Development of an analytical method to quantify PBDEs, OH-BDEs, HBCDs, 2,4,6-TBP, EH-TBB, and BEH-TEBP in human serum.
Development of an analytical method to quantify PBDEs, OH-BDEs, HBCDs, 2,4,6-TBP, EH-TBB, and BEH-TEBP in human serum.
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DOI：
10.1007/s00216-016-9340-3
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发表时间：
2016-04
影响因子：
4.3
通讯作者：
Stapleton HM
中科院分区：
文献类型：
--
作者：
Butt CM;Miranda ML;Stapleton HM
多溴二苯醚阻燃剂已于2000年代中期（五溴二苯醚和八溴二苯醚）和2013年（十溴二苯醚）逐步淘汰;然而，其羟基化代谢物（羟基溴二苯醚）仍然经常在人类血清中检测到。如今，Firemaster® 550（一种含有两种溴化化合物EH-TBB和BEH-TEBP的混合物）等新型阻燃剂在某些应用中被用作多溴二苯醚的替代品，因此需要开发一种综合分析方法，以评估传统多溴二苯醚和新型阻燃剂的接触情况。本研究建立了一种基于固相萃取（SPE）的方法来分析人体血清中的PBDEs、OH-BDEs、2，4，6-三溴苯酚（TBP）、六溴环十二烷异构体（HBCDs）、EH-TBB和BEH-TEBP。简言之，首先用甲酸使血清蛋白变性，然后使用SPE柱分离目标分析物。最后，使用硅胶SPE柱对提取物进行清洗和分级。通过向胎牛血清中加标1-2 ng目标分析物来评估方法性能，并通过与血清标准参比物质（SRM）进行比较来定量方法准确度。所开发的方法显示出良好的回收率和准确度的所有目标分析物的非常低和非常高的分子量的多溴二苯醚同系物除外。使用该方法，分析了从达勒姆，NC，USA的健康妊娠，健康婴儿研究（HPHB）队列中采集的43份血清样本的FR。一项新的发现是普遍检测到2，4，6-TBP，其水平高于单个多溴二苯醚同系物。此外，2，4，6-TBP与多溴联苯醚呈正相关，这表明它们可能有类似的接触源，或者2，4，6-TBP可能是多溴联苯醚在体内代谢的结果。
Polybrominated diphenyl ethers (PBDEs) flame retardants (FRs) were phased-out in the mid-2000s (penta- and octaBDE) and 2013 (decaBDE); however, their hydroxylated metabolites (OH-BDEs) are still commonly detected in human serum. Today, novel FRs such as Firemaster® 550, a mixture that contains two brominated compounds, EH-TBB and BEH-TEBP are used as replacements for PBDEs in some applications, and there is a need to develop a comprehensive analytical method to assess exposure to both legacy PBDEs and novel FRs. This study developed a solid-phase extraction (SPE)-based method to analyze PBDEs, OH-BDEs, 2,4,6-tribromophenol (TBP), hexabromocylcododecane isomers (HBCDs), EH-TBB, and BEH-TEBP in human serum. Briefly, serum proteins were first denatured with formic acid, and then the target analytes were isolated using a SPE column. Finally, the extract was cleaned and fractioned using a silica SPE column. Method performance was assessed by spiking fetal bovine serum with 1–2 ng of the target analytes, and method accuracy was quantified by comparison to a serum Standard Reference Material (SRM). The developed method showed good recovery and accuracy for all target analytes with the exception of the very low and very high molecular weight PBDE congeners. Using this method, 43 serum samples collected from the Healthy Pregnancy, Healthy Baby Study (HPHB) cohort in Durham, NC, USA were analyzed for FRs. A novel finding was the ubiquitous detection of 2,4, 6-TBP, at levels greater than the individual PBDE congeners. Furthermore, 2,4,6-TBP was positively correlated with PBDEs, suggesting that they may have a similar source of exposure, or that 2,4,6-TBP may result from metabolism of PBDEs in vivo.