Nano and sub-nano scale distribution of organic carbon species on soil particles revealed by Cs-STEM EELS

Abstract

Understanding the heterogeneous distribution of soil organic matter (SOM) on soil particles is essential for predicting the stability of organic carbon (C) in soil, but direct visualization of the microscopic distribution of organic C in soil is still challenging due to the complexity of soil particles. In this study, a paddy soil was fractionated and spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) coupled with electron energy loss spectroscopy (EELS) was employed to analyze the microscopic distribution of organic C species on clay-sized soil particles (<2000 nm) from the different size fractions (800–2000 nm, 100–800 nm and 0–100 nm) at the nano and sub-nano scale. The EELS results demonstrated that the relative abundance of both phenolic and aliphatic C was quite independent of the particle size fractions, while aromatic and carboxyl carbon demonstrated the largest variations between fractions. With the decrease in soil particle size from 800 to 2000 nm to 0–100 nm, the median abundance of carboxyl (oxidized) C increased from 23% to 35%, and aromatic (reduced) C decreased accordingly from 40% to 16%. The statistical analysis demonstrated that the local organic C concentration was the major factor accounting for the variations in oxidized and reduced C species in soil particles, in which selective sorption of the organic C abundant of acidic functional groups by reactive minerals was responsible for the enrichment of oxidized C in small clay size soil particles. Overall, the results of this study contribute to an improved understanding of the chemical diversity of SOM in organo-mineral interfaces and provide insights in the microscopic C stabilization mechanisms in natural soils.