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.

Stabilization of organic matter in soil is important for natural ecosystem to sequestrate carbon and mitigate greenhouse gas emission. It is largely unknown what factors govern the preservation of organic carbon in soil, casting shadow on predicting the response of soil to climate change. Iron oxide was suggested as an important mineral preserving soil organic carbon. However, ferric minerals are subject to reduction, potentially releasing iron and decreasing the stability of iron-bound organic carbon. Information about the stability of iron-bound organic carbon in the redox reaction is limited. Herein, we investigated the sorptive interactions of organic matter with hematite and reductive release of hematite-bound organic matter. Impacts of organic matter composition and conformation on its sorption by hematite and release during the reduction reaction were analyzed. We found that hematite-bound aliphatic carbon was more resistant to reduction release, although hematite preferred to sorb more aromatic carbon. Resistance to reductive release represents a new mechanism that aliphatic soil organic matter was stabilized by association with iron oxide. Selective stabilization of aliphatic over aromatic carbon can greatly contribute to the widely observed accumulation of aliphatic carbon in soil, which cannot be explained by sorptive interactions between minerals and organic matter.