Formation pathways of brominated products from benzophenone-4 chlorination in the presence of bromide ions

The brominated products, formed in chlorination treatment of benzophenone-4 in the presence of bromide ions, were identified, and the formation pathways were proposed.Under disinfection conditions, benzophenone-4 would undertake electrophilic substitution generating mono- or di-halogenated products, which would be oxidized to esters and further hydrolyzed to phenol derivatives. The generated catechol intermediate would be transformed into furan-like heterocyclic product. The product species were p H-dependent,while benzophenone-4 elimination was chlorine dose-dependent. When the chlorination treatment was performed on ambient water spiked with benzophenone-4 and bromide ions, most of brominated byproducts could be detected, and the acute toxicity significantly increased as well.     

二苯甲酮类紫外防晒剂发光菌急性毒性及QSAR研究

二苯甲酮类化合物广泛用于防晒剂、塑料添加剂、香味剂等。随着紫外防晒产品的大量使用,其环境及健康风险越来越受到人们的关注。为揭示二苯甲酮类污染物的毒性特征,选择了14种二苯甲酮类化合物作为目标化合物,测试了它们对发光细菌的急性毒性效应。分别运用二维、三维定量构效相关技术和分子对接技术探讨了目标化合物的分子结构特征对毒性效应的影响。结果表明14种二苯甲酮类化合物对发光菌急性毒性的EC50值在17.67到243.82 mg·L-1范围内,其中2-羟基-4-甲氧基-5-磺酸基二苯甲酮的急性毒性最低,2,2',4,4'-四羟基二苯甲酮的毒性最高。羟基取代的二苯甲酮化合物的急性毒性随着分子中羟基数量的增加而升高;具有相同羟基数量的二苯甲酮类化合物,羟基位于苯环4-位时毒性最高,3-位时次之,2-位时毒性最低。QSAR结果表明,运用静电场、氢键受体场和氢键供体场能很好解释这类化合物的毒性特征,若在苯环4-位引入带正电荷的官能团、在苯环2-,4-位引入氢键受体,都将导致毒性升高。上述研究结果将为科学评价该类化合物的潜在生态风险提供基础数据。     

Widespread occurrence of estrogenic UV-filters in aquatic ecosystems in Switzerland

We performed a trace analytical study covering nine hormonally active UV-filters by LC-MS/MS and GC-MS in river water and biota. Water was analysed at 10 sites above and below wastewater treatment plants in the river Glatt using polar organic chemical integrative samplers (POCIS). Four UV-filters occurred in the following order of decreasing concentrations; benzophenone-4 (BP-4) > benzophenone-3 (BP-3) > 3-(4-methyl)benzylidene-camphor (4-MBC) > 2-ethyl-hexyl-4-trimethoxycinnamate (EHMC). BP-4 ranged from 0.27 to 24.0 μg/POCIS, BP-3, 4-MBC and EHMC up to 0.1 μg/POCIS. Wastewater was the most important source. Levels decreased with higher river water flow. No significant in-stream removal occurred. BP-3, 4-MBC and EHMC were between 6 and 68 ng/L in river water. EHMC was accumulated in biota. In all 48 macroinvertebrate and fish samples from six rivers lipid-weighted EHMC occurred up to 337 ng/g, and up to 701 ng/g in 5 cormorants, suggesting food-chain accumulation. UV-filters are found to be ubiquitous in aquatic systems.