Phan Khoi, Mouakkad Lila, Juma Tom, Otim Ochan
Environmental Monitoring Division, City of Los Angeles, 12000 Vista Del Mar, Playa Del Rey, CA. 90293, USA.
Environmental Monitoring Division, City of Los Angeles, 12000 Vista Del Mar, Playa Del Rey, CA. 90293, USA; Department of Health and Sciences, University of California - Los Angeles, Los Angeles, CA 90024.
J Chromatogr A. 2025 Aug 30;1757:466141. doi: 10.1016/j.chroma.2025.466141. Epub 2025 Jun 11.
Polybrominated diphenyl ethers (PBDEs), a class of flame retardants used extensively in consumer products, have become ecological and public health hazards. Monitoring exposure to them has therefore become a priority as well. At the request of a regulating body, a cost-effective GC-ECD method that exploits advances in gas chromatography was developed in this study to monitor particularly PBDE-28, 47, 99, 100, 153, 154, 183 and 209 in treated municipal wastewater. The proposed method utilizes a programmable injector, an injection volume splitter, and two short open capillary columns (DB-5XLB and DB-5MS) in additoin to a pair of Ni-based halogen-specific electron capture detectors to analyze the PBDEs. All eight PBDEs and PCB-209 surrogate are baseline resolved within a 0.02 min retention time window. The analytes were also recovered quantitatively from single injections of fortified wastewater extracts (range: 76.2-101 % with relative percent deviation range: 2.4-11.7 %). The method detection limits were 1.0-3.4 ng/L for smaller PBDEs and 40 ng/L for PBDE-209. For quantitation, 16 six-point concentration calibration curves, eight for each column, were generated. The relative standard deviations range associated with the curves was 1.6-12 % (r > 0.998) for smaller PBDEs and 26-45 % (r: 0.984-0.994) for PBDE-209. Additionally, DB-5MS retention times (t range: 6.85-18.40 min) were found to relate strongly with DB-XLB retention times (t: 7.03-23.32 min) by the polynomial t =-0.02[t] + 1.33[t]-1.94 (r² =0.9997). The relationship suggests that the 182 congeners larger than PBDE-27, but not included here, could be detected and quantified by the proposed method.
多溴二苯醚（PBDEs）是一类广泛用于消费品的阻燃剂，已成为生态和公共健康危害。因此，监测人体对它们的暴露情况也已成为当务之急。应监管机构的要求，本研究开发了一种利用气相色谱技术进步的经济高效的气相色谱 - 电子捕获检测器（GC - ECD）方法，以监测经过处理的城市废水中的PBDE - 28、47、99、100、153、154、183和209。所提出的方法除了使用一对镍基卤素特异性电子捕获检测器外，还利用了可编程进样器、进样量分流器和两根短的开口毛细管柱（DB - 5XLB和DB - 5MS）来分析多溴二苯醚。所有八种多溴二苯醚和多氯联苯 - 209替代物在0.02分钟的保留时间窗口内实现基线分离。从强化废水提取物的单次进样中也能对分析物进行定量回收（范围：76.2 - 101%，相对百分偏差范围：2.4 - 11.7%）。较小的多溴二苯醚的方法检测限为1.0 - 3.4纳克/升，PBDE - 209的检测限为40纳克/升。为了进行定量分析，生成了16条六点浓度校准曲线，每根柱子各8条。较小的多溴二苯醚的曲线相关的相对标准偏差范围为1.6 - 12%（r > 0.998），PBDE - 209的相对标准偏差范围为26 - 45%（r：0.984 - 0.994）。此外，通过多项式t = -0.02[t]² + 1.33[t] - 1.94（r² = 0.9997）发现DB - 5MS的保留时间（t范围：6.85 - 18.40分钟）与DB - XLB的保留时间（t：7.03 - 23.32分钟）有很强的相关性。这种关系表明，所提出的方法可以检测和定量比PBDE - 27大但未包含在此处的182种同系物。
