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Mantle-derived noble gases in volcanic gases are powerful tracers of terrestrial volatile evolution, as they contain mixtures of both primordial (from Earth’s accretion) and secondary (e.g., radiogenic) isotope signals that characterize the composition of deep Earth. However, volcanic gases emitted through subaerial hydrothermal systems also contain contributions from shallow reservoirs (groundwater, crust, atmosphere). Deconvolving deep and shallow source signals is critical for robust interpretations of mantle-derived signals. Here, we use a novel dynamic mass spectrometry technique to measure argon, krypton, and xenon isotopes in volcanic gas with ultrahigh precision. Data from Iceland, Germany, United States (Yellowstone, Salton Sea), Costa Rica, and Chile show that subsurface isotope fractionation within hydrothermal systems is a globally pervasive and previously unrecognized process causing substantial nonradiogenic Ar-Kr-Xe isotope variations. Quantitatively accounting for this process is vital for accurately interpreting mantle-derived volatile (e.g., noble gas and nitrogen) signals, with profound implications for our understanding of terrestrial volatile evolution.

Terrestrial amplification (TA) of land warming relative to oceans is apparent in recent climatic observations. TA results from land-sea coupling of moisture and heat and is therefore important for predicting future warming and water availability. However, the theoretical basis for TA has never been tested outside the short instrumental period, and the spatial pattern and amplitude of TA remain uncertain. Here, we investigate TA during the Last Glacial Maximum (LGM; ~20 thousand years) in the low latitudes, where the theory is most applicable. We find remarkable consistency between paleotemperature proxies, theory, and climate model simulations of both LGM and future climates. Paleoclimate data thus provide crucial new support for TA, refining the range of future low-latitude, low-elevation TA to 1.37 − 0.23 + 0.27 (95% confidence interval), i.e., land warming ~40% more than oceans. The observed data model theory agreement helps reconcile LGM marine and terrestrial paleotemperature proxies, with implications for equilibrium climate sensitivity.

The magnitude of global cooling during the Last Glacial Maximum (LGM, the coldest multimillennial interval of the last glacial period) is an important constraint for evaluating estimates of Earth's climate sensitivity1,2. Reliable LGM temperatures come from high-latitude ice cores3,4, but substantial disagreement exists between proxy records in the low latitudes1,5-8, where quantitative low-elevation records on land are scarce. Filling this data gap, noble gases in ancient groundwater record past land surface temperatures through a direct physical relationship that is rooted in their temperature-dependent solubility in water9,10. Dissolved noble gases are suitable tracers of LGM temperature because of their complete insensitivity to biological and chemical processes and the ubiquity of LGM-aged groundwater around the globe11,12. However, although several individual noble gas studies have found substantial tropical LGM cooling13-16, they have used different methodologies and provide limited spatial coverage. Here we use noble gases in groundwater to show that the low-altitude, low-to-mid-latitude land surface (45degrees south to 35degrees north) cooled by 5.8±0.6degrees Celsius (mean±95% confidence interval) during the LGM. Our analysis includes four decades of groundwater noble gas data from six continents, along with new records from the tropics, all of which were interpreted using the same physical framework. Our land-based result broadly supports a recent reconstruction based on marine proxy data assimilation1 that suggested greater climate sensitivity than previous estimates5-7.

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

In central California, irrigation seepage perturbs groundwater inorganic carbon chemistry and complicates radiocarbon dating., Groundwater is an important source of drinking and irrigation water. Dating groundwater informs its vulnerability to contamination and aids in calibrating flow models. Here, we report measurements of multiple age tracers (14C, 3H, 39Ar, and 85Kr) and parameters relevant to dissolved inorganic carbon (DIC) from 17 wells in California’s San Joaquin Valley (SJV), an agricultural region that is heavily reliant on groundwater. We find evidence for a major mid-20th century shift in groundwater DIC input from mostly closed- to mostly open-system carbonate dissolution, which we suggest is driven by input of anthropogenic carbonate soil amendments. Crucially, enhanced open-system dissolution, in which DIC equilibrates with soil CO2, fundamentally affects the initial 14C activity of recently recharged groundwater. Conventional 14C dating of deeper SJV groundwater, assuming an open system, substantially overestimates residence time and thereby underestimates susceptibility to modern contamination. Because carbonate soil amendments are ubiquitous, other groundwater-reliant agricultural regions may be similarly affected.

Significance We report the discovery of anomalously high 3He/4He in “cold” geothermal fluids of central Panama, far from any active volcanoes. Combined with independent constraints from lava geochemistry, mantle source geochemical anomalies in Central America require a Galápagos plume contribution that is not derived from hotspot track recycling. Instead, these signals likely originate from large-scale transport of Galápagos plume material at sublithospheric depths. Mantle flow modeling and geophysical observations further indicate these geochemical anomalies could result from a Galápagos plume-influenced asthenospheric “mantle wind” that is actively “blowing” through a slab window beneath central Panama. The lateral transport of plume material represents a potentially widespread yet underappreciated mechanism that scatters enriched geochemical signatures in mantle domains far from plumes., It is well established that mantle plumes are the main conduits for upwelling geochemically enriched material from Earth's deep interior. The fashion and extent to which lateral flow processes at shallow depths may disperse enriched mantle material far (>1,000 km) from vertical plume conduits, however, remain poorly constrained. Here, we report He and C isotope data from 65 hydrothermal fluids from the southern Central America Margin (CAM) which reveal strikingly high 3He/4He (up to 8.9RA) in low-temperature (≤50 °C) geothermal springs of central Panama that are not associated with active volcanism. Following radiogenic correction, these data imply a mantle source 3He/4He >10.3RA (and potentially up to 26RA, similar to Galápagos hotspot lavas) markedly greater than the upper mantle range (8 ± 1RA). Lava geochemistry (Pb isotopes, Nb/U, and Ce/Pb) and geophysical constraints show that high 3He/4He values in central Panama are likely derived from the infiltration of a Galápagos plume–like mantle through a slab window that opened ∼8 Mya. Two potential transport mechanisms can explain the connection between the Galápagos plume and the slab window: 1) sublithospheric transport of Galápagos plume material channeled by lithosphere thinning along the Panama Fracture Zone or 2) active upwelling of Galápagos plume material blown by a “mantle wind” toward the CAM. We present a model of global mantle flow that supports the second mechanism, whereby most of the eastward transport of Galápagos plume material occurs in the shallow asthenosphere. These findings underscore the potential for lateral mantle flow to transport mantle geochemical heterogeneities thousands of kilometers away from plume conduits.

The Western U.S. is vulnerable to hydrological stress, and insights from past climate periods are helpful for providing historical benchmarks for future climate projections. Myriad evidence from coupled models and paleoclimatic proxies suggests a major reorganization of west coast hydroclimate during the Last Glacial Maximum (LGM, ∼17–25 ka), such that the Southwest U.S. was wetter than modern day and the Pacific Northwest was drier. Yet the fundamental mechanisms underlying these hydroclimatic shifts remain unclear. Here, we employ a suite of targeted model simulations to probe the influence of LGM Northern Hemisphere ice sheets on west coast atmospheric dynamics. Whereas previous modeling studies have suggested that the southward shift of LGM west coast precipitation was driven only by the mechanical steering of atmospheric circulation by elevated ice sheet topography, we find this to be an artifact of earlier simulations that neglected realistic air-sea interaction. Instead, our simulations indicate that ice sheet albedo induced a pattern of North Pacific sea surface temperatures, reinforced by ocean-atmosphere feedbacks, that shifted the large-scale atmospheric circulation as well as the latitudinal distribution of west coast precipitation southward during the LGM. Crucially, we find that atmosphere-ocean feedbacks that sustained this ice sheet albedo-induced temperature pattern in the LGM could drive similar hydroclimatic changes today.

Carbon dioxide emissions from active subaerial volcanoes represent 20–50% of the annual global volcanic CO2 flux (Barry et al., 2014). Passive degassing of carbon from the flanks of volcanoes, and the associated accumulation of dissolved inorganic carbon (DIC) within nearby groundwater, also represents a potentially important, yet poorly constrained flux of carbon to the surface (Werner et al., 2019). Here we investigate sources and sinks of DIC in groundwaters in the Lassen Peak region of California. Specifically, we report and interpret the relative abundance and isotopic composition of helium (3He, 4He) and carbon (12C, 13C, 14C) in 37 groundwater samples, from 24 distinct wells, collected between 20 and 60 km from Lassen Peak. Measured groundwater samples have air-corrected 3He/4He values between 0.19 and 7.44 RA (where RA = air 3He/4He = 1.39 × 10−6), all in excess of the radiogenic production value (~0.05 RA), indicating pervasive mantle-derived helium additions to the groundwater system in the Lassen Peak region. Stable carbon isotope ratios of DIC (δ13C) vary between −12.6 and − 27.7‰ (vs. VPDB). Measured groundwater DIC/3He values fall in the range of 2.2 × 1010 to 1.1 × 1012. Using helium and carbon isotope data, we explore several conceptual models to estimate surface carbon contributions and to differentiate between DIC derived from soil CO2 versus DIC derived from external (slab and mantle) carbon sources. Specifically, if we use 14C to identify soil-derived DIC (assuming decadal-to-centennial groundwater ages and a soil CO2 14C activity equal to that of the atmosphere), we calculate that a hypothetical external carbon source would have an apparent δ13C signature between −10.3 and − 59.3‰ (vs. Vienna Pee Dee Belemnite (VPDB)) and an apparent C/3He between 7.0 × 109 and 1.0 × 1012. These apparent δ13C and C/3He values are substantially isotopically lighter than and greater than canonical MORB values, respectively. We suggest that >95% of any external (non-soil-derived) DIC in groundwater must thus be non-mantle in origin (i.e., slab derived or assimilated organic carbon). We further investigate possible sources of external DIC to groundwater using two idealized conceptual approaches: a pure (unfractionated) source mixing model (after Sano and Marty, 1995) and a scenario that invokes fractionation due to calcite precipitation. Because the former model requires carbon contributions from an organic source component with unrealistically low δ13C (~ − 60‰), we suggest that the second scenario is more plausible. Importantly, however, we caution that all conceptual models are dependent on assumptions about initial 14C activity. Thus, we cannot rule out the possibility that the true fraction of non-surface-derived DIC in these samples is lower or negligible, despite the pervasive mantle-derived He isotope signatures throughout the region. Following the 14C approach to deconvolving sources of DIC, we determine that the maximum passive carbon flux could be up to ~2.2 × 106 kg/yr, which is lower than previous magmatic carbon flux estimates from the Lassen region ( Rose and Davisson, 1996 ). We find that the passive dissolved carbon flux could represent a maximum of ~4–18% of the total Lassen geothermal CO2 degassing flux (estimated to be ~3.5 × 107 kg/yr Rose and Davisson, 1996 ; Gerlach et al., 2008 ), which is still more than an order of magnitude smaller than soil gas CO2 flux estimates (7.3–11 × 107 kg/yr) for nearby volcanoes ( Sorey et al., 1998 ; Gerlach et al., 1999 ; Evans et al., 2002 ; Werner et al., 2014 ). We conclude that passive dissolved carbon fluxes should be combined with geothermal fluxes and soil gas fluxes to obtain a complete picture of volcanic carbon emissions globally. Our approach highlights the utility of measuring helium isotopes in concert with the full suite of noble gas abundances, tritium, δ13C and 14C, which when interpreted together can be used to better elucidate the various sources of DIC in groundwater.

Understanding the age and movement of groundwater is important for predicting the vulnerability of wells to contamination, constraining flow models that inform sustainable groundwater management, and interpreting geochemical signals that reflect past climate. Due to both the ubiquity of groundwater with order ten-thousand-year residence times and its importance for climate reconstruction of the last glacial period, there is a strong need for improving geochemical dating tools on this timescale. Whereas 14C of dissolved inorganic carbon and dissolved 4He are common age tracers for Late Pleistocene groundwater, each is limited by systematic uncertainties related to aquifer composition and lithology, and the extent of water-rock interaction. In principle, radiogenic 40Ar in groundwater acquired from decay of 40K in aquifer minerals should be insensitive to some processes that impact 14C and 4He and thus represent a useful, complementary age tracer. In practice, however, detection of significant radiogenic 40Ar signals in groundwater has been limited to a small number of studies of extremely old groundwater (>100 ka). Here we present the first high-precision (

Marine sediments, speleothems, paleo-lake elevations, and ice core methane and δ18O of O2 (δ18Oatm) 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 δ18Oatm and inferred changes in fractionation by the global terrestrial biosphere (ΔεLAND) 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 ΔεLAND are synchronous with or shortly follow small-amplitude WD CH4 peaks that occur within Heinrich stadials 1, 2, 4, and 5 – periods of low atmospheric CH4 concentrations. These local CH4 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 δ18O of terrestrial precipitation (the source water for atmospheric O2 production), we propose a simple mechanism by which ΔεLAND tracks the centroid latitude of terrestrial oxygen production. As intense rainfall and oxygen production migrate northward, ΔεLAND should decrease due to the underlying meridional gradient in rainfall δ18O. A southward shift should increase ΔεLAND. Monsoon intensity also influences δ18O 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 ΔεLAND unambiguously imply a southward shift of tropical rainfall. The exact magnitude of this shift, however, remains under-constrained by ΔεLAND.

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., In this study, a new analytical technique is employed to measure Kr and Xe isotopes in groundwater at high precision. These measurements indicate that gravitational signals of past water-table depth are preserved in ancient groundwater, representing a novel proxy for past terrestrial hydroclimate.

In 2017, fluid and gas samples were collected across the Costa Rican Arc. He and Ne isotopes, C isotopes as well as total organic and inorganic carbon concentrations were measured. The samples (n = 24) from 2017 are accompanied by (n = 17) samples collected in 2008, 2010 and 2012. He-isotopes ranged from arc-like (6.8 RA) to crustal (0.5 RA). Measured dissolved inorganic carbon (DIC) δ13CVPDB values varied from 3.55 to −21.57‰, with dissolved organic carbon (DOC) following the trends of DIC. Gas phase CO2 only occurs within ~20 km of the arc; δ13CVPDB values varied from −0.84 to −5.23‰. Onsite, pH, conductivity, temperature and dissolved oxygen (DO) were measured; pH ranged from 0.9–10.0, conductivity from 200–91,900 μS/cm, temperatures from 23–89 °C and DO from 2–84%. Data were used to develop a model which suggests that ~91 ± 4.0% of carbon released from the slab/mantle beneath the Costa Rican forearc is sequestered within the crust by calcite deposition with an additional 3.3 ± 1.3% incorporated into autotrophic biomass., Measurement(s)temperature of air • pH • Total Organic Carbon • carbon-13 atom • dissolved inorganic carbon content • dissolved organic carbon content • carbon dioxide • helium-3 atom • helium-4 atom • methaneTechnology Type(s)Temperature Probe Device • pH sensor • mass spectrometerFactor Type(s)time • location where data was collectedSample Characteristic - Environmentvolcanic arc • fumarole • hot spring • seepSample Characteristic - LocationCosta Rica Machine-accessible metadata file describing the reported data: 10.6084/m9.figshare.10293350

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. 136Xe/129Xe) 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 temperature-controlled 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 (Δm), decrease in magnitude with atomic number but are proportional to Δm 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.

The Baja California Peninsula is located within a complex geodynamic setting, marked by continental rifting immediately to the east in the Gulf of California, and abundant geothermal manifestations. We report helium and carbon isotopic and relative abundance data sampled from gas and fluid localities (n = 12) across northern Baja California, Mexico. Samples were collected in three distinct regions of Baja: Pacific Borderlands (PB) in northwestern Baja, Peninsula Ranges and Inland Valleys (PRIV) in central Baja, and the Gulf Extensional Province (GEP) in northeastern Baja. Helium isotopes (3He/4He), carbon isotopes (δ13CO2), and CO2/3He values all are highest in GEP samples, and lower in samples from the PB and PRIV. In the GEP, helium isotopes reach moderately mantle-like values (1.74 RA) (where RA = air 3He/4He), while in the PRIV and PB provinces values are more radiogenic (~0.11 RA). 3He/4He values suggest mixing between mantle-derived and crustal-derived radiogenic components, with a maximum mantle contribution of ~21% in the GEP samples. High He isotopes correlate with low mantle velocity zones at a depth of 25–40 km, suggesting a mantle source of He in the GEP, due to extensional crustal thinning. Carbon isotopes (δ13CO2) vary widely between −17.6 and 4.5‰ (vs. PDVB) and CO2/3He values vary over several orders of magnitude (2.0 × 105 to 1.1 × 1013). Variable δ13CO2 and CO2/3He values in the PRIV and PB localities are consistent with calcite precipitation in shallow-level (upper 5 km) hydrothermal systems. The bimodal nature of the He-CO2 data suggests fundamentally different transfer mechanisms in each of the three distinct regions, indicating complex interplay between regional mantle degassing, faulting-assisted migration of crustal fluids, and volatile sequestration via secondary processes (e.g., calcite precipitation). These results, along with literature data, allow for systematic assessment of both mantle sources and secondary processes, providing new insights into how volatiles are transported through the Baja California peninsula.