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).

Mineral elements bind to dissolved organic carbon (DOC) in permafrost soils, and this may contribute to the stabilization or the degradation of organic carbon along the soil to river continuum. Permafrost thaw enlarges the pool of soil constituents available for soil to river transfer. The unknown is how changes in hydrology upon permafrost degradation affect the connection between soil‐derived mineral element‐bound DOC and headwater streams. Here, we study Al, Fe, Ca, and DOC concentrations in water from a headwater stream at Eight Mile Lake, Alaska, USA (colloidal [0.22 μm–1 kDa] and truly dissolved [<1 kDa] fractions) and in soil pore waters sampled across a gradient of permafrost degradation at the same location. We target the peak flow to base flow transition to show that there is a narrow window of mineral element‐bound DOC colloid transport from soils to streams. We show that during spring thaw and maximum thaw there is an enhanced lateral transfer of mineral element‐bound DOC colloids in extensively degraded sites compared to minimally degraded sites. This is explained by a more rapid response of hydrology at peak flow to base flow transition at degraded sites. Our results suggest that ongoing permafrost degradation and the associated response of soils to changing hydrology can be detected by targeting the composition and size of mineral element‐DOC associations in soil waters and headwater streams during peak flow‐baseflow transitions.

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.

Abstract. Arctic warming and permafrost degradation are modifying northern ecosystems through changes in microtopography, soil water dynamics, nutrient availability, and vegetation succession. Upon permafrost degradation, the release of deep stores of nutrients, such as nitrogen and phosphorus, from newly thawed permafrost stimulates Arctic vegetation production. More specifically, wetter lowlands show an increase in sedges (as part of graminoids), whereas drier uplands favor shrub expansion. These shifts in the composition of vegetation may influence local mineral element cycling through litter production. In this study, we evaluate the influence of permafrost degradation on mineral element foliar stocks and potential annual fluxes upon litterfall. We measured the foliar elemental composition (Al, Ca, Fe, K, Mn, P, S, Si, and Zn) of ∼ 500 samples of typical tundra plant species from two contrasting Alaskan tundra sites, i.e., an experimental sedge-dominated site (Carbon in Permafrost Experimental Heating Research, CiPEHR) and natural shrub-dominated site (Gradient). The foliar concentration of these mineral elements was species specific, with sedge leaves having relatively high Si concentration and shrub leaves having relatively high Ca and Mn concentrations. Therefore, changes in the species biomass composition of the Arctic tundra in response to permafrost thaw are expected to be the main factors that dictate changes in elemental composition of foliar stocks and maximum potential foliar fluxes upon litterfall. We observed an increase in the mineral element foliar stocks and potential annual litterfall fluxes, with Si increasing with sedge expansion in wetter sites (CiPEHR), and Ca and Mn increasing with shrub expansion in drier sites (Gradient). Consequently, we expect that sedge and shrub expansion upon permafrost thaw will lead to changes in litter elemental composition and therefore affect nutrient cycling across the sub-Arctic tundra with potential implications for further vegetation succession.

The stabilizing properties of mineral-organic carbon (OC) interactions have been studied in many soil environments (temperate soils, podzol lateritic soils, and paddy soils). Recently, interest in their role in permafrost regions is increasing as permafrost was identified as a hotspot of change. In thawing ice-rich permafrost regions, such as the Yedoma domain, 327-466 Gt of frozen OC is buried in deep sediments. Interactions between minerals and OC are important because OC is located very near the mineral matrix. Mineral surfaces and elements could mitigate recent and future greenhouse gas emissions through physical and/or physicochemical protection of OC. The dynamic changes in redox and pH conditions associated with thermokarst lake formation and drainage trigger metal-oxide dissolution and precipitation, likely influencing OC stabilization and microbial mineralization. However, the influence of thermokarst processes on mineral-OC interactions remains poorly constrained. In this study, we aim to characterize Fe, Mn, Al, and Ca minerals and their potential protective role for OC. Total and selective extractions were used to assess the crystalline and amorphous oxides or complexed metal pools as well as the organic acids found within these pools. We analyzed four sediment cores from an ice-rich permafrost area in Central Yakutia, which were drilled (i) in undisturbed Yedoma uplands, (ii) beneath a recent lake formed within Yedoma deposits, (iii) in a drained thermokarst lake basin, and (iv) beneath a mature thermokarst lake from the early Holocene period. We find a decrease in the amount of reactive Fe, Mn, Al, and Ca in the deposits on lake formation (promoting reduction reactions), and this was largely balanced by an increase in the amount of reactive metals in the deposits on lake drainage (promoting oxidation reactions). We demonstrate an increase in the metal to C molar ratio on thermokarst process, which may indicate an increase in metal-C bindings and could provide a higher protective role against microbial mineralization of organic matter. Finally, we find that an increase in mineral-OC interactions corresponded to a decrease in CO 2 and CH 4 gas emissions on thermokarst process.

Cryogenic weathering is a key driver of periglacial sediment composition and properties. Selective mineral-grain weathering caused by freeze-thaw cycles in permafrost environments has the ability to dominate this process, leading to silt-rich grain-size distributions. The cryogenic weathering index (CWI) is a promising tool to quantify cryogenic weathering and freezing conditions. It considers the low resistance of quartz to freeze-thaw cycles compared to feldspars. Using this approach, this study aims to decipher post-depositional weathering by reconstructing cryogenic late Pleistocene Yedoma origins of the Yedoma stratotype exposure Duvanny Yar. To estimate the recent environmental endmember and to determine the initial mineral composition of sediment until freezing, the distribution of CWI in the active layer was studied. In addition to CWI, we studied mineral composition, heavy mineral distribution, grain size distribution and grain morphology. We suggest that cryogenic weathering likely altered polygenetic deposits (fluvial, nival, colluvial, lacustrine, alluvial, and aeolian processes) during sediment and ground ice accumulation. Moreover, we found two CWI distribution peaks in the late Pleistocene - Holocene sediments at the boundaries between glacial and interglacial ages. In conclusion, we see that the Duvanny Yar sediment facies varied by CWI, but also with grain-size distribution, suggesting environmental changes during formation. Nevertheless, post-depositional processes like cryogenic weathering have influenced sediment characteristics and should be considered in paleoenvironmental reconstructions.

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Abstract. Arctic warming and permafrost degradation are modifying northern ecosystems through changes in microtopography, soil water dynamics, nutrient availability, and vegetation succession. Upon permafrost degradation, the release of deep stores of nutrients such as nitrogen and phosphorus from newly thawed permafrost stimulates Arctic vegetation production. More specifically, wetter lowlands show an increase in sedges (as part of graminoids), whereas drier uplands favor shrub expansion. In turn, shifts in the composition of vegetation may influence local mineral element cycling through litter production. In this study, we evaluate the influence of permafrost degradation on mineral element foliar stocks and potential annual fluxes upon litterfall. We measured the foliar elemental composition (Al, Ca, Fe, K, Mn, P, S, Si, and Zn) on ~500 samples of typical tundra vegetation species from two contrasting Alaskan sites, i.e., under experimental (CiPEHR) and ambient (Gradient) warming. The foliar concentration of these mineral elements was species specific, with sedge leaves having relatively high Si concentration, and shrub leaves having relatively high Ca and Mn concentrations. Therefore, changes in the species biomass composition of the Arctic tundra in response to permafrost thaw are expected to be the main factors that dictate changes in elemental composition of foliar stocks and maximum potential foliar fluxes upon litterfall. We observed an increase in the mineral element foliar stocks and potential annual litterfall fluxes, with Si increasing with sedge expansion in wetter sites (CiPEHR), and Ca and Mn increasing with shrub expansion in drier sites (Gradient). Consequently, we expect that sedge and shrub expansion upon permafrost thaw will lead to changes in litter elemental composition, and affect nutrient cycling across the sub-Arctic tundra, with potential implications for further vegetation succession.