Microheterogeneity of element distribution and sulfur speciation in an organic surface horizon of a forested Histosol as revealed by synchrotron-based X-ray spectromicroscopy

In recent years, the relevance of physico-chemical heterogeneity patterns in soils at the micron and submicron scale for the regulation of biogeochemical processes has become increasingly evident. For an organic surface soil horizon from a forested Histosol in Germany, microspatial patterns of element distribution (sulfur, phosphorus, aluminium, silicon) and S speciation were investigated by synchrotron-based X-ray spectromicroscopy. Microspatial patterns of S, P, Al and Si contents in the organic topsoil were assessed for a sample region of 50 μm × 30 μm by spatially resolving μ-XRF. Sulfur speciation at four microsites was investigated by focused X-ray absorption near edge structure (μ-XANES) spectroscopy at the S K-edge. The results show a heterogeneous distribution of the investigated elements on the (sub)micron scale, allowing the identification of diatoms, aluminosilicate mineral particles and sulfide minerals in the organic soil matrix. Evaluation of the S K-edge μ-XANES spectra acquired at four different microsites by linear combination fitting revealed a substantial microspatial heterogeneity of S speciation, characterized by the presence of distinct enrichment zones of inorganic sulfide and zones with dominant organic disulfide S within a few micrometers distance, and coexistence of different S species (e.g. reduced inorganic and organic S compounds) at a spatial scale below the resolution of the instrument (60 nm × 60 nm; X-ray penetration depth: 30 μm).