Divergent Roles of Clay versus Iron (Hydr)oxide Minerals in Preserving Soil Organic Matter during Wildfire Heating

The interaction between soil minerals and soil organic matter (SOM) plays an important role in governing carbon release and sequestration in soil, yet understanding their behavior during wildfires remains poorly understood. This study examined the evolution of humic acid (HA, a representative of SOM) under simulated wildfire heating conditions (30-900 °C) in the presence of two representative soil minerals: montmorillonite (Mnt) and ferrihydrite (Fhy). Whereas Fhy accelerated the mineralization of HA, Mnt enhanced its preservation. These disparities stemmed from variations in the surface reactivity, structure, and transformations of Fhy and Mnt. Lewis acid sites, more abundant on Fhy surfaces than on Mnt surfaces, enhanced the decarboxylation of HA and caused carbon losses as CO₂. However, Brønsted acid sites, which are more abundant on Mnt surfaces than on Fhy surfaces, enhanced carbon preservation by promoting HA isomerization and aromatization. Above 350 °C, lattice oxygen release from Fhy promoted the oxidative decomposition of HA, while Fhy itself underwent reduction to form magnetite, wüstite, and zero-valent iron. The confinement of HA within the micro/mesopores created by Mnt's inert nanolayers prevented the thermal degradation of HA, enhancing carbon preservation. These findings advance our understanding of the specific roles of soil minerals in the decomposition, transformation, and preservation of SOM during wildfires.