Iron speciation changes and mobilization of colloids during redox cycling in Fe-rich, Icelandic peat soils

Soils of Iceland are characterized by an abundance of short-range order (SRO) iron (Fe) minerals and aluminosilicates. Interactions between these SRO mineral phases and soil organic carbon (OC) promote long-term stabilization of the latter through the formation of mineral-organic complexes and aggregates. However, Icelandic soils are also exposed to high rainfall events, which induce anoxic conditions, facilitate microbial reduction of ferric Fe, and may lead to the mobilization of mineral-associated OC. Here, we explored the fate of OC during Fe redox cycling by incubating six organic-rich soil horizons from three typical soil types across Iceland (Histosols, Histic and Gleyic Andosols) as soil slurries under anoxic conditions for up to 5 weeks and followed the effects of re-oxidation after 1, 2, and 5 weeks. Changes in solid-phase Fe speciation were assessed by combining Fe K-edge X-ray absorption spectroscopy with time-resolved parallel selective chemical extractions, and trends in aqueous element contents were measured in both the dissolved (<3 kDa) and fine colloidal fractions (3 kDa to 0.45 µm). In all soils, anoxic incubation resulted in microbial reduction of Fe(III) and concomitant increases in soil solution pH. However, soils containing SRO Fe minerals underwent more extensive Fe reduction. Rapid (<1 wk) increases in aqueous element contents (including Fe, Al, and OC) were recorded in all soil slurries, and mobilization of colloids occurred in soil horizons which reached the highest pH values (>4.6). Mobilized colloids persisted during re-oxidation of the soil slurries, which also resulted in the formation of new Fe mineral phases, the composition of which was influenced by initial soil Fe mineralogy. Collectively, our results suggest that increases in the frequency of redox cycles in Icelandic soils are likely to result in shifts in Fe mineralogy and may contribute to the increased mobilization of soil OC as organic-Fe-/Al-colloids.