Iron speciation in organic matter fractions isolated from soils amended with biochar and organic fertilizers

The role and distribution of iron (Fe) species in physical soil fractions has received remarkably little attention in field-scale systems. Here, we identify and quantify the Fe phases in two fractions (fine sand, FSa, and fine silt and clay, FSi+Cl), isolated from an agricultural soil non-amended and amended with different organic materials, by Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. Linear combination fitting and wavelet transform of EXAFS data revealed noticeable differences between unamended FSa and FSi+Cl fractions. Specifically, the FSi+Cl fraction was mainly characterized by ferrihydrite (48%) and Fe(III)-soil organic matter (SOM) complexes (37%), whereas in the FSa fraction ferrihydrite still represented a major phase (44%), with a lower contribution from Fe(III)-SOM (18%). In the FSa fraction, the addition of the organic amendments resulted in an increase of Fe-SOM complexes (31-35%) and a decrease of ferrihydrite (28-29%). By contrast, in the amended FSi+Cl fractions, the added organic matter led to negligible changes in percent ferrihydrite. Therefore, regardless of the amendment type, the addition of organic matter to soil increased the capability of the coarse fraction (FSa) to stabilize organic carbon, thus pointing out that the role of FSa in carbon sequestration in agricultural soils at a global scale may be overlooked.