Dipartimento di Chimica, Università di Torino, Via Pietro Giuria 5, 10125 Torino, Italy.
Université Clermont Auvergne, CNRS, INP Clermont Auvergne, Institut de Chimie de Clermont-Ferrand, F-63000 Clermont-Ferrand, France.
Sci Total Environ. 2023 Jun 10;876:162729. doi: 10.1016/j.scitotenv.2023.162729. Epub 2023 Mar 10.
Benzoate (Bz) and acetophenone (AcPh) are aromatic compounds known to be produced by sunlight irradiation of polystyrene aqueous suspensions. Here we show that these molecules could react with OH (Bz) and OH + CO (AcPh) in sunlit natural waters, while other photochemical processes (direct photolysis and reaction with singlet oxygen, or with the excited triplet states of chromophoric dissolved organic matter) are unlikely to be important. Steady-state irradiation experiments were carried out using lamps, and the time evolution of the two substrates was monitored by liquid chromatography. Photodegradation kinetics in environmental waters were assessed by a photochemical model (APEX: Aqueous Photochemistry of Environmentally-occurring Xenobiotics). In the case of AcPh, a competitive process to aqueous-phase photodegradation would be volatilisation followed by reaction with gas-phase OH. As far as Bz is concerned, elevated dissolved organic carbon (DOC) levels could be important in protecting this compound from aqueous-phase photodegradation. Limited reactivity of the studied compounds with the dibromide radical (Br, studied by laser flash photolysis) suggests that OH scavenging by bromide, which yields Br, would be poorly offset by Br-induced degradation. Therefore, photodegradation kinetics of Bz and AcPh should be slower in seawater (containing [Br] ~ 1 mM) compared to freshwaters. The present findings suggest that photochemistry would play an important role in both formation and degradation of water-soluble organic compounds produced by weathering of plastic particles.
苯甲酸盐(Bz)和苯乙酮(AcPh)是已知通过阳光照射聚苯乙烯水悬浮液而产生的芳香族化合物。在这里,我们表明这些分子可以与 OH(Bz)和 OH+CO(AcPh)在阳光充足的天然水中反应,而其他光化学过程(直接光解和与单线态氧反应,或与发色溶解有机物的激发三重态反应)不太可能很重要。使用灯进行稳态辐照实验,并通过液相色谱监测两种基质的时间演变。通过光化学模型(APEX:环境中出现的异生物质的水相光化学)评估环境水中的光降解动力学。就 AcPh 而言,与水相光降解竞争的过程将是挥发,然后与气相 OH 反应。就 Bz 而言,溶解有机碳 (DOC) 水平升高可能对保护该化合物免受水相光降解很重要。研究化合物与二溴化物自由基(Br,通过激光闪光光解研究)的有限反应性表明,由溴化物产生的 Br 对 OH 的清除作用不会被 Br 诱导的降解很好地抵消。因此,与淡水相比,Bz 和 AcPh 的光降解动力学在海水中(含 [Br]~1mM)应该更慢。本研究结果表明,光化学在由塑料颗粒风化产生的水溶性有机化合物的形成和降解中都将发挥重要作用。