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With permafrost thaw, significant amounts of organic carbon (OC) previously stored in frozen deposits are unlocked and become potentially available for microbial mineralization. This is particularly the case in ice-rich regions such as the Yedoma domain. Excess ground ice degradation exposes deep sediments and their OC stocks, but also mineral elements, to biogeochemical processes. Interactions of mineral elements and OC play a crucial role for OC stabilization and the fate of OC upon thaw, and thus regulate carbon dioxide and methane emissions. In addition, some mineral elements are limiting nutrients for plant growth or microbial metabolic activity. A large ongoing effort is to quantify OC stocks and their lability in permafrost regions, but the influence of mineral elements on the fate of OC or on biogeochemical nutrient cycles has received less attention and there is an overall lack of mineral element content analyses for permafrost sediments. Here, we combine portable X-ray fluorescence (pXRF) with a bootstrapping technique to provide i) the first large-scale Yedoma domain Mineral Concentrations Assessment (YMCA) dataset, and ii) estimates of mineral element stocks in never thawed (since deposition) ice-rich Yedoma permafrost and previously thawed and partly refrozen Alas deposits. The pXRF method for mineral element quantification is non-destructive and offers a complement to the classical dissolution and measurement by optical emission spectrometry (ICP-OES) in solution. Using this method, mineral element concentrations (Si, Al, Fe, Ca, K, Ti, Mn, Zn, Sr and Zr) were assessed on 1,292 sediment samples from the Yedoma domain with lower analytical effort and lower costs relative to the ICP-OES method. The pXRF measured concentrations were calibrated using alkaline fusion and ICP-OES measurements on a subset of 144 samples (R2 from 0.725 to 0.996). The results highlight that i) the mineral element stock in sediments of the Yedoma domain (1,387,000 km2) is higher for Si, followed by Al, Fe, K, Ca, Ti, Mn, Zr, Sr, and Zn, and that ii) the stock in Al and Fe (598 ± 213 and 288 ± 104 Gt) is in the same order of magnitude as the OC stock (327–466 Gt).

Ice-rich permafrost has been subject to abrupt thaw and thermokarst formation in the past and is vulnerable to current global warming. The ice-rich permafrost domain includes Yedoma sediments that have never thawed since deposition during the late Pleistocene and Alas sediments that were formed by previous thermokarst processes during the Lateglacial and Holocene warming. Permafrost thaw unlocks organic carbon (OC) and minerals from these deposits and exposes OC to mineralization. A portion of the OC can be associated with iron (Fe), a redox-sensitive element acting as a trap for OC. Post-depositional thaw processes may have induced changes in redox conditions in these deposits and thereby affected Fe distribution and interactions between OC and Fe, with knock-on effects on the role that Fe plays in mediating present day OC mineralization. To test this hypothesis, we measured Fe concentrations and proportion of Fe oxides and Fe complexed with OC in unthawed Yedoma and previously thawed Alas deposits. Total Fe concentrations were determined on 1,292 sediment samples from the Yedoma domain using portable X-ray fluorescence; these concentrations were corrected for trueness using a calibration based on a subset of 144 samples measured by inductively coupled plasma optical emission spectrometry after alkaline fusion (R2 = 0.95). The total Fe concentration is stable with depth in Yedoma deposits, but we observe a depletion or accumulation of total Fe in Alas deposits, which experienced previous thaw and/or flooding events. Selective Fe extractions targeting reactive forms of Fe on unthawed and previously thawed deposits highlight that about 25% of the total Fe is present as reactive species, either as crystalline or amorphous oxides, or complexed with OC, with no significant difference in proportions of reactive Fe between Yedoma and Alas deposits. These results suggest that redox driven processes during past thermokarst formation impact the present-day distribution of total Fe, and thereby the total amount of reactive Fe in Alas versus Yedoma deposits. This study highlights that ongoing thermokarst lake formation and drainage dynamics in the Arctic influences reactive Fe distribution and thereby interactions between Fe and OC, OC mineralization rates, and greenhouse gas emissions.