Key Laboratory of Agro-Forestry Environmental Processes and Ecological Regulation of Hainan Province, School of Ecology and Environment, Hainan University, Haikou, Hainan 570228, PR China.
Key Laboratory of Tropical Biological Resources of Ministry of Education, Key Laboratory for Marine Drugs of Haikou, School of Pharmaceutical Sciences, Hainan University, Haikou, Hainan 570228, PR China.
Sci Total Environ. 2023 Jul 10;881:163498. doi: 10.1016/j.scitotenv.2023.163498. Epub 2023 Apr 15.
Diethylamino hydroxybenzoyl hexyl benzoate (DHHB), an ultraviolet (UV) filter, can be found in sunscreens and other personal care products and thus can be introduced into swimming pools through the swimmers. In outdoor pools, DHHB will inevitably interact with free chlorine and sunlight. Therefore, the mechanism of solar‑chlorine chemical transformation of DHHB, as well as the environmental risk, were investigated in this work. In chlorinated with solar (Cl + solar) process, free chlorine was the dominant contributor to 85% of the DHHB degradation, while hydroxyl radicals and reactive chlorine species contributed only 15% because of low free radical generation and fast DHHB and free chlorine reaction rates. Scavenging matrices, such as Cl, NH, and dissolved organic matter (DOM), inhibited the degradation of DHHB in the Cl + solar process, while Br, HCO, NO, and urea promoted DHHB degradation. DHHB degradation was inhibited in tap water swimming pool samples, while it was enhanced in seawater pool samples by the Cl + solar process. Seven transformation by-products (TBPs) including mono-, dichlorinated, dealkylate, and monochloro-hydroxylated TBPs were identified. Three degradation pathways, chlorine substitution, chlorine and hydroxyl substitution, and dealkylation were proposed for DHHB transformation in the Cl + solar process. Both Quantitative structure-activity relationship and Aliivibrio fischeri toxicity tests demonstrated increased toxicity for the chlorinated TBPs. A risk assessment of the DHHB and its TBPs suggested that both DHHB and its chlorinated TBPs pose a significant health risk.
二乙氨基羟基苯甲酰基己基苯甲酸酯(DHHB)是一种紫外线(UV)滤光剂,存在于防晒霜和其他个人护理产品中,因此可以通过游泳者进入游泳池。在户外游泳池中,DHHB 不可避免地会与游离氯和阳光相互作用。因此,本工作研究了 DHHB 的太阳-氯化学转化机制及其环境风险。在氯化与太阳(Cl + solar)过程中,游离氯是导致 85%的 DHHB 降解的主要因素,而羟基自由基和活性氯物种仅贡献了 15%,因为自由基生成率低且 DHHB 和游离氯的反应速率较快。Cl、NH 和溶解有机物(DOM)等捕获基质抑制了 Cl + solar 过程中 DHHB 的降解,而 Br、HCO、NO 和尿素促进了 DHHB 的降解。在自来水游泳池样品中,DHHB 的降解受到抑制,而在海水游泳池样品中,Cl + solar 过程增强了 DHHB 的降解。鉴定了包括单氯、二氯、脱烷基和单氯羟基化 TBPs 在内的七种转化副产物(TBPs)。提出了 DHHB 在 Cl + solar 过程中的三种转化途径,即氯取代、氯和羟基取代以及脱烷基。定量构效关系和发光菌毒性测试都表明氯化 TBPs 的毒性增加。DHHB 及其 TBPs 的风险评估表明,DHHB 及其氯化 TBPs 都对健康构成重大风险。