Transformations of Ferrihydrite-Extracellular Polymeric Substance Coprecipitates Driven by Dissolved Sulfide: Interrelated Effects of Carbon and Sulfur Loadings.

The association of poorly crystalline iron (hydr)oxides with organic matter (OM), such as extracellular polymeric substances (EPS), exerts a profound effect on Fe and C cycles in soils and sediments, and their behaviors under sulfate-reducing conditions involve complicated mineralogical transformations. However, how different loadings and types of EPS and water chemistry conditions affect the sulfidation still lacks quantitative and systematic investigation. We here synthesized a set of ferrihydrite-organic matter (Fh-OM) coprecipitates with various model compounds for plant and microbial exopolysaccharides (polygalacturonic acids, alginic acid, and xanthan gum) and bacteriogenic EPS (extracted from Bacillus subtilis). Combining wet chemical analysis, X-ray diffraction, and X-ray absorption spectroscopic techniques, we systematically studied the impacts of C and S loadings by tracing the temporal evolution of Fe mineralogy and speciation in aqueous and solid phases. Our results showed that the effect of added OM on sulfidation of Fh-OM coprecipitates is interrelated with the amount of loaded sulfide. Under low sulfide loadings (S(-II)/Fe < 0.5), transformation to goethite and lepidocrocite was the main pathway of ferrihydrite sulfidation, which occurs more strongly at pH 6 compared to that at pH 7.5, and it was promoted and inhibited at low and high C/Fe ratios, respectively. While under high sulfide loadings (S(-II)/Fe > 0.5), the formation of secondary Fe-S minerals such as mackinawite and pyrite dominated ferrihydrite sulfidation, and it was inhibited with increasing C/Fe ratios. Furthermore, all three synthetic EPS proxies unanimously inhibited mineral transformation, while the microbiogenic EPS has a more potent inhibitory effect than synthetic EPS proxies compared at equivalent C/Fe loadings. Collectively, our results suggest that the quantity and chemical characteristics of the associated OM have a strong and nonlinear influence on the extent and pathways of mineralogical transformations of Fh-OM sulfidation.