling activities and solid waste in China.

Analysis of polybrominated diphenyl ethers, hexabromocyclododecanes, and legacy and emerging phosphorus flame retardants in human hair.

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.