Micro- and nano-environments of C sequestration in soil: A multi-elemental STXM-NEXAFS assessment of black C and organomineral associations

Black C is an essential component of the terrestrial C pool and its formation is often credited as a CO₂ sink by transferring the fast-cycling C from the atmosphere-biosphere system into slower cycling C in the geosphere. This study is the first multi-element K- (C, N, Ca, Fe, Al and Si) soft-X-ray STXM-NEXAFS investigation conducted at a submicron-scale spatial resolution specifically targeting black C and its interaction with the mineral and non-black C organic matter in the organomineral assemblage. The STXM-NEXAFS micrographs and spectra demonstrated that pyrogenic C was dominated by quinoide, aromatic, phenol, ketone, alcohol, carboxylic and hydroxylated- and ether-linked C species. There was also evidence for the presence of pyridinic, pyridonic, pyrrolic, amine and nitril N functionalities. The non-black C organic matter contained amino acids, amino sugars, nucleic acids and polysaccharides known to exhibit negatively charged carboxylic, phenolic, enolic, thiolate and phosphate functionalities highly reactive towards metal ions and black C. The metal-rich mineral matrix was composed of phyllosilicate clay minerals, Fe and Al hydroxypolycations, oxides, hydroxides and oxyhydroxide that can attract and bind organic biopolymers. STXM-NEXAFS provided evidence for interactive association between pyrogenic C, non-black C organic matter and the mineral oxide and oxyhydroxide communities in the organomineral interface. These intimate associations occurred through a "two-way" direct linkage between black C and the mineral or non-black C organic matter or via a "three-way" indirect association where non-black C organic matter could serve as a molecular cross-linking agent binding black C with the mineral matrix or vice versa where inorganic oxides, hydroxides and polycations could act as a bridge to bind black C with non-black C organic matter. The binding and sequestration of black C in the investigated micro- and nano-C repository environments seem to be the combined action of physical entrapment in seemingly terminal biotic exclusion zone through the action of metal oxides and organic matter induced microaggregation and through molecular-level association ranging from ligand exchange, polyvalent cation bridging to weak hydrophobic interactions including van der Waals and H-bonding.