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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.

Microbial communities in terrestrial geothermal systems often contain chemolithoautotrophs with well-characterized distributions and metabolic capabilities. However, the extent to which organic matter produced by these chemolithoautotrophs supports heterotrophs remains largely unknown. Here we compared the abundance and activity of peptidases and carbohydrate active enzymes (CAZymes) that are predicted to be extracellular identified in metagenomic assemblies from 63 springs in the Central American and the Andean convergent margin (Argentinian backarc of the Central Volcanic Zone), as well as the plume-influenced spreading center in Iceland. All assemblies contain two orders of magnitude more peptidases than CAZymes, suggesting that the microorganisms more often use proteins for their carbon and/or nitrogen acquisition instead of complex sugars. The CAZy families in highest abundance are GH23 and CBM50, and the most abundant peptidase families are M23 and C26, all four of which degrade peptidoglycan found in bacterial cells. This implies that the heterotrophic community relies on autochthonous dead cell biomass, rather than allochthonous plant matter, for organic material. Enzymes involved in the degradation of cyanobacterial- and algal-derived compounds are in lower abundance at every site, with volcanic sites having more enzymes degrading cyanobacterial compounds and non-volcanic sites having more enzymes degrading algal compounds. Activity assays showed that many of these enzyme classes are active in these samples. High temperature sites (> 80°C) had similar extracellular carbon-degrading enzymes regardless of their province, suggesting a less well-developed population of secondary consumers at these sites, possibly connected with the limited extent of the subsurface biosphere in these high temperature sites. We conclude that in < 80°C springs, chemolithoautotrophic production supports heterotrophs capable of degrading a wide range of organic compounds that do not vary by geological province, even though the taxonomic and respiratory repertoire of chemolithoautotrophs and heterotrophs differ greatly across these regions.

East Africa hosts significant reserves of untapped geothermal energy. Most exploration has focused on geologically young (

The episodic growth of high-elevation orogenic plateaux is controlled by a series of geodynamic processes. However, determining the underlying mechanisms that drive plateau growth dynamics over geological history and constraining the depths at which growth originates, remains challenging. Here we present He-CO2-N2 systematics of hydrothermal fluids that reveal the existence of a lithospheric-scale fault system in the southeastern Tibetan Plateau, whereby multi-stage plateau growth occurred in the geological past and continues to the present. He isotopes provide unambiguous evidence for the involvement of mantle-scale dynamics in lateral expansion and localized surface uplift of the Tibetan Plateau. The excellent correlation between 3He/4He values and strain rates, along the strike of Indian indentation into Asia, suggests non-uniform distribution of stresses between the plateau boundary and interior, which modulate southeastward growth of the Tibetan Plateau within the context of India-Asia convergence. Our results demonstrate that deeply-sourced volatile geochemistry can be used to constrain deep dynamic processes involved in orogenic plateau growth., Deeply-sourced volatiles are releasing from orogenic plateau regions, providing windows to plateau growth dynamics occurring at variable depths. Here the authors show that mantle-derived volatiles reveal the involvement of mantle dynamics in southeastward growth of the Tibetan Plateau.

Volatile elements (water, carbon, nitrogen, sulfur, halogens, and noble gases) played an essential role in the secular evolution of the solid Earth and emergence of life. Here we provide an overview of Earth's volatile inventories and describe the mechanisms by which volatiles are conveyed between Earth's surface and mantle reservoirs, via subduction and volcanism. Using literature data, we compute volatile concentration and flux estimates for Earth's major volatile reservoirs and provide an internally balanced assessment of modern global volatile recycling. Using a nitrogen isotope box model, we show that recycling of N (and possibly C and S) likely began before 2 Ga and that ingassing fluxes have remained roughly constant since this time. In contrast, our model indicates recycling of H2O(and most likely noble gases) was less efficient in the past. This suggests a decoupling of major volatile species during subduction through time, which we attribute to the evolving thermal regime of subduction zones and the different stabilities of the carrier phases hosting each volatile. ▪ This review provides an overview of Earth's volatile inventory and the mechanisms by which volatiles are transferred between Earth reservoirs via subduction. ▪ The review frames the current thinking regarding how Earth acquired its original volatile inventory and subsequently evolved through subduction processes and volcanism.

The subsurface is among Earth’s largest biomes, but the extent to which microbial communities vary across tectonic plate boundaries or interact with subduction-scale geological processes remains unknown. Here we compare bacterial community composition with deep-subsurface geochemistry from 21 hot springs across the Costa Rican convergent margin. We find that cation and anion compositions of the springs reflect the dip angle and position of the underlying tectonic structure and also correlate with the bacterial community. Co-occurring microbial cliques related to cultured chemolithoautotrophs that use the reverse tricarboxylic acid cycle (rTCA) as well as abundances of metagenomic rTCA genes correlate with concentrations of slab-volatilized carbon. This, combined with carbon isotope evidence, suggests that fixation of slab-derived CO2 into biomass may support a chemolithoautotrophy-based subsurface ecosystem. We calculate that this forearc subsurface biosphere could sequester 1.4 × 109 to 1.4 × 1010 mol of carbon per year, which would decrease estimates of the total carbon delivered to the mantle by 2 to 22%. Based on the observed correlations, we suggest that distribution and composition of the subsurface bacterial community are probably affected by deep tectonic processes across the Costa Rican convergent margin and that, by sequestering carbon volatilized during subduction, these chemolithoautotrophic communities could in turn impact the geosphere. The subsurface biosphere across a convergent margin may reflect tectonic processes and reduce carbon transfer to the mantle, according to bacterial and geochemical correlations from hot springs across the Costa Rican margin.

Commercial helium systems have been found to date as a serendipitous by-product of petroleum exploration. There are nevertheless significant differences in the source and migration properties of helium compared with petroleum. An understanding of these differences enables prospects for helium gas accumulations to be identified in regions where petroleum exploration would not be tenable. Here we show how the basic petroleum exploration playbook (source, primary migration from the source rock, secondary longer distance migration, trapping) can be modified to identify helium plays. Plays are the areas occupied by a prospective reservoir and overlying seal associated with a mature helium source. This is the first step in identifying the detail of helium prospects (discrete pools of trapped helium). We show how these principles, adapted for helium, can be applied using the Rukwa Basin in the Tanzanian section of the East African Rift as a case study. A thermal hiatus caused by rifting of the continental basement has resulted in a surface expression of deep crustal gas release in the form of high-nitrogen gas seeps containing up to 10%4He. We calculate the total likely regional source-rock helium generative capacity, identify the role of the Rungwe volcanic province in releasing the accumulated crustal helium and show the spatial control of helium concentration dilution by the associated volcanic CO2. Nitrogen, both dissolved and as a free-gas phase, plays a key role in the primary and secondary migration of crustal helium and its accumulation into what might become a commercially viable gas pool. This too is examined. We identify and discuss evidence that structures and seals suitable for trapping hydrocarbon and CO2 gases will likely also be efficient for helium accumulation on the timescale of the Rukwa Basin activity. The Rukwa Basin prospective recoverable P50 resources of helium have been independently estimated to be about 138 BSCF (billion standard cubic ft: 2.78 × 109 m3 at STP). If this volume is confirmed it would represent about 25% of the current global helium reserve. Two exploration wells, Tai 1 and Tai 2, completed by August 2021 have proved the presence of seal and reservoir horizons with the reservoirs containing significant helium shows.

Noble gases record fluid interactions in multiphase subsurface environments through fractionation processes during fluid equilibration. Water in the presence of hydrocarbons at the subsurface acquires a distinct elemental signature due to the difference in solubility between these two fluids. We find the atmospheric noble gas signature in produced water is partially preserved after hydrocarbons production and water disposal to unlined ponds at the surface. This signature is distinct from meteoric water and can be used to trace oil-field water seepage into groundwater aquifers. We analyse groundwater (n = 30) and fluid disposal pond (n = 2) samples from areas overlying or adjacent to the Fruitvale, Lost Hills, and South Belridge Oil Fields in the San Joaquin Basin, California, USA. Methane (2.8 × 10−7 to 3 × 10−2 cm3 STP/cm3) was detected in 27 of 30 groundwater samples. Using atmospheric noble gas signatures, the presence of oil-field water was identified in 3 samples, which had equilibrated with thermogenic hydrocarbons in the reservoir. Two (of the three) samples also had a shallow microbial methane component, acquired when produced water was deposited in a disposal pond at the surface. An additional 6 samples contained benzene and toluene, indicative of interaction with oil-field water; however, the noble gas signatures of these samples are not anomalous. Based on low tritium and 14C contents (≤ 0.3 TU and 0.87–6.9 pcm, respectively), the source of oil-field water is likely deep, which could include both anthropogenic and natural processes. Incorporating noble gas analytical techniques into the groundwater monitoring programme allows us to 1) differentiate between thermogenic and microbial hydrocarbon gas sources in instances when methane isotope data are unavailable, 2) identify the carrier phase of oil-field constituents in the aquifer (gas, oil-field water, or a combination), and 3) differentiate between leakage from a surface source (disposal ponds) and from the hydrocarbon reservoir (either along natural or anthropogenic pathways such as faulty wells).

Volatile elements are concentrated at Earth's surface, forming a rich atmosphere and oceans which enabled the eventual emergence of life. However, volatiles are also abundant in solid Earth reservoirs, such as the crust and mantle, and these reservoirs play a key role in moderating volatile movement throughout the planet. Continental cratons represent a potentially large, yet under-constrained volatile reservoir. When cratonic regions are catastrophically disrupted by large volcanic and/or rifting events, they release massive amounts of volatiles into Earth's atmosphere on geologically-abrupt timescales (e.g., Lowenstern et al., 2014 ; Muirhead et al., 2020 ). Here, we report gas data (He-Ne-N2-Ar-CO2) from seeps along the flanks of the Tanzanian craton, within the western branch of the East African Rift System (EARS) - a region where the stable continental craton is actively being broken apart by rifting and simultaneously heated by plume-induced volcanism. Bulk gas and noble gas isotopic data are reported in seeps from three regions: 1) the Rukwa Rift Basin (RRB), 2) the Lupa Hydrothermal System (LHS) and 3) the Rungwe Volcanic Province (RVP). Seep gases from the RRB are dominantly comprised of N2 and He, with >90% N2 concentrations, high 4He concentrations (2.4–6.9%) and radiogenic He isotopes (0.16–0.20 RA). Seeps in the LHS - located between RRB and RVP - are characterized by little-to-no N2, high CO2 contents (72–84%), relatively low He contents (0.008–0.15%), and higher 3He/4He (0.95–0.99 RA). RVP gases have high CO2 (78%) and low 4He (0.0003%) and more mantle-like He isotopes (3.27–4.00 RA) consistent with previous findings ( Pik et al., 2006 ; Barry et al., 2013 ). All neon isotopes can be explained by mixing between air, high O/F crust and depleted Mid Oceanic Ridge Basalt (MORB) mantle-like signatures. RVP neon isotope seep data potentially suggest a solar-like deep mantle contribution, consistent with findings in rocks from the area ( Halldorsson et al., 2014 ), however we note that this signal is difficult to discern from mass dependent fractionation (MDF). The largest 40Ar/36Ar anomalies occur in RRB, with resolvable excess 40Ar derived from radiogenic production in the crust. Using a noble gas solubility model, we calculate volumetric gas to water ratios (Vg/Vw) and show that Vg/Vw values are low for RRB (0.1), consistent with longer migration distances, whereas Vg/Vw are higher for LHS (Vg/Vw = 0.1–10) and RVP (Vg/Vw = 3–12), suggesting a more direct conduit for volatiles from source to surface. In summary, these data demonstrate interaction between two distinct helium sources, one of which is crustal in origin (most prominent in RRB) and the other being mantle-derived (enriched in RVP). The extent of mixing between the two is shown to be influenced by proximity to rift-related fault structures, groundwater interaction and magmatic heat.

The migration of hydrocarbons from source-rock to reservoir is a critical stage in petroleum system evolution. However, as migration occurs along confined pathways over geologically rapid timescales it is challenging to place quantitative constraints on migration behaviour in terms of interaction with other basinal fluids, flux, and lengthscales associated with this process. Due to their inert nature, noble gases are ideal tracers of fluid provenance and physical processes in a variety of subsurface systems, and thus can serve as a potential geochemical indicator of migration distance. The recent proliferation of unconventional hydrocarbon production (i.e., production directly from source-rocks) allows for the analysis of fluids from these strata. Here we present noble gas data from natural gas samples produced from 27 related conventional and unconventional wells within the East Texas basin. These data enable characterisation of fluids during migration from source-rock to conventional reservoir. Unconventional gases and fluids are produced from the Haynesville shale (n = 8), and conventional gases and fluids are sourced from the overlying Cotton Valley (n = 5), Travis Peak (n = 9), and James Lime (n = 5) formations. Samples consist primarily of methane (>70%), with small contributions from longer-chain hydrocarbons, and other gases including CO2 and N2. Atmosphere-derived 36Ar, which is introduced into natural gas accumulations via interaction with groundwater during hydrocarbon generation and migration, is consistently higher in samples that have undergone a greater migration distance from the source interval. Thus, calculated volume ratios of gas-water interaction (Vg/Vw) show a far greater incidence of groundwater interaction in migrated samples. Radiogenically-produced 40Ar is also consistently elevated in migrated samples, despite these reservoirs being located in geologically younger strata. We derive the representative volume of rock required to produce the observed radiogenic 40Ar in each sample and show that samples that have migrated further have acquired radiogenic isotopes from larger volumes of rock. Furthermore, our volumetric parameters derived from atmospheric and radiogenic isotopes are consistent with a simple conceptual model of migration. We quantitatively apply this model to demonstrate that migration occurs along relatively localised pathways. Helium (3He/4He) and argon (40Ar/36Ar) isotopes are correlated and show elevated amounts of mantle-derived 3He and radiogenic 40Ar in migrated samples. We interpret this to represent mixing between a pristine source-rock signature and an endmember characterised by elevated 3He/4He and 40Ar/36Ar, likely representative of mantle-enriched groundwater circulating in the wider hydrogeological basin. Finally, we use an advection-diffusion model to show that enriched mantle 3He in the shallower strata and towards the southern edge of the basin can be explained by influx of mantle helium along the fault-bounded southern edge of the basin over timescales of millions of years. Together these approaches represent the first complete noble gas based characterization of a hydrocarbon system, sampling migration from source-rock to trap. We show conclusively that both atmospheric and radiogenic noble gases are entrained in the hydrocarbon phase during migration and that concentrations scale proportionally with migration distance, as greater volumes of groundwater and host rock are encountered.

Hydrocarbon systems with declining or viscous oil production are often stimulated using enhanced oil recovery (EOR) techniques, such as the injection of water, steam, and CO2, in order to increase oil and gas production. As EOR and other methods of enhancing production such as hydraulic fracturing have become more prevalent, environmental concerns about the impact of both new and historical hydrocarbon production on overlying shallow aquifers have increased. Noble gas isotopes are powerful tracers of subsurface fluid provenance and can be used to understand the impact of EOR on hydrocarbon systems and potentially overlying aquifers. In oil systems, produced fluids can consist of a mixture of oil, water and gas. Noble gases are typically measured in the gas phase; however, it is not always possible to collect gases and therefore produced fluids (which are water, oil, and gas mixtures) must be analyzed. We outline a new technique to separate and analyze noble gases in multiphase hydrocarbon-associated fluid samples. An offline double capillary method has been developed to quantitatively isolate noble gases into a transfer vessel, while effectively removing all water, oil, and less volatile hydrocarbons. The gases are then cleaned and analyzed using standard techniques. Air-saturated water reference materials (n = 24) were analyzed and results show a method reproducibility of 2.9% for 4He, 3.8% for 20Ne, 4.5% for 36Ar, 5.3% for 84Kr, and 5.7% for 132Xe. This new technique was used to measure the noble gas isotopic compositions in six produced fluid samples from the Fruitvale Oil Field, Bakersfield, California.

Carbon and other volatiles in the form of gases, fluids or mineral phases are transported from Earth's surface into the mantle at convergent margins, where the oceanic crust subducts beneath the continental crust. The efficiency of this transfer has profound implications for the nature and scale of geochemical heterogeneities in Earth's deep mantle and shallow crustal reservoirs, as well as Earth's oxidation state. However, the proportions of volatiles released from the forearc and backarc are not well constrained compared to fluxes from the volcanic arc front. Here we use helium and carbon isotope data from deeply sourced springs along two cross-arc transects to show that about 91 per cent of carbon released from the slab and mantle beneath the Costa Rican forearc is sequestered within the crust by calcite deposition. Around an additional three per cent is incorporated into the biomass through microbial chemolithoautotrophy, whereby microbes assimilate inorganic carbon into biomass. We estimate that between 1.2 × 108 and 1.3 × 1010 moles of carbon dioxide per year are released from the slab beneath the forearc, and thus up to about 19 per cent less carbon is being transferred into Earth's deep mantle than previously estimated.

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.

Significance Volatile elements play a critical role in the evolution of Earth. Nevertheless, the mechanism(s) by which Earth acquired, and was able to preserve its volatile budget throughout its violent accretionary history, remains uncertain. In this study, we analyzed noble gas isotopes in volcanic gases from the Yellowstone mantle plume, thought to sample the deep primordial mantle, to determine the origin of volatiles on Earth. We find that Kr and Xe isotopes within the deep mantle have a similar chondritic origin to those found previously in the upper mantle. This suggests that the Earth has retained chondritic volatiles throughout the accretion and, therefore, terrestrial volatiles cannot not solely be the result of late additions following the Moon-forming impact., Identifying the origin of noble gases in Earth’s mantle can provide crucial constraints on the source and timing of volatile (C, N, H2O, noble gases, etc.) delivery to Earth. It remains unclear whether the early Earth was able to directly capture and retain volatiles throughout accretion or whether it accreted anhydrously and subsequently acquired volatiles through later additions of chondritic material. Here, we report high-precision noble gas isotopic data from volcanic gases emanating from, in and around, the Yellowstone caldera (Wyoming, United States). We show that the He and Ne isotopic and elemental signatures of the Yellowstone gas requires an input from an undegassed mantle plume. Coupled with the distinct ratio of 129Xe to primordial Xe isotopes in Yellowstone compared with mid-ocean ridge basalt (MORB) samples, this confirms that the deep plume and shallow MORB mantles have remained distinct from one another for the majority of Earth’s history. Krypton and xenon isotopes in the Yellowstone mantle plume are found to be chondritic in origin, similar to the MORB source mantle. This is in contrast with the origin of neon in the mantle, which exhibits an isotopic dichotomy between solar plume and chondritic MORB mantle sources. The co-occurrence of solar and chondritic noble gases in the deep mantle is thought to reflect the heterogeneous nature of Earth’s volatile accretion during the lifetime of the protosolar nebula. It notably implies that the Earth was able to retain its chondritic volatiles since its earliest stages of accretion, and not only through late additions.

International audience; Nitrogen is the main constituent of the Earth's atmosphere, but its provenance in the Earth's mantle remains uncertain. The relative contribution of primordial nitrogen inherited during the Earth's accretion versus that subducted from the Earth's surface is unclear 1-6. Here we show that the mantle may have retained remnants of such primordial nitrogen. We use the rare 15 N 15 N isotopologue of N 2 as a new tracer of air contamination in volcanic gas effusions. By constraining air contamination in gases from Iceland, Eifel (Germany) and Yellowstone (USA), we derive estimates of mantle δ 15 N (the fractional difference in 15 N/ 14 N from air), N 2 / 36 Ar and N 2 / 3 He. Our results show that negative δ 15 N values observed in gases, previously regarded as indicating a mantle origin for nitrogen 7-10 , in fact represent dominantly air-derived N 2 that experienced 15 N/ 14 N fractionation in hydrothermal systems. Using two-component mixing models to correct for this effect, the 15 N 15 N data allow extrapolations that characterize mantle endmember δ 15 N, N 2 / 36 Ar and N 2 / 3 He values. We show that the Eifel region has slightly increased δ 15 N and N 2 / 36 Ar values relative to estimates for the convective mantle provided by mid-ocean-ridge basalts 11 , consistent with subducted nitrogen being added to the mantle source. In contrast, we find that whereas the Yellowstone plume has δ 15 N values substantially greater than that of the convective mantle, resembling surface components 12-15 , its N 2 / 36 Ar and N 2 / 3 He ratios are indistinguishable from those of the convective mantle. This observation raises the possibility that the plume hosts a primordial component. We provide a test of the subduction hypothesis with a two-box model, describing the evolution of mantle and surface nitrogen through geological time. We show that the effect of subduction on the deep nitrogen cycle may be less important than has been suggested by previous investigations. We propose instead that high mid-ocean-ridge basalt and plume δ 15 N values may both be dominantly primordial features. Differentiated bodies from our Solar System have rocky mantles with 15 N/ 14 N ratios within ±15‰ of modern terrestrial air 16,17. This is true for Earth's convective mantle, which has a δ 15 N value of approximately −5 ± 3‰, based on measurements from diamonds 5,18 and basalts that have been filtered for air contamination 3,11. Conversely, volatile-rich chondritic meteorites exhibit highly variable δ 15 N values between −20 ± 11‰ for enstatite chondrites and 48 ± 9‰ for CI carbonaceous chondrites 16,19. The distinct 15 N/ 14 N of rocky mantles relative to the chon-drites may reflect inheritance of N from a heterogeneous mixture of chondritic precursors 3. Alternatively, the relatively high 15 N/ 14 N values could be the result of evaporative losses 20 , or equilibrium partitioning of N isotopes between metal cores and rocky mantles 21,22. For Earth, plate tectonics allows for another interpretation 1. Geo-chemists have suggested that mantle δ 15 N values reflect subduction of nitrogen from the surface. Some of the evidence comes from studies of gases from mantle plumes. On Earth, mantle plumes with high 3 He/ 4 He ratios relative to mid-ocean-ridge basalts (MORBs) result from melting of relatively undegassed portions of the deep mantle 23. Nitrogen data are sparse, but plumes with both high and low 3 He/ 4 He values have δ 15 N values between 0 and +3‰ (refs. 2,4), higher than the values attributed to the convective mantle and similar to both sediments and altered oceanic crust (Extended Data Fig. 1) 12,13,15,24. One hypothesis is that the convective and deep mantle reservoirs both initially had identical but low enstatite chondrite-like δ 15 N values 6. Over geological time, these

The recent proliferation of tight or unconventional petroleum bearing reservoirs as an energy resource enables a more detailed investigation of the geochemical behaviour of these systems. In addition, it provides an opportunity to improve our understanding of low-permeability crustal fluid systems at depth. Organic-rich shales are not only the source-rocks in conventional petroleum systems, but potential seals, which may be important for the trapping and storage of CO2 and/or nuclear waste. The use of noble gas isotopes as tracers of fluid provenance and physical exchange processes is well established in other crustal fluid systems. Noble gas concentrations and isotopic characteristics were determined in 10 natural gas samples produced from the Eagle Ford shale, Texas, along with the concentration and δ13C and δD of hydrocarbon gases. By sampling gases produced directly from unconventional reservoirs we are able to determine their residence time and the extent of interaction of these fluids with other fluids in the wider hydrogeological system. The large range in thermal maturity exhibited across the basin, as demonstrated by the range in δ13C of methane from −37.8 to −47.5‰ VPDB, allows us to constrain the evolution of the noble gas signature within a source-rock during hydrocarbon generation and expulsion. For the first time, we show that 36Ar concentrations in hydrocarbon gases are not simply controlled by solubility exchange with formation water. Instead, they are shown to decrease dramatically (from 2.6 × 10−7 to 7.0 × 10−9 cm3STPcm−3) with increasing thermal maturity, which we attribute to a dilution effect as more short-chain hydrocarbon compounds are generated through cracking of kerogen and secondary cracking of oil. We develop a model that combines 36Ar concentrations with δ13C data in order to quantify the retention capacity for generated hydrocarbons, and show that between 40 and 80% of the hydrocarbons generated by the Eagle Ford shale are retained within the formation. We also calculate that radiogenic 4He concentrations within the Eagle Ford are well in excess of that which could have accumulated internally since deposition and requires contributions from external 4He sources. The identification of both hydrocarbon expulsion and helium addition to nominally ‘tight’ formations now provides a process driven and quantitative understanding of the fluid migration dynamics and processes controlling these critical formations.

Volatiles, such as carbon and noble gases, are continuously degassed from Earth's mantle and crust to Earth's surface in continental rifting systems. Here, we present He-Ne-Ar abundances and isotopes as well as major gas chemistry (CO2, He, Ar and CH4) data for (n = 13) naturally-degassing seeps in the Rungwe Volcanic Province (RVP) of the East African Rift System (EARS) in southwestern Tanzania, Africa. Helium isotopes (3He/4He) suggest that trace gases are derived from mantle sources, with moderate crustal additions, in agreement with previous studies from RVP (e.g., Pik et al., 2006; Barry et al., 2013). Samples broadly fall into two groups: 1) dominantly mantle-like, with 3He/4He ranging from 5.2–6.3RA, which can be explained by release of magmatic volatiles, and 2) those with slightly lower 3He/4He (3.0–4.1RA), representing more 4He (i.e., crustal) additions. Furthermore, we report the first Ne and Ar isotopes from RVP, which show 20Ne/22Ne from 9.67–10.0 and 40Ar/36Ar from 301.2–412.2, respectively, which are broadly air-like. We employ a solubility degassing model to show that elemental ratios (4He/40Ar*, CO2/40Ar* and CO2/3He) in the gases can be explained by variable extents of open and closed system degassing from a melt with an initial mantle-like composition. However, we note that CO2/3He observations require additional carbon assimilation, likely derived from the thick nearby cratonic crust.

In regions where water resources are scarce and in high demand, it is important to safeguard against contamination of groundwater aquifers by oil-field fluids (water, gas, oil). In this context, the geochemical characterisation of these fluids is critical so that anthropogenic contaminants can be readily identified. The first step is characterising pre-development geochemical fluid signatures (i.e., those unmodified by hydrocarbon resource development) and understanding how these signatures may have been perturbed by resource production, particularly in the context of enhanced oil recovery (EOR) techniques. Here, we present noble gas isotope data in fluids produced from oil wells in several water-stressed regions in California, USA, where EOR is prevalent. In oil-field systems, only casing gases are typically collected and measured for their noble gas compositions, even when oil and/or water phases are present, due to the relative ease of gas analyses. However, this approach relies on a number of assumptions (e.g., equilibrium between phases, water-to-oil ratio (WOR) and gas-to-oil ratio (GOR) in order to reconstruct the multiphase subsurface compositions. Here, we adopt a novel, more rigorous approach, and measure noble gases in both casing gas and produced fluid (oil-water-gas mixtures) samples from the Lost Hills, Fruitvale, North and South Belridge (San Joaquin Basin, SJB) and Orcutt (Santa Maria Basin) Oil Fields. Using this method, we are able to fully characterise the distribution of noble gases within a multiphase hydrocarbon system. We find that measured concentrations in the casing gases agree with those in the gas phase in the produced fluids and thus the two sample types can be used essentially interchangeably. EOR signatures can readily be identified by their distinct air-derived noble gas elemental ratios (e.g., 20Ne/36Ar), which are elevated compared to pre-development oil-field fluids, and conspicuously trend towards air values with respect to elemental ratios and overall concentrations. We reconstruct reservoir 20Ne/36Ar values using both casing gas and produced fluids and show that noble gas ratios in the reservoir are strongly correlated (r2 = 0.88–0.98) to the amount of water injected within ~500 m of a well. We suggest that the 20Ne/36Ar increase resulting from injection is sensitive to the volume of fluid interacting with the injectate, the effective water-to-oil ratio, and the composition of the injectate. Defining both the pre-development and injection-modified hydrocarbon reservoir compositions are crucial for distinguishing the sources of hydrocarbons observed in proximal groundwaters, and for quantifying the transport mechanisms controlling this occurrence.

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.

The transport of helium from the crystalline continental basement and overlying Phanerozoic sedimentary formations to the near surface can be controlled by both diffusive and advective processes. The relative role of each is vital to helium resource prediction, and important in quantifying the residence times of fluids relevant to groundwater resources, hydrocarbon systems, geologic repositories for nuclear waste and carbon sequestration. The Williston Basin, North America, is a prominent sedimentary basin, providing an excellent natural laboratory to assess these processes. Here, we report noble gas isotopic and composition data for 28 gas samples from natural gas wells that sample different stratigraphic horizons down to the basement (Cretaceous to the Cambrian). Helium isotope ratios show a resolvable mantle 3He component (up to 4.7%) in most samples. Neon isotopic compositions of the Cambrian samples are consistent with a crystalline basement gas contribution. Both helium and neon isotopic observations provide evidence for the contribution of conservative noble gases from the crystalline basement or deeper into the overlying sedimentary basin. 4He groundwater concentrations in the sedimentary formations, calculated from 4He/20Ne values in gas samples, are in excess of in situ U+Th 4He production in some shallow units and depleted in others, providing further evidence of cross formation gas contributions. The highest 4He groundwater concentrations can be compared with the results obtained from a fully-coupled vertical scale transport model characterising diffusive-dominated transport through a static groundwater column. The model includes the 4He flux into the basin from the Precambrian basement and quantifies the apparent basement 4He flux to be between 0.8 - 1.6 × 10 − 6 mol 4He/m2 yr, comparable to the steady-state flux estimated for the average continental crust (1.47 × 10 − 6 mol 4He/m2 yr) ( Torgersen, 2010 ). The lithologies in which 4He concentrations are significantly lower than the reference model predictions are consistent with a history of water flooding and produced water disposal in those formations over decades of hydrocarbon production. While an advective component cannot be ruled out, this work demonstrates the importance of both diffusion and the basin architecture development in controlling 4He flux into and out of different lithologies. The assumption of negligible 4He loss from the top surface of a lithology is often made when determining the 4He age of its groundwater. In the Williston Basin, this study shows that deeper lithologies may reach steady state at different stages of basin development, with shallower lithologies sometimes also showing significant 4He loss from their top surface. In the Williston Basin, 4He diffusive loss from the target lithology must be considered to accurately interpret 4He groundwater residence times and accumulation potential.

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 (

How much nitrogen and light noble gases are recycled in modern subduction zones is unclear. Fumaroles act as a means for passive degassing in arcs. They receive variable contributions of volatiles from arc magmas, themselves sourced from the mantle wedge. The gas compositions reflect the extent of volatile enrichment in sub-arc mantle sources and constrain slab dehydration. However, contributions from atmospheric components in fumaroles are unavoidable. For N2, neon and argon, the atmospheric components are challenging to discern from slab-derived components. Here, we report 15N15N measurements from eight fumaroles and seven bubbling springs, along the Central American arc. Our new 15N15N data are coupled with noble gases measurements and show that air-derived components in volcanic gas discharges can easily be underestimated, in both fumaroles and springs, using conventional stable isotope or noble gases methods. We show that, in the absence of 15N15N data, previously used tracers for air (e.g., δ 15 N, N2/Ar, N2/He, among others) may lead to erroneous conclusions regarding the origin of volatiles in mixed gases. In contrast, 15N15N data provide quantitative constraints on the nature and contributions of both atmospheric and magmatic components. Most springs are heavily dominated by air-derived N2, while fumaroles show substantial contributions of volcanic endmembers. Based on the fumarole data, we show that magma sources beneath the central American arc are enriched in all volatiles relative to 3He, by two to three orders of magnitude compared to the MORB source. We use new 15N15N data to obtain source N2/3He, 3He/36Ar and 3He/22Ne ratios which we then use to compute volcanic N2, Ar and Ne degassing fluxes. Using this approach, we show that outgassing fluxes appear to match subduction fluxes in the Central America subduction zone. We determine an N2 outgassing flux of between 4.0 × 10 8 and 1.0 × 10 9 mol N2/y, comparable to the subduction flux of 5.7 × 10 8 mol N2/yr determined previously. We obtain a similar conclusion for 22Ne and 36Ar. Overall, the volatile fluxes in the central American subduction zone no longer seem to require net transfer of N2, Ar, and Ne, to the deep mantle.

Deep carbon emissions from historically inactive volcanoes, hydrothermal, and tectonic structures are among the greatest unknowns in the long-term (∼Myr) carbon cycle. Recent estimates of diffuse CO2 flux from the Eastern Rift of the East African Rift System (EARS) suggest this could equal emissions from the entire mid-ocean ridge system. We report new CO2 surveys from the Main Ethiopian Rift (MER, northernmost EARS), and reassess the rift-related CO2 flux. Since degassing in the MER is concentrated in discrete areas of volcanic and off-edifice activity, characterization of such areas is important for extrapolation to a rift-scale budget. Locations of hot springs and fumaroles along the rift show numerous geothermal areas away from volcanic edifices. With these new data, we estimate total CO2 emissions from the central and northern MER as 0.52–4.36 Mt yr−1. Our extrapolated flux from the Eastern Rift is 3.9–32.7 Mt yr−1 CO2, overlapping with lower end of the range presented in recent estimates. By scaling, we suggest that 6–18 Mt yr−1 CO2 flux can be accounted for by magmatic extension, which implies an important role for volatile-enriched lithosphere, crustal assimilation, and/or additional magmatic intrusion to account for the upper range of flux estimates. Our results also have implications for the nature of volcanism in the MER. Many geothermal areas are found >10 km from the nearest volcanic center, suggesting ongoing hazards associated with regional volcanism.

An innovative collaboration is investigating how geobiological processes alter fluxes of carbon and other materials between the deep Earth and the surface.

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

Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range = 0.010-0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p < 0.001, ρ = 0.90, range = 145-15,900 mg/L), Mn + Fe concentrations (p < 0.001, ρ = 0.82, range =

The Yangtze craton (YC), in eastern China, is one of the oldest cratons in the world and is characterized by a complex tectonic and geodynamic evolution. This evolution regards most of the eastern China craton, which since Mesozoic time has undergone significant thinning (> 200 km) of Archean lithosphere. This thinning favored the refertilization of the old refractory subcontinental lithospheric mantle (SCLM) by the upwelling of younger fertile asthenosphere. Whether this feature is localized only beneath certain areas of eastern China or is a more widespread characteristic of the mantle, including the YC, is a matter of debate. In order to constrain the history of the YC SCLM, we have measured the He- and Ar-isotopic compositions of fluid inclusions hosted in mantle xenoliths in the Lianshan area, which is part of the poorly investigated YC in south-east China. We also report new mineral chemistry and trace element compositions of clinopyroxenes from the same suite of samples, for comparison with noble gases. Two distinct types of xenoliths can be identified: Type 1, characterized by mantle-like He-isotopic (3He/4He) ratios (up to 9.1 Ra), represents fragments of a fertile lithospheric mantle; Type 2, showing 3He/4He values in the SCLM range (3He/4He < 7 Ra), represents shallow relicts of a refractory mantle. The patterns of rare-earth elements as well as the Y and Yb concentrations in the clinopyroxenes normalized to primitive mantle (YN and YbN, respectively) indicate that fractional partial melting might have affected the local mantle by < 3% in Type 1 and up to 20% in Type 2 xenoliths from Lianshan, respectively. The range of 4He/40Ar* (40Ar* is corrected for atmospheric contamination) ranges from 4.9 × 10− 4 to 3.6 × 10− 1, which is below the typical production ratio of the mantle (4He/40Ar* = 1–5); this range is however compatible with this fractional partial melting. The variable 3He/4He and 4He/40Ar* values in Lianshan xenoliths suggest that the local mantle source was also influenced by kinetic fractionation, possibly triggered by metasomatic melts. Metasomatism associated with carbonatitic melts, together with fluxing by CO2-rich fluids, have permeated the mantle beneath Lianshan, generating the observed decoupling between noble gases and trace elements. The interpretative framework is also applicable for other mantle xenoliths from eastern China, indicating that the refertilization of the SCLM by ascending mantle-like melts is common also to YC, which can be identified using noble gases.

Geothermal systems are complex environments where geochemical signatures are controlled by the influx of deep mantle fluids as well as near-surface processes that result from the high temperatures. Noble gas isotope ratios (e.g. 3He/4He, 20Ne/22Ne) are well-established tracers of deep mantle fluid provenance, and elemental fractionation of atmosphere-derived isotopes is widely used for tracing shallow processes such as solubility-dependent phase partitioning in groundwater and hydrocarbon fluids. Utilisation of these tracers for the latter purpose has been limited in geothermal systems, where they could be further extended to consider boiling and/or steam condensation. Here we report new noble gas isotope and abundance data for 21 vapour phase geothermal fluid samples collected from geothermal boreholes and naturally degassing fumaroles in Iceland. The samples were collected from active parts of the neovolcanic rift zone and include several key high-temperature geothermal localities of the Northern Rift Zone (NRZ), the Western Rift Zone (WRZ) and the Mid-Iceland Belt (MIB). Helium isotope ratios are MORB-like in the NRZ, whilst samples from the WRZ show values in excess of MORB, up to 15.9 Ra. Neon isotopes plot close to the air value, but may show a small plume mantle contribution. Argon isotopes show distinct mantle-derived 40Ar excesses (40Ar/36Ar up to 361.2), which to our knowledge are the largest measured anomalies in free geothermal fluids from Iceland. The atmosphere-derived noble gas signatures (20Ne, 36Ar, 84Kr) are consistent with high-temperature vapour-liquid phase partitioning. Atmosphere-derived xenon (130Xe) on the other hand is not consistent with the observations from the other atmosphere-derived noble gases, suggesting an additional complexity that likely relates to its unique sorption and bonding behaviour. We show that the abundance of 20Ne, 36Ar, 84Kr in the vapour phase is temperature-dependent, presenting a promising technique that can be used to estimate the temperature at which partitioning occurs in the subsurface. Using multiple noble gas species allows the effects of secondary atmospheric contamination to be corrected when using this method. We predict partitioning temperatures of 229 to 345 °C for the samples measured here, consistent with temperatures predicted using conventional geothermometers. The inert nature of the noble gases means that the technique presented here is not reliant on many of the assumptions that underpin conventional geothermometers. We suggest that this technique represents a novel and powerful geochemical tool to investigate the thermal properties of geothermal systems.

The Siberian flood basalts (SFB) erupted at the end of the Permian period (∼250 Ma) in response to a deep-rooted mantle plume beneath the Siberian Sub-Continental Lithospheric Mantle (SCLM). Plume-lithosphere interaction can lead to significant changes in the structure and chemistry of the SCLM and trigger the release of metasomatic material that was previously stored within the stable craton. Here, we investigate the nature of the Siberian-SCLM (S-SCLM) by measuring nitrogen abundances and isotopes ( δ 15 N) in 11 samples of two petrologically-distinct suites of peridotitic xenoliths recovered from kimberlites which bracket the eruption of the SFB: the 360 Myr old Udachnaya and 160 Myr old Obnazhennaya pipes. Nitrogen isotope ( δ 15 N) values range from -5.85 ± 1.29‰ to +3.94 ± 0.63‰, which encompasses the entire range between depleted Mid-Ocean Ridge Basalt (MORB) mantle (DMM; -5 ± 2‰) and plume-derived (+3 ± 2‰) endmembers. In addition, we present neon (n=7) and argon (n=8) abundance and isotope results for the same two suites of samples. The 20Ne/22Ne and 21Ne/22Ne range from atmospheric-like values of 9.88 up to 11.35 and from 0.0303 to 0.0385, respectively, suggesting an admixture of DMM and plume-derived components. Argon isotopes (40Ar/36Ar) range from 336.7 to 1122 and correlate positively with 40Ar contents. We show that volatile systematics of Siberian xenoliths: (1) exhibit evidence of ancient metasomatic and/or recycled signatures, and (2) show evidence of subsequent plume-like re-fertilization, which we attribute to the emplacement of the SFB. Metasomatic fluids are highly enriched in radiogenic gases and have elevated Br/Cl and I/Cl values, consistent with an ancient subducted crustal component. The metasomatic component is marked by light N isotope signatures, suggesting it may be derived from an anoxic Archean subducted source. Taken together, these N2-Ne-Ar isotope results suggest that mantle plume impingement has profoundly modified the S-SCLM, and that N, Ne and Ar isotopes are sensitive tracers of metasomatism in the S-SCLM. Metasomatic fluids that permeate the S-SCLM act to archive a “subduction-fingerprint” that can be used to probe relative volatile-element recycling efficiencies and thus provide insight into volatile transport between the surface and mantle reservoirs over Earth history.