Iron speciation in soil size fractions under different land uses

Iron (Fe) (oxyhydr)oxides represent a significant phase for the organic carbon (OC) stabilization. Due to their high surface areas, short-range-ordered Fe minerals, like ferrihydrite, show a higher ability to stabilize OC than crystalline secondary minerals, like lepidocrocite, goethite, and magnetite. However, how Fe phases and their crystallinity relate to soil organic matter (SOM) composition is still not completely known. We investigated Fe solid phase speciation in two soil particle size fractions (i.e., fine sand — FSa — and fine silt and clay — FSi + Cl —), isolated from coniferous (CF) and broadleaved forest soils (BF), grassland soils (GL), and technosols (TS). All samples were characterized by Fe K-edge extended X-ray absorption fine structure (EXAFS) and X-ray diffraction, and a subset by 57Fe Mössbauer spectroscopy. Further, ramped combustion thermal analyses (coupled differential scanning calorimetry (DSC) and CO2 evolved gas analysis (CO2-EGA)) were used to evaluated SOM stability. With the only exception of TS, goethite was the main Fe phase in FSa fractions, whereas less crystalline phases (i.e., ferrihydrite, based on EXAFS) dominated the FSi + Cl fractions. The proportion of goethite and ferrihydrite in both fractions decreased with increasing OC content, while that of Fe(III)-SOM in FSa increased with increasing OC content. Mössbauer and EXAFS data clearly indicated a presence of hematite in GL soils. Our data suggest that more crystalline Fe forms, like goethite and hematite, may be important for OC abundance in the FSa fraction and in soils with high OC contents, like GL. Thermal analysis showed the dominance of mineral associated organic matter in low-OC soils, and of plant residues in high-OC soils. As a whole, we posit that the FSi + Cl fractions contain Fe phases of less crystallinity because of presumed association with SOM, and that SOM in the FSi + Cl fraction is also more thermodynamically stable than in FSa, although differences are observed across land uses. Our observations suggest that the nature of Fe-SOM interactions can vary substantially with soil particle size and land use, which has important implication for SOM persistence.