Iron Oxidation-Reduction Processes in Warming Permafrost Soils and Surface Waters Expose a Seasonally Rusting Arctic Watershed

Landscape-scalechanges in the Arctic as a result of climate changeaffect the soil thermal regime and impact the depth to permafrostin vulnerable tundra watersheds. When top-down thaw of permafrostoccurs, oxygen and porewaters infiltrate deeper in the soil columnexposing fresh, previously frozen material and altering redox conditionsthat govern the mobility of geochemical constituents. Redox conditionsplay a critical role in the carbon cycle processes that link permafrostcarbon stocks with potential feedbacks to climate warming. As such,there remains a gap in knowledge understanding how redox stratificationsin thawing permafrost impact the geochemistry of watersheds in responseto climate change and how investigations into redox may be scaledby coupling extensive geophysical mapping techniques. In this study,we collected soils and soil porewaters from three soil pits and surfacewater samples from an Arctic watershed on the North Slope of Alaskaand analyzed for trace metals iron (Fe) and manganese (Mn) and Feoxidation state using bulk and microscale techniques, including X-raysynchrotron spectroscopy. We also used geophysical mapping and soilthermistors to measure active layer depths across the watershed torelate accelerating permafrost thaw to watershed geochemistry. Wefound that Fe(II) and Fe(III) co-occur in the soils, porewaters, andsurface waters of Imnavait Creek watershed with Fe(II) comprisingup to 37% of the total Fe concentrations in the 40-60 cm soildepth and up to 17% in the 60-80 cm soil depth. In comparisonto the surface (0-20 cm) and deeper in the permafrost (80-100cm), Fe(II) was found to be enriched in the soils at the permafrost-activelayer transition zone in two of the three soil pits and that translatedto mobilization of Fe(II) to porewaters upon thaw at 40-60cm, contributing up to 72% of the total Fe. Further, Fe(II) was foundto be mobilized in all porewater samples from 60 to 100 cm depth andcomprised 56-70% of the total Fe. In the surface water, Feand Mn concentrations were linked to seasonality with higher concentrationscoinciding with the deepest yearly extent of the active layer thawprogression. Overall, we found evidence that Fe and Mn could be usefulas geochemical indicators of permafrost thaw and release of Fe(II)from thawing permafrost and further oxidation to Fe(III) could translateto a higher degree of seasonal rusting coinciding with the warmingand thawing of near surface-permafrost.