Rapid industrialization and urbanization have resulted in elevated concentrations of contaminants in the groundwaters and subsurface soils, posing a growing hazard to humans and ecosystems. The transformation of most contaminants is closely linked to the mineralogy of ferric (hydr)oxides. Sulfidation of ferric (hydr)oxides is one of the most significant biogeochemical reactions in the anoxic environments, causing reductive dissolution and recrystallization of ferric (hydr)oxides and further affecting the transformation of iron-associated contaminants. This paper provides a comprehensive review on the sulfidation process of ferric (hydr)oxides and the transformation of relevant contaminants. This review presents detailed reaction mechanisms between ferric (hydr)oxides and dissolved sulfide, and elucidates the factors (e.g. crystallinity of ferric (hydr)oxides, the ratio of sulfide concentration to the surface area concentration of ferric (hydr)oxides) that control the formation of surface associated Fe(II), iron sulfide minerals, as well as transformation of secondary minerals. Then, we summarized the transformation mechanisms of a variety of typical environmentally relevant contaminants existing in groundwater and subsurface soils, including heavy metals, metal(loid) oxyanions (arsenic, antimony, chromium), radionuclides (uranium, technetium), organic contaminants and phosphate/nitrate species. The general mechanisms of contaminant transformation involve a combination of release, reduction and re-adsorption/incorporation processes, the specific pathway of which is highly dependent on the properties of the contaminant itself and the extent of sulfidation. Moreover, the challenge of extending our knowledge towards in situ remediation, as well as further research needs are identified.

This paper discusses the abiotic and biotic processes in the in-situ control of biogenic hydrogen sulfide generated from microbial sulfate reduction by ferric (FeIII) (hydr)oxides (FeOOH) granules in the sediments of polluted urban waters. Granular ferric hydroxide (GFH, β-FeOOH) and granular ferric oxide (GFO, α-FeOOH) dosed in the organic- and sulfate-rich sediments had 180% and 19% higher sulfide removal capacities than those used for the purely abiotic removal of dissolved sulfide, respectively. The enhancement was attributable to the involvement of the biotic pathways, besides the abiotic pathways (mainly sulfide oxidation). The FeOOH granules stimulated the microbial reduction of surface FeIII by iron-reducing bacteria (e.g., Desulfovibrio and Carnobacterium), and increased the microbial sulfate reduction by 24%-30% under an organic-rich condition, likely due to the enhanced organic fermentation. The microbial iron reduction significantly enhanced the removal of the formed biogenic hydrogen sulfide through increasing sulfide precipitation because it remarkably promoted the release of Fe2+ ions from the granule surface, likely due to the involvement of siderophores as ligands. This biotic pathway led to the formation of amorphous FeS(s) as a major sulfur product (56%-81%), instead of elemental sulfur. The enhancement in the sulfide control performance was much more pronounced when the poorly ordered GFH was used, because of the faster Fe2+ release, compared to the highly ordered GFO. The abiotic and biotic mechanisms elucidated in this study provide insights into the iron-sulfur chemistry in the sediments of various polluted waters (e.g., storm drains, urban rivers, and estuary), where the manually-dosed and naturally-occurring FeIII (hydr)oxides control biogenic hydrogen sulfide.