Organic matter stabilization in soil microaggregates: implications from spatial heterogeneity of organic carbon contents and carbon forms

This study investigates the spatial distribution of organic carbon (C) in free stable microaggregates (20–250 μm; not encapsulated within macroaggregates) from one Inceptisol and two Oxisols in relation to current theories of the mechanisms of their formation. Two-dimensional micro- and nano-scale observations using synchrotron-based Fourier-transform infrared (FTIR) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy yielded maps of the distribution of C amounts and chemical forms. Carbon deposits were unevenly distributed within microaggregates and did not show any discernable gradients between interior and exterior of aggregates. Rather, C deposits appeared to be patchy within the microaggregates. In contrast to the random location of C, there were micron-scale patterns in the spatial distribution of aliphatic C–H (2922 cm−1), aromatic C=C and N–H (1589 cm−1) and polysaccharide C–O (1035 cm−1). Aliphatic C forms and the ratio of aliphatic C/aromatic C were positively correlated (r 2 of 0.66–0.75 and 0.27–0.59, respectively) to the amount of O–H on kaolinite surfaces (3695 cm−1), pointing at a strong role for organo-mineral interactions in C stabilization within microaggregates and at a possible role for molecules containing aliphatic C-H groups in such interactions. This empirical relationship was supported by nanometer-scale observations using NEXAFS which showed that the organic matter in coatings on mineral surfaces had more aliphatic and carboxylic C with spectral characteristics resembling microbial metabolites than the organic matter of the entire microaggregate. Our observations thus support models of C stabilization in which the initially dominant process is adsorption of organics on mineral surfaces rather than occlusion of organic debris by adhering clay particles.