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  1. Gas exchange between the atmosphere and ocean interior profoundly impacts global climate and biogeochemistry. However, our understanding of the relevant physical processes remains limited by a scarcity of direct observations. Dissolved noble gases in the deep ocean are powerful tracers of physical air-sea interaction due to their chemical and biological inertness, yet their isotope ratios have remained underexplored. Here, we present high-precision noble gas isotope and elemental ratios from the deep North Atlantic (~32°N, 64°W) to evaluate gas exchange parameterizations using an ocean circulation model. The unprecedented precision of these data reveal deep-ocean undersaturation of heavy noble gases and isotopes resulting from cooling-driven air-to-sea gas transport associated with deep convection in the northern high latitudes. Our data also imply an underappreciated and large role for bubble-mediated gas exchange in the global air-sea transfer of sparingly soluble gases, including O 2 , N 2 , and SF 6 . Using noble gases to validate the physical representation of air-sea gas exchange in a model also provides a unique opportunity to distinguish physical from biogeochemical signals. As a case study, we compare dissolved N 2 /Ar measurements in the deep North Atlantic to physics-only model predictions, revealing excess N 2 from benthic denitrification in older deep waters (below 2.9 km). These data indicate that the rate of fixed N removal in the deep Northeastern Atlantic is at least three times higher than the global deep-ocean mean, suggesting tight coupling with organic carbon export and raising potential future implications for the marine N cycle. 
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  3. Abstract

    Constraining the magnitude of past hydrological change may improve understanding and predictions of future shifts in water availability. Here we demonstrate that water-table depth, a sensitive indicator of hydroclimate, can be quantitatively reconstructed using Kr and Xe isotopes in groundwater. We present the first-ever measurements of these dissolved noble gas isotopes in groundwater at high precision (≤0.005‰ amu−1; 1σ), which reveal depth-proportional signals set by gravitational settling in soil air at the time of recharge. Analyses of California groundwater successfully reproduce modern groundwater levels and indicate a 17.9 ± 1.3 m (±1 SE) decline in water-table depth in Southern California during the last deglaciation. This hydroclimatic transition from the wetter glacial period to more arid Holocene accompanies a surface warming of 6.2 ± 0.6 °C (±1 SE). This new hydroclimate proxy builds upon an existing paleo-temperature application of noble gases and may identify regions prone to future hydrological change.

     
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  4. Abstract

    Confining clay layers typically protect groundwater aquifers against downward intrusion of contaminants. In the context of groundwater arsenic in Bangladesh, we challenge this notion here by showing that organic carbon drawn from a clay layer into a low-arsenic pre-Holocene (>12 kyr-old) aquifer promotes the reductive dissolution of iron oxides and the release of arsenic. The finding explains a steady rise in arsenic concentrations in a pre-Holocene aquifer below such a clay layer and the repeated failure of a structurally sound community well. Tritium measurements indicate that groundwater from the affected depth interval (40–50 m) was recharged >60 years ago. Deeper (55–65 m) groundwater in the same pre-Holocene aquifer was recharged only 10–50 years ago but is still low in arsenic. Proximity to a confining clay layer that expels organic carbon as an indirect response to groundwater pumping, rather than directly accelerated recharge, caused arsenic contamination of this pre-Holocene aquifer.

     
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  5. Abstract

    The potential for molecular hydrogen () generated via serpentinization to fuel subsurface microbial ecosystems independent from photosynthesis has prompted biogeochemical investigations of serpentinization‐influenced fluids. However, investigations typically sample via surface seeps or open‐borehole pumping, which can mix chemically distinct waters from different depths. Depth‐indiscriminate sampling methods could thus hinder understanding of the spatial controls on nutrient availability for microbial life. To resolve distinct groundwaters in a low‐temperature serpentinizing environment, we deployed packers (tools that seal against borehole walls during pumping) in two‐deep, peridotite‐hosted wells in the Samail Ophiolite, Oman. Isolation and pumping of discrete intervals as deep astobelow ground level revealed multiple aquifers that ranged in pH from 8 to 11. Chemical analyses and 16S rRNA gene sequencing of deep, highly reactedgroundwaters bearing up to,methane () andsulfate () revealed an ecosystem dominated by Bacteria affiliated with the class Thermodesulfovibrionia, a group of chemolithoheterotrophs supported byoxidation coupled toreduction. In shallower, oxidizedgroundwaters, aerobic and denitrifying heterotrophs were relatively more abundant. Highandof(up toand, respectively) indicated microbialoxidation, particularly inwaters with evidence of mixing withwaters. This study demonstrates the power of spatially resolving groundwaters to probe their distinct geochemical conditions and chemosynthetic communities. Such information will help improve predictions of where microbial activity in fractured rock ecosystems might occur, including beyond Earth.

     
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