Mapping redox conditions in a tar-oil contaminated technosol by S K-edge XANES at the micrometer scale

At numerous open pits worldwide, carcinogenic and geno‐toxic tar oil is still exposed to the environment. To understand ongoing tar degradation under different environmental conditions we studied soil structure, water retention, tar composition, and microbial biomass of a technosol under a small tar-oil spill at a former brown coal processing site. We observed that microbial biomass increased with pore volume on our study site: Generally, contaminated layers of the technosol were more porous than uncontaminated control soils and accommodated more microbes. However, the relationship was not linear. We therefore wondered whether the redox regimes within the aggregates of the different layers provide comparable conditions for microbial degradation. We used the chemical state of S as a proxy for the prevailing redox-conditions and µXANES on thin sections (5 µm spatial resolution) to analyze the S speciation in relation to soil structure. First results show that the tar is not homogeneously composed and that the proportion of reduced S compounds increases with soil depth: Particularly S-rich domains within the tar are often roundish, up to 200 µm in size and composed of varying proportions of inorganic sulfide-S, organic monosulfide-S or thiol-S, sulfoxide-S, and sulfonate-S. The topmost layer (0-5 cm) of the technosol is very porous. Here, the tar matrix is dominated by sulfonate-S. At more than 5 cm depth, the soil also has a high porosity due to large pores > 50 µm but at the same time includes mm-sized, compact aggregates with only few small pores (1-10 µm and 10-50 µm). The tar matrix within these aggregates contains sulfidic S in addition to the sulfonate-rich component. However, adjacent to pore surfaces we observe 5-15 µm thick (oxidized) rims with only sulfonate-S. Our data show that the tar is not only chemically complex, but also heterogeneous in composition at the µm scale. Below a soil depth of 5 cm, we can assume that microbial tar degradation is slowed down because of the anoxic conditions within the aggregates, although pores > 50 µm are abundant and bacterial cell counts are high.