Groundwater in the McMurdo Dry Valleys of Antarctica is commonly enriched in calcium and chloride, in contrast to surface and groundwater in temperate regions, where calcium chemistry is largely controlled by the dissolution of carbonates and sulfates. These Antarctic Ca-Cl brines have extremely low freezing points, which leads to moist soil conditions that persist unfrozen and resist evaporation, even in cold, arid conditions. Several hypotheses exist to explain these unusual excess-calcium solutions, including salt deliquescence and differential salt mobility and cation exchange. Although the cation exchange mechanism was shown to explain the chemistry of pore waters in permafrost cores from several meters depth, it has not been evaluated for near-surface groundwater and wetland features (water tracks) in which excess-calcium pore-water solutions are common. Here, we use soluble salt and exchangeable cation concentrations to determine whether excess calcium is present in water-track brines and if cation exchange could be responsible for calcium enrichment in these cold desert groundwaters. We show that calcium enrichment by cation exchange is not occurring universally across the McMurdo Dry Valleys. Instead, evidence of the present-day formation of Ca-Cl−rich brines by cation exchange is focused in a geographically specific location in Taylor Valley, with hydrological position, microclimate, soil depth, and organic matter influencing the spatial extent of cation exchange reactions. Up-valley sites may be too cold and dry for widespread exchange, and warm and wet coastal sites are interpreted to host sediments whose exchange reactions have already gone to completion. We argue that exchangeable cation ratios can be used as a signature of past freeze-concentration of brines and exchange reactions, and thus could be considered a geochemical proxy for past groundwater presence in planetary permafrost settings. Correlations between water-track organic matter, fine sediment concentration, and cation exchange capacity suggest that water tracks may be sites of enhanced biogeochemical cycling in cold desert soils and serve as a model for predicting how active layers in the Antarctic will participate in biogeochemical cycling during periods of future thaw. 
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                            Evidence for late winter biogeochemical connectivity in permafrost soils
                        
                    
    
            Abstract The permafrost active layer is a key supplier of soil organic carbon and mineral nutrients to Arctic rivers. In the active layer, sites of soil-water exchange are locations for organic carbon and nutrient mobilization. Previously these sites were considered as connected during summer months and isolated during winter months. Whether soil pore waters in active layer soils are connected during shoulder seasons is poorly understood. In this study, exceptionally heavy silicon isotope compositions in soil pore waters show that during late winter, there is no connection between isolated pockets of soil pore water in soils with a shallow active layer. However, lighter silicon isotope compositions in soil pore waters reveal that soils are biogeochemically connected for longer than previously considered in soils with a deeper active layer. We show that an additional 21% of the 0–1 m soil organic carbon stock is exposed to soil - water exchange. This marks a hot moment during a dormant season, and an engine for organic carbon transport from active layer soils. Our findings mark the starting point to locate earlier pathways for biogeochemical connectivity, which need to be urgently monitored to quantify the seasonal flux of organic carbon released from permafrost soils. 
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                            - PAR ID:
- 10553066
- Publisher / Repository:
- Springer
- Date Published:
- Journal Name:
- Communications Earth & Environment
- Volume:
- 4
- Issue:
- 1
- ISSN:
- 2662-4435
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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