Strong Substance Exchange at Paddy Soil-Water Interface Promotes Nonphotochemical Formation of Reactive Oxygen Species in Overlying Water

Abstract

Photochemically generated reactive oxygen species (ROS) are widespread on the earth’s surface under sunlight irradiation. However, the nonphotochemical ROS generation in surface water (e.g., paddy overlying water) has been largely neglected. This work elucidated the drivers of nonphotochemical ROS generation and its spatial distribution in undisturbed paddy overlying water, by combining ROS imaging technology with in situ ROS monitoring. It was found that H₂O₂ concentrations formed in three paddy overlying waters could reach 0.03–16.9 μM, and the ROS profiles exhibited spatial heterogeneity. The O₂ planar-optode indicated that redox interfaces were not always generated at the soil–water interface but also possibly in the water layer, depending on the soil properties. The formed redox interface facilitated a rapid turnover of reducing and oxidizing substances, creating an ideal environment for the generation of ROS. Additionally, the electron-donating capacities of water at soil–water interfaces increased by 4.5–8.4 times compared to that of the top water layers. Importantly, field investigation results confirmed that sustainable •OH generation through nonphotochemical pathways constituted of a significant proportion of total daily production (>50%), suggesting a comparable or even greater role than photochemical ROS generation. In summary, the nonphotochemical ROS generation process reported in this study greatly enhances the understanding of natural ROS production processes in paddy soils.