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Triplet-State Photochemistry of Dissolved Organic Matter: Triplet-State Energy Distribution and Surface Electric Charge Conditions

DOI:10.1021/acs.est.8b06574 期刊:Environmental Science & Technology 出版年份:2019 更新时间:2025-11-19 16:56:35
摘要: Excited triplet states of chromophoric dissolved organic matter (3CDOM*) are highly reactive species in sunlit surface waters and play a critical role in reactive oxygen species (ROS) formation and pollutant attenuation. In the present study, a series of chemical probes, including sorbic acid, sorbic alcohol, sorbic amine, trimethylphenol, and furfuryl alcohol, were employed to quantitatively determine 3CDOM* and 1O2 in various organic matters. Using a high concentration of sorbic alcohol as high-energy triplet states quencher, 3CDOM* can be first distinguished as high-energy triplet states (>250 kJ mol?1) and low-energy triplet states (<250 kJ mol?1). The terrestrial-origin natural organic matter (NOM) was found to mainly consist of low-energy triplet states, while high-energy triplet states were predominant in autochthonous-origin NOM and effluent/wastewater organic matter (EfOM/WWOM). The 1O2 quantum yields and electron transfer quantum yield coefficients (f TMP) generated from low-energy triplet states remained constant in all tested organic matters. External phenolic compound showed quenching effects on triplet-state formation and tended to have a higher quenching efficiency for aromatic ketone triplet states, which are the main high-energy triplet states. In comparison with terrestrial-origin NOM, autochthonous-origin NOM and EfOM/WWOM presented lower reaction rate constants for sorbic amines and higher reaction rate constants for sorbic acid, and these differences are likely due to dissimilar surface electric charge conditions. Understanding the triplet-state photochemistry of CDOM is essential for providing useful insights into their photochemical effects in aquatic systems.
作者: Huaxi Zhou,Weihua Song,Lushi Lian,Shuwen Yan
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Investigating the triplet-state energy distribution, phenolic constituents, and surface electric charge conditions of chromophoric dissolved organic matter (CDOM) to understand their photochemical reactivity in aquatic systems.

The study demonstrates that triplet-state energy distribution, phenolic content, and surface charge conditions significantly influence CDOM photochemical reactivity. High-energy triplet states dominate in autochthonous and wastewater-derived OM, leading to higher reactivity. Phenolic compounds quench triplet states more effectively for aromatic ketones. Surface charge differences alter reaction rates with charged probes. These findings improve understanding of organic contaminant degradation in aquatic systems.

The study uses model compounds and specific probes which may not fully represent all natural conditions. The kO2 and kdT values are averages from literature, which might not be precise for all samples. The quenching effects and charge interactions are based on controlled laboratory conditions, which may differ in real environmental settings.

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