Speciation of sulphur in soils and soil particles by X-ray spectromicroscopy

Current wet chemical methods for the speciation of sulphur (S) in soils are inaccurate and do not allow one to assess the S speciation of individual soil particles and colloids. X-ray microscopy and Near Edge X-ray Absorption Fine structure Spectroscopy (NEXAFS) can be used to study individual species of S at the K-adsorption edge. We have used these techniques to identify and quantify S species in bulk soil, soil particles and colloids from Oh and Bh horizons of two forested Podzols. The partitioning of soil sulphur as determined on bulk samples of the Oh horizons by X-ray spectromicroscopy agreed fairly well with the results of a conventional S speciation for the soil at Schluchsee, and reasonably well for that at Rotherdbach. The NEXAFS analyses on individual soil particles revealed that they are richer in reduced organic sulphur than the bulk soil for the Schluchsee Oh and richer in sulphate for Rotherdbach Oh. The techniques can be used reliably to separate and quantify sulphur species with different oxidation states in the soil. The combination of X-ray transmission and sulphur fluorescence images with unfocused and focused NEXAFS spectra at the K-adsorption edge of sulphur at specific microsites allowed us to compare the distribution of S species in bulk soil with that of distinct soil particles and soil colloids. Moreover, we can use it to assess the spatial distribution of different S species on soil particles on a scale of a few hundred nanometres.