Production of Hydroxylated Polybrominated Diphenyl Ethers (OH-PBDEs) from Bromophenols by Manganese Dioxide
Production of Hydroxylated Polybrominated Diphenyl Ethers (OH-PBDEs) from Bromophenols by Manganese Dioxide
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二氧化锰从溴酚生产羟基化多溴二苯醚（OH-PBDEs）
DOI：
10.1021/es403583b
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发表时间：
2014-01-07
影响因子：
11.4
通讯作者：
Gan, Jay
中科院分区：
文献类型：
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作者：
Lin, Kunde;Yan, Chao;Gan, Jay
羟基多溴二苯醚(OH-PBDEs)因其比多溴联苯醚(PBDEs)更强的毒理作用而备受关注。到目前为止，研究将羟基多溴二苯醚的来源归因于多溴二苯醚的生物新陈代谢和环境中的自然产生。然而，目前还不清楚羟基多溴二苯醚是如何自然形成的。在这项研究中，我们探索了通过水钠石(Delta-MnO2)氧化转化简单的溴苯酚(如4-BP、2，4-DBP和2，4，6-TBP)来形成OH-PBbE。结果表明，β-MnO2以BPS为前驱体很容易生成羟基多溴二苯醚。例如，用Delta-MnO2氧化2，4-DBP生成2‘-OH-BDE-68和2’，5‘-OH-BDE-25。在与4-BP和2，4，6-TBP的反应中还检测到了6-OH-BDE-13，2‘，5’-OH-BDE-3，4‘-OH-BDE-121和2’，5‘-OH-BDE-69。OH-PBDEs的形成可能是溴苯氧基自由基氧化偶联的结果。弱酸性条件增强，而共存阳离子(如Na+、Mg2+和Ca2+)抑制转化。鉴于苯系物和β-MnO2的普遍存在，β-MnO2和其他金属氧化物对苯系物的氧化很可能是环境中形成OH-PBDEs的一种非生物途径。
Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are of significant concern because of their enhanced toxicological effects compared to PBDEs. Research to date has attributed the origin of OH-PBDEs to biological metabolism of PBDEs and natural production in the environment. However, it is unclear how OH-PBDEs are formed naturally. In this study, we explored the formation of OH-PBbEs via the oxidative transformation of simple bromophenols (BPs, e.g., 4-BP, 2,4-DBP, and 2,4,6-TBP) by birnessite (delta-MnO2). Results showed that OH-PBDEs were readily produced by delta-MnO2 with BPs as precursors. For example, oxidation of 2,4-DBP by delta-MnO2 yielded 2'-OH-BDE-68 and 2',5'-OH-BDE-25. Other OH-PBDEs, such as 6-OH-BDE-13, 2',5'-OH-BDE-3, 4'-OH-BDE-121, and 2',5'-OH-BDE-69, were detected from the reaction with 4-BP and 2,4,6-TBP. The formation of OH-PBDEs likely resulted from the oxidative coupling of bromophenoxy radicals. Mild acidic conditions enhanced while coexisting cations (e.g., Na+, Mg2+, and Ca2+) suppressed the transformation. Given the ubiquity of BPs and delta-MnO2, oxidation of BPs by delta-MnO2 and other metal oxides is likely an abiotic route for the formation of OH-PBDEs in the environment.