Identification of Three Novel Chloroalkyl Organophosphate Triesters in House Dust Using Halogenation-Guided Nontarget Screening Combined with Suspect Screening

Several haloalkyl organophosphate triester (OPTE) flame retardants have been restricted in some countries due to their potential health risks, but the usage of alternative haloalkyl OPTEs is of concern. In this study, we comprehensively screened for haloalkyl OPTEs in house dust using high-resolution mass spectrometry. Through halogenation-guided nontarget screening, a rare chloroalkyl OPTE, diethylene glycol bis­(bis­(2-chloroisopropyl)­phosphate) (DEGBBCPP), was unequivocally identified (Level 1) in house dust of Beijing, North China. In addition, by screening a suspect list of 61 haloalkyl OPTEs from the EPA’s CompTox Chemicals Dashboard, we tentatively identified diethylene glycol bis­(bis­(2-chloroethyl)­phosphate) (DEGBBCEP) and ethylene bis­[bis­(2-chloroethyl)­phosphate] (EBBCEP) (Level 2). DEGBBCPP was detected in all 45 house dust samples, and the median concentration was 98.4 ng/g (13.6–6217 ng/g), that is, approximately one-half that of tris­(1,3-dichloro-2-propyl) phosphate, a traditional high-production chloroalkyl OPTE. The detection frequencies of DEGBBCEP and EBBCEP were 96% and 98%, respectively, but at relatively low median concentrations of 10.6 ng/g (from not detected to 152 ng/g) and 3.79 ng/g (from not detected to 130 ng/g), respectively. In standard house dust SRM2585, DEGBBCEP and EBBCEP were detected at 160 ± 15.7 and 1897 ± 38.8 ng/g, respectively, but DEGBBCPP was not detected. Future studies should evaluate the potential adverse health effects of these emerging flame retardants.

由于潜在健康风险，部分国家已对部分卤代烷基磷酸三酯（haloalkyl organophosphate triester, OPTE）阻燃剂实施管制，但替代型卤代烷基磷酸三酯的使用情况仍备受关注。本研究采用高分辨质谱法，对室内灰尘中的卤代烷基磷酸三酯开展全面筛查。通过卤代导向非靶向筛查策略，在华北北京的室内灰尘样品中明确鉴定出一种罕见的氯代烷基磷酸三酯——二甘醇双(双(2-氯异丙基)磷酸酯)（DEGBBCPP），鉴定级别为一级（Level 1）。此外，本研究通过筛查美国环境保护署（Environmental Protection Agency, EPA）CompTox化学品数据库中的61种卤代烷基磷酸三酯疑似清单，初步鉴定出二甘醇双(双(2-氯乙基)磷酸酯)（DEGBBCEP）与亚乙基双[双(2-氯乙基)磷酸酯]（EBBCEP），鉴定级别为二级（Level 2）。DEGBBCPP在全部45份室内灰尘样品中均被检出，中位浓度为98.4 ng/g（范围13.6~6217 ng/g），约为传统高产量氯代烷基磷酸三酯磷酸三(1,3-二氯-2-丙基)酯浓度的一半。DEGBBCEP与EBBCEP的检出率分别为96%与98%，但中位浓度相对较低，分别为10.6 ng/g（未检出~152 ng/g）与3.79 ng/g（未检出~130 ng/g）。在标准室内灰尘参考物质SRM2585中，DEGBBCEP与EBBCEP的浓度分别为160±15.7 ng/g与1897±38.8 ng/g，但未检出DEGBBCPP。未来研究应评估这类新型阻燃剂潜在的不良健康影响。