Iron oxide minerals play an important role in stabilizing organic carbon (OC) and regulating the biogeochemical cycles of OC on the earth surface. To predict the fate of OC, it is essential to understand the amount, spatial variability, and characteristics of Fe-bound OC in natural soils. In this study, we investigated the concentrations and characteristics of Fe-bound OC in soils collected from 14 forests in the United States and determined the impact of ecogeographical variables and soil physicochemical properties on the association of OC and Fe minerals. On average, Fe-bound OC contributed 37.8 % of total OC (TOC) in forest soils. Atomic ratios of OC : Fe ranged from 0.56 to 17.7, with values of 1–10 for most samples, and the ratios indicate the importance of both sorptive and incorporative interactions. The fraction of Fe-bound OC in TOC (f_Fe-OC) was not related to the concentration of reactive Fe, which suggests that the importance of association with Fe in OC accumulation was not governed by the concentration of reactive Fe. Concentrations of Fe-bound OC and f_Fe-OC increased with latitude and reached peak values at a site with a mean annual temperature of 6.6 °C. Attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR) and near-edge X-ray absorption fine structure (NEXAFS) analyses revealed that Fe-bound OC was less aliphatic than non-Fe-bound OC. Fe-bound OC also was more enriched in ¹³C compared to the non-Fe-bound OC, but C ∕ N ratios did not differ substantially. In summary, ¹³C-enriched OC with less aliphatic carbon and more carboxylic carbon was associated with Fe minerals in the soils, with values of f_Fe-OC being controlled by both sorptive and incorporative associations between Fe and OC. Overall, this study demonstrates that Fe oxides play an important role in regulating the biogeochemical cycles of C in forest soils and uncovers the governing factors for the spatial variability and characteristics of Fe-bound OC.

Soil organic matter (SOM) is a key reservoir for global carbon (C), supporting soil fertility and influencing greenhouse gas emissions. Microbial residues, composed of dead cells and cellular fragments, are major contributors to SOM formation. Yet, mechanisms by which minerals enhance the accumulation of microbial residues remain poorly understood. Here, we used ¹³C-labeled glucose in a year-long incubation to trace microbial residue in sandy and silty soils. Across both soils, approximately 89% of retained microbial ¹³C was recovered in the fine (<53 μm) mineral-associated organic matter (MAOM) pool. Within this pool, the light MAOM fraction, enriched in poorly crystalline Fe minerals, held 4.3 times more ¹³C than the heavy, phyllosilicate-dominated MAOM fraction, despite accounting for only 17.2% of the total MAOM mass and 12.3% of the total soil mass. Along with ¹³C enrichment, the light MAOM fraction showed greater abundance of N-containing groups, e.g., (amides and amino groups), indicative of microbial-derived compounds like proteins and amino sugars. Fe oxides in light MAOM from both soils were spatially dispersed. Microbial residue accumulation was greater in finer-textured silty soil. These findings demonstrate that mineral composition and texture jointly regulate microbial necromass accrual, highlighting light MAOM as a key pool for enhancing soil C storage.

Solar photoexcitation of chromophoric groups in dissolved organic matter (DOM), when coupled to photoreduction of ubiquitous Fe(III)-oxide nanoparticles, can significantly accelerate DOM degradation in near-surface terrestrial systems, but the mechanisms of these reactions remain elusive. We examined the photolysis of chromophoric soil DOM coated onto hematite nanoplatelets featuring (001) exposed facets using a combination of molecular spectroscopies and density functional theory (DFT) computations. Reactive oxygen species (ROS) probed by electron paramagnetic resonance (EPR) spectroscopy revealed that both singlet oxygen and superoxide are the predominant ROS responsible for DOM degradation. DFT calculations confirmed that Fe(II) on the hematite (001) surface, created by interfacial electron transfer from photoexcited chromophores in DOM, can reduce dioxygen molecules to superoxide radicals (^•O₂^-) through a one-electron transfer process. ¹H nuclear magnetic resonance (NMR) and electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) spectroscopies show that the association of DOM with hematite enhances the cleavage of aromatic groups during photodegradation. The findings point to a pivotal role for organic matter at the interface that guides specific ROS generation and the subsequent photodegradation process, as well as the prospect of using ROS signatures as a forensic tool to help interpret more complicated field-relevant systems.