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A Model Study of the Photochemical Fate of As(III) in Paddy-Water

DOI:10.3390/molecules22030445 期刊:Molecules 出版年份:2017 更新时间:2025-09-23 15:22:29
摘要: The APEX (Aqueous Photochemistry of Environmentally-occurring Xenobiotics) software previously developed by one of us was used to model the photochemistry of As(III) in paddy-field water, allowing a comparison with biotic processes. The model included key paddy-water variables, such as the shielding effect of the rice canopy on incident sunlight and its monthly variations, water pH, and the photochemical parameters of the chromophoric dissolved organic matter (CDOM) occurring in paddy fields. The half-life times (t1/2) of As(III) photooxidation to As(V) would be ~20–30 days in May. In contrast, the photochemical oxidation of As(III) would be much slower in June and July due to rice-canopy shading of radiation because of plant growth, despite higher sunlight irradiance. At pH < 8 the photooxidation of As(III) would mainly be accounted for by reaction with transient species produced by irradiated CDOM (here represented by the excited triplet states 3CDOM*, neglecting the possibly more important reactions with poorly known species such as the phenoxy radicals) and, to a lesser extent, with the hydroxyl radicals (HO?). However, the carbonate radicals (CO3??) could be key photooxidants at pH > 8.5 provided that the paddy-water 3CDOM* is sufficiently reactive toward the oxidation of CO32?. In particular, if paddy-water 3CDOM* oxidizes the carbonate anion with a second-order reaction rate constant near (or higher than) 106 M?1·s?1, the photooxidation of As(III) could be quite fast at pH > 8.5. Such pH conditions can be produced by elevated photosynthetic activity that consumes dissolved CO2.
作者: Luca Carena,Davide Vione
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To model the photochemical fate of As(III) in paddy-field water using the APEX software, comparing it with biotic processes and assessing the effects of variables like rice canopy shading, water pH, and CDOM photochemical parameters.

Photochemical modeling indicates that As(III) photooxidation in paddy floodwater is significant in May with half-life times of 20-30 days, primarily due to reactions with 3CDOM* and HO?, but is negligible in June and July due to rice canopy shading. At pH > 8.5, carbonate radicals could enhance oxidation if CDOM is sufficiently reactive. Photochemical processes may be slower than microbial redox processes in some cases, but under specific conditions, they could play a key role in arsenic cycling.

The model neglects reactions with phenoxy radicals and other poorly known species due to insufficient knowledge, potentially underestimating photochemical oxidation rates. It assumes wavelength-independent light transmittance and constant water depth, which may not fully represent real conditions. The reactivity of paddy-water CDOM with carbonate anions is unknown and requires further investigation.

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