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钴/过一硫酸盐氧化降解四溴双酚S过程中溴化副产物的形成

Formation of brominated by-products during the degradation of tetrabromobisphenol S by Co/peroxymonosulfate oxidation.

作者信息

Wang Lu, Yu Yaqun, Liu Guoqiang, Lu Junhe

机构信息

School of Life Science, Shaoxing University, Shaoxing, 312000, China; Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing, 210095, China.

Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing, 210095, China.

出版信息

J Environ Manage. 2022 Jul 15;314:115091. doi: 10.1016/j.jenvman.2022.115091. Epub 2022 Apr 23.

DOI:10.1016/j.jenvman.2022.115091
PMID:35472837
Abstract

Tetrabromobisphenol S (TBBPS), an emerging brominated flame retardant, can cause neurotoxic and cytotoxic effects to human physiology. In this study, the degradation of TBBPS in Co activated peroxymonosulfate (PMS) oxidation process was explored. In particular, brominated by-products formed during the degradation of the TBBPS were examined. It was found that TBBPS could be effectively removed in the Co/PMS oxidation process. The pseudo-first-order rate constants were 0.13 min at 0.2 mM PMS and 0.5 μM Co initially. It appeared that TBBPS degradation occurred via and HO attacks, but played a dominant role. The presence of natural organic matter (NOM) greatly inhibited the transformation of the TBBPS, which can be explained by the scavenging of the radical species. β-Scission, debromination, and cross-coupling were identified as the main reaction pathways of TBBPS degradation in the Co/PMS system. Further oxidation and ring-opening of the intermediates generated brominated by-products including bromoform, monobromoacetic acid, and dibromoacetic acid. The formation of the brominated by-products increased gradually in approximately 48 h. But, the presence of NOM reduced the yields of the brominated -by-products. The findings of this study indicate that organic bromine contaminants can be effectively removed but lead to brominated by-products in the activated PMS oxidation process, which should be taken into consideration when -based oxidation technology is applied.

摘要

四溴双酚 S(TBBPS)是一种新型溴化阻燃剂,可对人体生理产生神经毒性和细胞毒性作用。本研究探讨了 TBBPS 在钴活化过一硫酸盐(PMS)氧化过程中的降解情况。特别地,对 TBBPS 降解过程中形成的溴化副产物进行了检测。结果发现,TBBPS 在 Co/PMS 氧化过程中能够被有效去除。初始条件为 0.2 mM PMS 和 0.5 μM 钴时,伪一级反应速率常数为 0.13 min⁻¹。TBBPS 的降解似乎是通过·OH 攻击发生的,但 起主导作用。天然有机物(NOM)的存在极大地抑制了 TBBPS 的转化,这可以通过自由基物种的清除来解释。β-断裂、脱溴和交叉偶联被确定为 Co/PMS 体系中 TBBPS 降解的主要反应途径。中间体的进一步氧化和开环产生了溴化副产物,包括溴仿、一溴乙酸和二溴乙酸。溴化副产物的形成在大约 48 小时内逐渐增加。但是,NOM 的存在降低了溴化副产物的产率。本研究结果表明,有机溴污染物在活化 PMS 氧化过程中可以被有效去除,但会产生溴化副产物,在应用基于 PMS 的氧化技术时应予以考虑。

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