Ultrahigh-precision noble gas isotope analyses reveal pervasive subsurface fractionation in hydrothermal systems.

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.

Origin of life-forming volatile elements in the inner Solar System.

Volatile elements such as hydrogen, carbon, nitrogen and oxygen are essential ingredients to build habitable worlds like Earth, but their origin and evolution on terrestrial planets remain highly debated. Here we discuss the processes that distributed these elements throughout the early Solar System and how they then became incorporated into planetary building blocks. Volatiles on Earth and the other terrestrial planets appear to have been heterogeneously sourced from different Solar System reservoirs. The sources of planetary volatiles and the timing at which they were accreted to growing planets probably play a crucial role in controlling planet habitability.

High 3He/4He in central Panama reveals a distal connection to the Galápagos plume.

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.

Fossil records of early solar irradiation and cosmolocation of the CAI factory: A reappraisal.

Calcium-aluminum­rich inclusions (CAIs) in meteorites carry crucial information about the environmental conditions of the nascent Solar System prior to planet formation. Based on models of 50V­10Be co-production by in-situ irradiation, CAIs are considered to have formed within ~0.1 AU from the proto-Sun. Here, we present vanadium (V) and strontium (Sr) isotopic co-variations in fine- and coarse-grained CAIs and demonstrate that kinetic isotope effects during partial condensation and evaporation best explain V isotope anomalies previously attributed to solar particle irradiation. We also report initial excesses of 10Be and argue that CV CAIs possess essentially a homogeneous level of 10Be, inherited during their formation. Based on numerical modeling of 50V­10Be co-production by irradiation, we show that CAI formation during protoplanetary disk build-up likely occurred at greater heliocentric distances than previously considered, up to planet-forming regions (~1AU), where solar particle fluxes were sufficiently low to avoid substantial in-situ irradiation of CAIs.

Groundwater residence time estimates obscured by anthropogenic carbonate.

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.

Isotopic evidence for the formation of the Moon in a canonical giant impact.

Isotopic measurements of lunar and terrestrial rocks have revealed that, unlike any other body in the solar system, the Moon is indistinguishable from the Earth for nearly every isotopic system. This observation, however, contradicts predictions by the standard model for the origin of the Moon, the canonical giant impact. Here we show that the vanadium isotopic composition of the Moon is offset from that of the bulk silicate Earth by 0.18 ± 0.04 parts per thousand towards the chondritic value. This offset most likely results from isotope fractionation on proto-Earth during the main stage of terrestrial core formation (pre-giant impact), followed by a canonical giant impact where ~80% of the Moon originates from the impactor of chondritic composition. Our data refute the possibility of post-giant impact equilibration between the Earth and Moon, and implies that the impactor and proto-Earth mainly accreted from a common isotopic reservoir in the inner solar system.

Identification of chondritic krypton and xenon in Yellowstone gases and the timing of terrestrial volatile accretion.

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.

The origin and fate of volatile elements on Earth revisited in light of noble gas data obtained from comet 67P/Churyumov-Gerasimenko.

The origin of terrestrial volatiles remains one of the most puzzling questions in planetary sciences. The timing and composition of chondritic and cometary deliveries to Earth has remained enigmatic due to the paucity of reliable measurements of cometary material. This work uses recently measured volatile elemental ratios and noble gas isotope data from comet 67P/Churyumov-Gerasimenko (67P/C-G), in combination with chondritic data from the literature, to reconstruct the composition of Earth's ancient atmosphere. Comets are found to have contributed ~20% of atmospheric heavy noble gases (i.e., Kr and Xe) but limited amounts of other volatile elements (water, halogens and likely organic materials) to Earth. These cometary noble gases were likely mixed with chondritic - and not solar - sources to form the atmosphere. We show that an ancient atmosphere composed of chondritic and cometary volatiles is more enriched in Xe relative to the modern atmosphere, requiring that 8-12 times the present-day inventory of Xe was lost to space. This potentially resolves the long-standing mystery of Earth's "missing xenon", with regards to both Xe elemental depletion and isotopic fractionation in the atmosphere. The inferred Kr/H2O and Xe/H2O of the initial atmosphere suggest that Earth's surface volatiles might not have been fully delivered by the late accretion of volatile-rich carbonaceous chondrites. Instead, "dry" materials akin to enstatite chondrites potentially constituted a significant source of chondritic volatiles now residing on the Earth's surface. We outline the working hypotheses, implications and limitations of this model in the last section of this contribution.

Geochemical evidence for high volatile fluxes from the mantle at the end of the Archaean.

The exchange of volatile species-water, carbon dioxide, nitrogen and halogens-between the mantle and the surface of the Earth has been a key driver of environmental changes throughout Earth's history. Degassing of the mantle requires partial melting and is therefore linked to mantle convection, whose regime and vigour in the Earth's distant past remain poorly constrained1,2. Here we present direct geochemical constraints on the flux of volatiles from the mantle. Atmospheric xenon has a monoisotopic excess of 129Xe, produced by the decay of extinct 129I. This excess was mainly acquired during Earth's formation and early evolution3, but mantle degassing has also contributed 129Xe to the atmosphere through geological time. Atmospheric xenon trapped in samples from the Archaean eon shows a slight depletion of 129Xe relative to the modern composition4,5, which tends to disappear in more recent samples5,6. To reconcile this deficit in the Archaean atmosphere by mantle degassing would require the degassing rate of Earth at the end of the Archaean to be at least one order of magnitude higher than today. We demonstrate that such an intense activity could not have occurred within a plate tectonics regime. The most likely scenario is a relatively short (about 300 million years) burst of mantle activity at the end of the Archaean (around 2.5 billion years ago). This lends credence to models advocating a magmatic origin for drastic environmental changes during the Neoarchaean era, such as the Great Oxidation Event.

Primordial heavy noble gases in the pristine Paris carbonaceous chondrite.

The Paris carbonaceous chondrite represents the most pristine carbonaceous chondrite, providing a unique opportunity to investigate the composition of early solar system materials prior to the onset of significant aqueous alteration. A dual origin (namely from the inner and outer solar system) has been demonstrated for water in the Paris meteorite parent body (Piani et al. 2018). Here, we aim to evaluate the contribution of outer solar system (cometary-like) water ice to the inner solar system water ice using Xe isotopes. We report Ar, Kr, and high-precision Xe isotopic measurements within bulk CM 2.9 and CM 2.7 fragments, as well as Ne, Ar, Kr, and Xe isotope compositions of the insoluble organic matter (IOM). Noble gas signatures are similar to chondritic phase Q with no evidence for a cometary-like Xe component. Small excesses in the heavy Xe isotopes relative to phase Q within bulk samples are attributed to contributions from presolar materials. CM 2.7 fragments have lower Ar/Xe relative to more pristine CM 2.9 fragments, with no systematic difference in Xe contents. We conclude that Kr and Xe were little affected by aqueous alteration, in agreement with (1) minor degrees of alteration and (2) no significant differences in the chemical signature of organic matter in CM 2.7 and CM 2.9 areas (Vinogradoff et al. 2017). Xenon contents in the IOM are larger than previously published data of Xe in chondritic IOM, in line with the Xe component in Paris being pristine and preserved from Xe loss during aqueous alteration/thermal metamorphism.

Origin and significance of cosmogenic signatures in vesicles of lunar basalt 15016.

Lunar basalt 15016 (~3.3 Ga) is among the most vesicular (50% by volume) basalts recovered by the Apollo missions. We investigated the possible occurrence of indigenous lunar nitrogen and noble gases trapped in vesicles within basalt 15016, by crushing several cm-sized chips. Matrix/mineral gases were also extracted from crush residues by fusion with a CO 2 laser. No magmatic/primordial component could be identified; all isotope compositions, including those of vesicles, pointed to a cosmogenic origin. We found that vesicles contained ~0.2%, ~0.02%, ~0.002%, and ~0.02% of the total amount of cosmogenic 21Ne, 38Ar, 83Kr, and 126Xe, respectively, produced over the basalt's 300 Myr of exposure. Diffusion/recoil of cosmogenic isotopes from the basaltic matrix/minerals to intergrain joints and vesicles is discussed. The enhanced proportion of cosmogenic Xe isotopes relative to Kr detected in vesicles could be the result of kinetic fractionation, through which preferential retention of Xe isotopes over Kr within vesicles might have occurred during diffusion from the vesicle volume to the outer space through microleaks. This study suggests that cosmogenic loss, known to be significant for 3He and 21Ne, and to a lesser extent for 36Ar (Signer et al. 1977), also occurs to a negligible extent for the heaviest noble gases Kr and Xe.

Archean kerogen as a new tracer of atmospheric evolution: Implications for dating the widespread nature of early life.

Understanding the composition of the Archean atmosphere is vital for unraveling the origin of volatiles and the environmental conditions that led to the development of life. The isotopic composition of xenon in the Archean atmosphere has evolved through time by mass-dependent fractionation from a precursor comprising cometary and solar/chondritic contributions (referred to as U-Xe). Evaluating the composition of the Archean atmosphere is challenging because limited amounts of atmospheric gas are trapped within minerals during their formation. We show that organic matter, known to be efficient at preserving large quantities of noble gases, can be used as a new archive of atmospheric noble gases. Xe isotopes in a kerogen isolated from the 3.0-billion-year-old Farrel Quartzite (Pilbara Craton, Western Australia) are mass fractionated by 9.8 ± 2.1 per mil (‰) (2σ) per atomic mass unit, in line with a progressive evolution toward modern atmospheric values. Archean atmospheric Xe signatures in kerogens open a new avenue for following the evolution of atmospheric composition through time. The degree of mass fractionation of Xe isotopes relative to the modern atmosphere can provide a time stamp for dating Archean kerogens and therefore narrowing the time window for the diversification of early life during the Archean eon.