基于电感耦合等离子体质谱技术的OH-PBDEs检测新方法及其在备孕女性体内PBDEs及OH-PBDEs暴露监测中的应用研究

Polybrominated diphenyl ethers (PBDEs) were a group of widely used flame retardants which have been banned due to their environmental persistence and toxicity. However, decabromodiphenyl ether (BDE-209) is still in use in China and has become one of the most abundant analogue in environment. The hydroxylation of PBDEs has been confirmed as an important metabolic pathway. The metabolites (OH-PBDEs) were considered as contaminants with higher toxicity than PBDEs. The occurrence of PBDEs and OH-PBDEs in pregnant woman and neonate has been confirmed by several researches and the potential healthy damage aroused concerns. As one of the largest producer and user, limited information of this topic can be obtained in China. This research proposed a Online SPE-HPLC-ICP-MS method which could simultaneously analyze PBDEs and OH-PBDEs without derivation of OH-PBDEs. Meanwhile, this method could avoid the degradation of BDE-209 during analysis process. The ionization efficiency in ICP was a satisfaction for PBDEs analysis. The simultaneous determination of PBDEs and OH-PBDEs simplified the pretreatment procedure and made the best use of limited serum samples. The developed method was applied for the analysis of serum sample from pre-pregnant woman in Tianjin City which is a coastal city. The results could provide data for the exposure estimation. Besides, the comparison between pollution profiles in serum and local sea food could be an approach for preliminary investigation and parsing of pollutants sources.

羟基多溴二苯醚（OH-PBDEs）是多溴二苯醚（PBDEs）的羟基化产物，主要来源为海洋环境天然形成或生物体内代谢产生。OH-PBDEs对生物体的毒性效应已被证实要高于PBDEs。研究表明在孕妇和胎儿体内均可能检出OH-PBDEs和PBDEs，并可能会对其健康产生负面效应。我国作为PBDEs生产使用大国，相关环境污染与健康的研究数据仍十分匮乏。随着对PBDEs的禁用，十溴联苯醚（BDE-209）逐步成为我国环境中比重最大的单体，对其分析检测不容忽视。本研究首次提出应用Online SPE-HPLC-ICP-MS方法对有机溴代污染物进行分析检测，在提高高溴代单体测量能力的同时实现对PBDEs和OH-PBDEs的同时分析，应用该方法分析沿海城市天津的备孕女性血清中溴代污染物的赋存浓度，为其暴露监测提供技术和数据支持，同时，还可结合当地代表性海产品中OH-PBDEs的污染特征进行初步源解析。

多溴二苯醚（PBDEs）是一类新型持久性有机污染物，羟基多溴二苯醚（OH-PBDEs）是其重要的代谢产物。综合其污染来源及环境行为，沿海城市是这两类污染物人体暴露的典型区域。本研究选取环境中常见的PBDEs及其主要的OH-PBDEs代谢产物作为研究对象，建立可以同时分析两类污染物的检测新方法并对天津地区部分待孕青年血清中赋存情况进行了初步分析。综合在线固相萃取（Online SPE）的富集效率、高效液相色谱（HPLC）的分离定性以及电感耦合等离子体质谱（ICPMS）的元素定性定量性能，建立了Online SPE-HPLC-ICPMS方法同时检测PBDEs和其主要羟基代谢产物。通过优化OnlineSPE的关键参数（固相萃取柱、上样速率、流速等），HPLC条件（流动相组成、流速、梯度等），ICPMS关键参数（可选气体比例、碰撞模式等），实现了在样品量有限（≤0.5 mL）的条件下对痕量/超痕量目标物的准确检测，方法灵敏度（定量限<1 ng/L）、稳定性（相对标准偏差<10%，n=3）、准确度（回收率61. 8% -77.7%）均满足实际血清样品分析的需求，且在线技术的集成可适用于大批量样品的检测。将建立的方法应用于采集自天津地区300个待孕青年血清样品的分析，共检出4种PBDEs（BDE-28，-47，-99和-153）和5种OH-PBDEs （3-OH-BDE-47, 5-OH-BDE-47, 6-OH-BDE-47, 5’-OH-BDE-47和 6’-OH-BDE-47），通过对人群信息和检出结果的分析，研究区域中目标物检出率均小于20%，20-30岁区间男性检出率略高于同年龄段女性及30-40岁的女性，这可能与生活习惯及代谢特征相关。而20-30岁女性的检出率及浓度水平与30-40岁女性基本一致，未发现明显的区别。较低的检出浓度表明该类污染物的暴露量造成的健康风险仍在可控范围。综上，本研究所建立的Online SPE-HPLC-ICPMS技术及初步暴露特征研究可为PBDEs及OH-PBDEs的健康风险研究提供技术和数据支持。