Sulfur speciation in well‐aerated and wetland soils in a forested catchment assessed by sulfur K‐edge X‐ray absorption near‐edge spectroscopy (XANES)

In forested catchments, retention and remobilization of S in soils and wetlands regulate soil and water acidification. The prediction of long‐term S budgets of forest ecosystems under changing environmental conditions requires a precise quantification of all relevant soil S pools, comprising S species with different remobilization potential. In this study, the S speciation in topsoil horizons of a soil toposequence with different groundwater influence and oxygen availability was assessed by synchrotron‐based X‐ray absorption near‐edge spectroscopy (XANES). Our investigation was conducted on organic (O, H) and mineral topsoil (A, AE) horizons of a Cambisol–Stagnosol–Histosol catena. We studied the influence of topography (i.e., degree of groundwater influence) and oxygen availability on the S speciation. Soil sampling and pretreatment were conducted under anoxic conditions. With increasing groundwater influence and decreasing oxygen availability in the sequence Cambisol–Stagnosol–Histosol, the C : S ratio in the humic topsoil decreased, indicating an enrichment of soil organic matter in S. Moreover, the contribution of reduced S species (inorganic and organic sulfides, thiols) increased systematically at the expense of intermediate S species (sulfoxide, sulfite, sulfone, sulfonate) and oxidized S species (ester sulfate, SO ). These results support the concept of different S‐retention processes for soils with different oxygen availability. Sulfur contents and speciation in two water‐logged Histosols subject to permanently anoxic and temporarily oxic conditions, respectively, were very different. In the anoxic Histosol, reduced S accounted for 57% to 67% of total S; in the temporarily oxic Histosol, reduced S was only 43% to 54% of total S. Again, the extent of S accumulation and the contribution of reduced S forms to total S closely reflected the degree of O₂ availability. Our study shows that XANES is a powerful tool to elucidate key patterns of the biogeochemical S cycling in oxic and anoxic soil environments. In contrast to traditional wet‐chemical methods, it particularly allows to distinguish organic S compounds in much more detail. It can be used to elucidate microbial S‐metabolism pathways in soils with different oxygen availability by combining soil inventories and repeated analyses of a sample in different stages of field or laboratory incubation experiments under controlled boundary conditions and also to study (sub)microspatial patterns of S speciation in aggregated soils.