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Dissolved noble gases are ideal conservative tracers of physical processes in the Earth system due to their chemical and biological inertness. Although bulk concentrations of dissolved Ar, Kr, and Xe are commonly measured to constrain physical models of atmosphere, ocean, and terrestrial hydrosphere processes, stable isotope ratios of these gases (e.g. 136 Xe/ 129 Xe) are seldom used because of low signal-to-noise ratios. Here we present the first results from a new method of dissolved gas sampling, extraction and analysis that permits measurement of stable Ar, Kr, and Xe isotope ratios at or below ∼5 per meg amu −1 precision (1σ), two orders-of-magnitude below conventional Kr and Xe isotopic measurements. This gain in precision was achieved by quantitative extraction and subsequent purification of dissolved noble gases from 2-L water samples via helium sparging and viscous dual-inlet isotope ratio mass spectrometry. We have determined the solubility fractionation factors (α sol) for stable Ar, Kr, and Xe isotope ratios between ∼2 and 20 • C via laboratory equilibration experiments. We have also conducted temperaturecontrolled air-water gas exchange experiments to estimate the kinetic fractionation factors (α kin) of these isotope ratios. We find that both α sol and α kin , normalized by isotopic mass difference (m), decrease in magnitude with atomic number but are proportional to m for isotope ratios of the same element. With the new ability for high precision isotopic measurements, we suggest that dissolved Kr and Xe isotope ratios in groundwater represent a promising, novel geochemical tool with important applications for groundwater modeling, water resource management, and paleoclimate.

Abstract. Marine sediments, speleothems, paleo-lake elevations, and ice core methane and δ 18 O of O 2 (δ 18 O atm ) records provide ample evidence for repeated abrupt meridional shifts in tropical rainfall belts throughout the last glacial cycle. To improve understanding of the impact of abrupt events on the global terrestrial biosphere, we present composite records of δ 18 O atm and inferred changes in fractionation by the global terrestrial biosphere ( ε LAND ) from discrete gas measurements in the WAIS Divide (WD) and Siple Dome (SD) Antarctic ice cores. On the common WD timescale, it is evident that maxima in ε LAND are synchronous with or shortly follow small-amplitude WD CH 4 peaks that occur within Heinrich stadials 1, 2, 4, and 5 -periods of low atmospheric CH 4 concentrations. These local CH 4 maxima have been suggested as markers of abrupt climate responses to Heinrich events. Based on our analysis of the modern seasonal cycle of gross primary productivity (GPP)-weighted δ 18 O of terrestrial precipitation (the source water for atmospheric O 2 production), we propose a simple mechanism by which ε LAND tracks the centroid latitude of terrestrial oxygen production. As intense rainfall and oxygen production migrate northward, ε LAND should decrease due to the underlying meridional gradient in rainfall δ 18 O. A southward shift should increase ε LAND . Monsoon intensity also influences δ 18 O of precipitation, and although we cannot determine the relative contributions of the two mechanisms, both act in the same direction. Therefore, we suggest that abrupt increases in ε LAND unambiguously imply a southward shift of tropical rainfall. The exact magnitude of this shift, however, remains under-constrained by ε LAND .

Past studies of noble gas concentrations in the deep ocean have revealed widespread, several percent undersaturation of Ar, Kr, and Xe. However, the physical explanation for these disequilibria remains unclear. To gain insight into undersaturation set by deep‐water formation, we measured heavy noble gas isotope and elemental ratios from the deep North Pacific using a new analytical technique. To our knowledge, these are the first high‐precision seawater profiles of 38Ar/36Ar and Kr and Xe isotope ratios. To interpret isotopic disequilibria, we carried out a suite of laboratory experiments to measure solubility fractionation factors in seawater. In the deep North Pacific, we find undersaturation of heavy‐to‐light Ar and Kr isotope ratios, suggesting an important role for rapid cooling‐driven, diffusive air‐to‐sea gas transport in setting the deep‐ocean undersaturation of heavy noble gases. These isotope ratios represent promising new constraints for quantifying physical air‐sea gas exchange processes, complementing noble gas concentration measurements.

To explore steady state fractionation processes in the unsaturated zone (UZ), we measured argon, krypton, and xenon isotope ratios throughout a ∼110 m deep UZ at the United States Geological Survey (USGS) Amargosa Desert Research Site (ADRS) in Nevada, USA. Prior work has suggested that gravitational settling should create a nearly linear increase in heavy‐to‐light isotope ratios toward the bottom of stagnant air columns in porous media. Our high‐precision measurements revealed a binary mixture between (1) expected steady state isotopic compositions and (2) unfractionated atmospheric air. We hypothesize that the presence of an unsealed pipe connecting the surface to the water table allowed for direct inflow of surface air in response to extensive UZ gas sampling prior to our first (2015) measurements. Observed isotopic resettling in deep UZ samples collected a year later, after sealing the pipe, supports this interpretation. Data and modeling each suggest that the strong influence of gravitational settling and weaker influences of thermal diffusion and fluxes of CO2 and water vapor accurately describe steady state isotopic fractionation of argon, krypton, and xenon within the UZ. The data confirm that heavy noble gas isotopes are sensitive indicators of UZ depth. Based on this finding, we outline a potential inverse approach to quantify past water table depths from noble gas isotope measurements in paleogroundwater, after accounting for fractionation during dissolution of UZ air and bubbles.

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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