A Novel Perspective on the Role of Hydroxyl Radicals in Soil Organic Carbon Mineralization within the Detritusphere: Stimulating C-Degrading Enzyme Activities

Detritusphere is a hotspot of carbon cycling in terrestrial ecosystems, yet the mineralization of soil organic carbon (SOC) within this microregion associated with reactive oxygen species (ROS) remains unclear. Herein, we investigated ROS production and distribution in the detritusphere of six representative soils and evaluated their contributions to SOC mineralization. We found that ROS production was significantly correlated with several soil chemical and biological factors, including pH, water-soluble phenols, water-extractable organic carbon, phenol oxidase activity, surface-bound or complexed Fe(II) and Fe(II) in low-crystalline minerals, highly crystalline Fe(II)-bearing minerals, and SOC. These factors collectively contributed to 99.6% of the variation in ROS production, as revealed by redundancy analyses. Among ROS, hydroxyl radicals (^•OH) were key contributors to SOC mineralization, responsible for 10.4%-38.7% of CO₂ emissions in ROS quenching experiments. Inhibiting ^•OH production decreased C-degrading enzyme activities, indicating that ^•OH stimulates CO₂ emissions by increasing enzyme activity. Structural equation modeling further demonstrated that ^•OH promotes C-degrading enzyme activities by degrading water-soluble phenols to unlock the "enzyme latch" and by increasing SOC availability to upregulate C-degrading gene expression. These pathways contributed equally to SOC mineralization and exceeded its direct effect. These findings provide detailed insight into the mechanistic pathways of ^•OH-mediated carbon dynamics within the detritusphere.