In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO●), singlet oxygen (1O2), and triplet excited states of chromophoric dissolved organic matter (3CDOM*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23?±?0.07)?×?10–2 and (7.99?±?1.61)?×?10–3 mol Einstein?1, respectively. In contrast, reactions with HO● radicals and 3CDOM* dominate their degradation, with 1O2 exhibiting rates three to five orders of magnitude lower. The values of kIMD,HO● and kAMT,HO● were (3.51?±?0.06)?×?109 and (4.97?±?0.37)?×?109 L mol?1 s?1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with kIMD,3AQ2S*?=?(1.02?±?0.08)?×?109 L mol?1 s?1 and kIMD,3CBBP*?=?(3.17?±?0.14)?×?108 L mol?1 s?1; on the contrary, the values found for AMT are close, kAMT,3AQ2S*?=?(8.13?±?0.35)?×?108 L mol?1 s?1 and kAMT,3CBBP*?=?(7.75?±?0.80)?×?108 L mol?1 s?1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO3?, NO2?, CO32?, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.
相似文献Singlet oxygen (1O2), hydroxyl radicals (•OH), and excited triplet states of organic matter (3OM*) play a key role in the degradation of pollutants in aquatic environments. The formation rates and quantum yields (Φ) of these reactive intermediates (RI) through photosensitized reactions of dissolved organic matter (DOM) have been reported in the literature for decades. Urban biowaste-derived substances (UW-BOS), a form of organic matter derived from vegetative and urban waste, have recently been shown to be efficient sensitizers in the photo-degradation of different contaminants. Nevertheless, no quantitative measurements of photo-oxidant generation by UW-BOS have been reported. In this study, the formation quantum yields of 1O2 and •OH, as well as quantum yield coefficients of TMP degradation (indicative of 3OM* formation), were quantified for two UW-BOS samples, under 254-nm UV radiation or simulated sunlight and compared to a DOM standard from the Suwanee River (SRNOM). Values of Φ for UW-BOS samples ranged from Φ(+1O2) = 8.0 to 8.8 × 10−3, Φ(+•OH) = 4.1 to 4.3 × 10−6, and f TMP = 1.22 to 1.23 × 102 L Einstein−1 under simulated sunlight and from Φ(+1O2) = 1.4 to 2.3 × 10−2, Φ(+•OH) = 1.3 to 3.5 × 10−3, and f TMP = 3.3 to 3.9 × 102 L Einstein−1 under UV. Although UW-BOS are not necessarily better than natural DOM regarding photosensitizing properties, they do sensitize the production of RI and could potentially be used in engineered treatment systems.
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