Dynamic Production of Hydroxyl Radicals during the Flooding–Drainage Process of Paddy Soil: An In Situ Column Study

Frequent cycles of flooding and drainage in paddy soils lead to the reductive dissolution of iron (Fe) minerals and the reoxidation of Fe(II) species, all while generating a robust and consistent output of reactive oxygen species (ROS). In this study, we present a comprehensive assessment of the temporal and spatial variations in Fe species and ROS during the flooding–drainage process in a representative paddy soil. Our laboratory column experiments showed that a decrease in dissolved O2 concentration led to rapid Fe reduction below the water–soil interface, and aqueous Fe(II) was transformed into solid Fe(II) phases over an extended flooding time. As a result, the •OH production capacity of liquid phases was reduced while that of solid phases improved. The •OH production capacity of solid phases increased from 227–271 μmol kg–1 (within 1–11 cm depth) to 500–577 to 499–902 μmol kg–1 after 50 day, 3 month, and 1 year incubation, respectively. During drainage, dynamic •OH production was triggered by O2 consumption and Fe(II) oxidation. ROS-trapping film and in situ capture revealed that the soil surface was the active zone for intense H2O2 and •OH production, while limited ROS production was observed in the deeper soil layers (>5 cm) due to the limited oxygen penetration. These findings provide more insights into the complex interplay between dynamic Fe cycling and ROS production in the redox transition zones of paddy fields.