Organic carbon distribution, speciation, and elemental correlations within soil microaggregates: Applications of STXM and NEXAFS spectroscopy

Soils contain the largest inventory of organic carbon on the Earth’s surface. Therefore, it is important to understand how soil organic carbon (SOC) is distributed in soils. This study directly measured SOC distributions within soil microaggregates and its associations with major soil elements from three soil groups (Phaeozem, Cambisol, and Ultisol), using scanning transmission X-ray microscopy (STXM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy at a spatial resolution of 30 nm. Unlike previous studies, small intact soil microaggregates were examined directly in order to avoid preparatory procedures that might alter C speciation. We found that SOC exists as distinct particles (10s to 100s of nm) and as ubiquitous thin coatings on clay minerals and iron-oxides coatings. The distinct SOC particles have higher fractions of aromatic C than the coatings. NEXAFS spectra of the C coatings within individual microaggregates were relatively similar. In the Phaeozem soil, the pervasive spectral features were those of phenolic and carboxylic C, while in the Cambisol soil the most common spectral feature was the carboxyl peak. The Ultisol soil displayed a diffuse distribution of aromatic, phenolic, and carboxylic C peaks over all surfaces. In general, a wide range of C functional groups coexist within individual microaggregates. In this work we were able to, for the first time, directly quantify the major mineral elemental (Si, Al, Ca, Fe, K, Ti) compositions simultaneously with C distribution and speciation at the nm to μm scale. These direct microscale measurements will help improve understanding on SOC–mineral associations in soil environments.