Atmospheric Noble Gases Research Articles

Multidiffusion mechanisms for noble gases (He, Ne, Ar) in silicate glasses and melts in the transition temperature domain: Implications for glass polymerization

Noble gases are ideal probes to study the structure of silicate glasses and melts as the modifications of the silicate network induced by the incorporation of noble gases are negligible. In addition, there are systematic variations in noble gas atomic radii and several noble gas isotopes with which the influence of the network itself on diffusion may be investigated. Noble gases are therefore ideally suited to constrain the time scales of magma degassing and cooling. In order to document noble gas diffusion behavior in silicate glass, we measured the diffusivities of three noble gases (4He, 20Ne and 40Ar) and the isotopic diffusivities of two Ar isotopes (36Ar and 40Ar) in two synthetic basaltic glasses (G1 and G2; 20Ne and 36Ar were only measured in sample G1). These new diffusion results are used to re-interpret time scales of the acquisition of fractionated atmospheric noble gas signatures in pumices.The noble gas bearing glasses were synthesized by exposing the liquids to high noble gas partial pressures at high temperature and pressure (1750–1770K and 1.2GPa) in a piston-cylinder apparatus. Diffusivities were measured by step heating the glasses between 423 and 1198K and measuring the fraction of gas released at each temperature step by noble gas mass spectrometry. In addition we measured the viscosity of G1 between 996 and 1072K in order to determine the precise glass transition temperature and to estimate network relaxation time scales. The results indicate that, to a first order, that the smaller the size of the diffusing atom, the greater its diffusivity at a given temperature: D(He)>D(Ne)>D(Ar) at constant T. Significantly, the diffusivities of the noble gases in the glasses investigated do not display simple Arrhenian behavior: there are well-defined departures from Arrhenian behavior which occur at lower temperatures for He than for Ne or Ar. We propose that the non-Arrhenian behavior of noble gases can be explained by structural modifications of the silicate network itself as the glass transition temperature is approached: as the available free volume (available site for diffusive jumps) is modified, noble gas diffusion is no longer solely temperature-activated but also becomes sensitive to the kinetics of network rearrangements. The non-Arrhenian behavior of noble gas diffusion close to Tg is well described by a modified Vogel–Tammann–Fulcher (VTF) equation:Da2=A1a2∗exp-B1R(T-T2)-CRTwhere D is the diffusion coefficient, a the diffusion domain size (taken to be the size of the sample), A1 and C are respectively equivalent to the pre-exponential factor and to the activation energy (Ea in Jmol−1) of the classical Arrhenius equation, B1 can be interpreted as a “pseudo-activation energy” that reflects the influence of the silicate network relaxation, T2 is the temperature where the diffusion regime switches from Arrhenian to non-Arrhenian, and R is the gas constant (=8.314JK−1mol−1).Finally, our step heating diffusion experiments suggest that at T close to Tg, noble gas isotopes may suffer kinetic fractionation at a degree larger than that predicted by Graham’s law. In the case of 40Ar and 36Ar, the traditional assumption based on Graham’s law is that the ratio D40Ar/D36Ar should be equal to 0.95 (the square root of the ratio of the mass of 36Ar over the mass of 40Ar). In our experiment with glass G1, D40Ar/D36Ar rapidly decreased with decreasing temperature, from near unity (0.98±0.14) at T>1040K to 0.76 when close to Tg (T=1003K). Replicate experiments are needed to confirm the strong kinetic fractionation of heavy noble gases close to the transition temperature.

Atmospheric contamination of the primary Ne and Ar signal in mid-ocean ridge basalts and its implications for ocean crust formation

Both, terrestrial and extra-terrestrial applications of noble gases have demonstrated their importance as tracers for source identification, process characterisation and mass and heat flux quantification. However, the interpretation of noble gas isotope data from terrestrial igneous rocks is often complicated by the ubiquitous presence of heavy noble gases (Ne, Ar, Kr, Xe) with an atmospheric origin. Up to now there has been no consensus on how atmospheric noble gases are entrained into igneous rocks. Suggested processes range from contamination during sample preparation to mantle recycling through subduction. Here we present Ne, Ar, Mg, K, and Cl data of fresh glasses from the Mid-Atlantic Ridge north and south of the Ascension Fracture Zone which show that incorporation of atmospheric noble gases into igneous rocks is in general a two-step process: (1) magma contamination by assimilation of altered oceanic crust results in the entrainment of noble gases from air-equilibrated seawater; (2) atmospheric noble gases are adsorbed onto grain surfaces during sample preparation. This implies, considering the ubiquitous presence of the contamination signal, that magma contamination by assimilation of a seawater-sourced component is an integral part of mid-ocean ridge basalt evolution. Combining the results obtained from noble gas and Cl/K data with estimates of crystallisation pressures for the sample suite shows that the magma contamination must have taken place at a depth between 9 and 13km. Taking thickness estimates for the local oceanic crust into account, this implies that seawater penetration in this area reaches lower crustal levels, indicating that hydrothermal circulation might be an effective cooling mechanism even for the deep parts of the oceanic crust.

Ultralight Oxygen in Corundum-Bearing Rocks of North Karelia, Russia, as a Result of Isotope Separation by Thermal Diffusion (Soret Effect) in Endogenous Fluid Flow

Helium and argon isotopes in fluid inclusions in minerals of corundum bearing rocks with anomalous light oxygen of the Khitoostrov (North Karelia, Russia) were studied. It was found that atmospheric noble gas component is missing. Therefore, all previously proposed models of participation in the fluid surface ice meltwater are not valid. Proposed and justified endogenous mechanism of isotope fractionation of oxygen and other chemical elements by the mechanism of thermal diffusion. Geologically justified existence of the cascading effect for a number of the separation thermodiffusion cells, which lead to significant isotope effects. Cascading is realized due to the “fluid pump”, in which role are acting amphibolized gabbro in the contact with corundum metasomatites. It is assumed that the mechanism is not specific for the case corundum metasomatic rocks, which are a special case of manifestation of such a scenario in processes involving endogenous fluid flows.

Noble gases in the sediments of Lake Van – solute transport and palaeoenvironmental reconstruction

Sediment samples acquired in 2010 from the long cores of the International Continental Scientific Drilling Program (ICDP) PaleoVan drilling project on Lake Van for noble-gas analysis in the pore water allow determination of the local terrestrial He-gradient as a function of depth within a sediment column of more than 200 m. These measurements yield first insights into the physical transport mechanisms of terrigenic He through the uppermost part of unconsolidated lacustrine sediments overlying the continental crust.In line with our previous work on the spatial distribution of the terrigenic He release into Lake Van, we identify a high He concentration gradient in the uppermost 10 m of the sediment column. The He concentration gradient decreases below this depth down to approx. 160m following in general the expectations of the modelling of radiogenic He production and transport in a sediment column with homogeneous fluid transport properties. Overall the in-situ radiogenic He production due to the decay of U and Th in the mineral phases of the sediments accounts for about 80% of the He accumulation. At approx. 190m we observe a very high He concentration immediately below a large lithological unit characterised by strong deformations. We speculate that this local enrichment is the result of the lower effective diffusivities in the pore space that relate to the abrupt depositional history of this deformed unit. This particular lithological unit seems to act as a barrier that limits the transport of solutes in the pore space and hence might “trap” information on the past geochemical conditions in the pore water of Lake Van.The dissolved concentrations of atmospheric noble gases in the pore waters of the ICDP PaleoVan cores are used to geochemically reconstruct salinity on the time scale of 0–55 ka BP. Higher salinities in the pore water at a depth of about 20 m suggest a significantly lower lake level of Lake Van in the past.

Determination of natural in vivo noble-gas concentrations in human blood.

Although the naturally occurring atmospheric noble gases He, Ne, Ar, Kr, and Xe possess great potential as tracers for studying gas exchange in living beings, no direct analytical technique exists for simultaneously determining the absolute concentrations of these noble gases in body fluids in vivo. In this study, using human blood as an example, the absolute concentrations of all stable atmospheric noble gases were measured simultaneously by combining and adapting two analytical methods recently developed for geochemical research purposes. The partition coefficients determined between blood and air, and between blood plasma and red blood cells, agree with values from the literature. While the noble-gas concentrations in the plasma agree rather well with the expected solubility equilibrium concentrations for air-saturated water, the red blood cells are characterized by a distinct supersaturation pattern, in which the gas excess increases in proportion to the atomic mass of the noble-gas species, indicating adsorption on to the red blood cells. This study shows that the absolute concentrations of noble gases in body fluids can be easily measured using geochemical techniques that rely only on standard materials and equipment, and for which the underlying concepts are already well established in the field of noble-gas geochemistry.

Noble gases (Ar, Kr, Xe) and halogens (Cl, Br, I) in fluid inclusions from the Athabasca Basin (Canada): Implications for unconformity-related U deposits

The formation of unconformity-related uranium deposits in the Proterozoic Athabasca Basin (Canada) involved basin-scale circulation of U-bearing brines during high-grade diagenesis (150–200°C) at ∼1.6–1.5Ga. The UO2 ores occur both sides of the unconformity and are associated with extensive brecciation and illite–sudoite–dravite alteration. Quartz and dolomite cementing veins and breccias are associated with alteration and mineralisation and contain a fairly uniform population of fluid inclusions characterised by variable Na:Ca and salinities of 25–35wt.% salts and high U concentrations of up to 600ppm U. In order to further constrain the origin of these U-rich brines, we analysed the naturally occurring isotopes of Ar, Kr and Xe, together with halogens (Cl, Br and I), K, Ca and U in irradiated quartz and dolomite samples containing representative fluid inclusions. This was achieved by the noble gas method for halogen measurement (extended 40Ar–39Ar methodology) using a combination of noble gas extraction techniques.The fluid inclusions opened by crushing quartz and dolomite samples in vacuum have similar molar Br/Cl ratios of 5.8×10−3 to 10.4×10−3, and molar I/Cl ratios of 1.8×10−6 to 8.2×10−6. These compositions lie over the top half of the modern-day seawater evaporation trajectory, consistent with the fluids deriving the bulk of their salinity by subaerial evaporation of seawater, beyond the point of halite saturation. The I/Cl ratios are much lower than is typical of fluids that have interacted with I-rich organic matter present in many sedimentary basins or fluid inclusions found in Mississippi Valley type (MVT) Pb–Zn ore deposits. This is significant because provided the U-rich fluid inclusions are representative of the ore-stage fluids, the low I/Cl ratios of the fluid inclusions do not favour fluid interaction with organic matter (or hydrocarbons), as a major process for localising U mineralisation.The majority of samples contain fluid inclusions with age-corrected 40Ar/36Ar of between the modern atmospheric value of ∼300 and 450. These values are considered representative of the fluid's initial composition and are typical of upper crustal sedimentary formation waters. The fluid inclusions non-radiogenic 84Kr/36Ar and 129Xe/36Ar ratios are slightly enriched in 129Xe relative to air and the fluid inclusions are estimated to contain 0.5–17.3×10−10molg−136Ar which is up to twenty times the 36Ar concentration of air-saturated seawater. The data are interpreted to reflect acquisition of atmospheric noble gases from sedimentary rocks and suggest acquisition of radiogenic 40Ar within K-rich basement rocks, that would have been an important source of excess 40Ar, was limited by temperatures of less than 200°C.Taken together the halogen and noble gas composition of the U-bearing fluid inclusions are strongly controlled by subaerial evaporation and subsequent interaction with sedimentary rocks, showing that low temperature evaporitic brines dominated the mineralising system. Mineralisation is unlikely to have been triggered by fluid interaction with organic matter, or mixing with voluminous basement-derived fluids; however, the data do not completely preclude a role for volumetrically minor fluid or gas phases introduced by deep-seated basement faults preferentially located at the sites of mineralisation.

Noble gas concentrations in fluid inclusions as tracer for the origin of coarse-crystalline cryogenic cave carbonates

The chemically inert behaviour of noble gases, their well-known solubility in water and the long-term constancy of atmospheric noble gas mixing ratios make them a unique tool for paleoclimate studies of groundwater. This concept has recently been extended to fluid inclusions in speleothems. Here we use noble gas concentrations of fluid inclusions contained in calcite crystals to constrain the formation history of coarse crystalline cryogenic cave calcites from Heilenbecker Cave (Germany).Cryogenic cave carbonates form under conditions related to the freezing of cave pools and are a new archive for paleo-permafrost timing and extent. The cryogenic origin of these carbonates is typically deduced from their crystal habit and the carbon and oxygen isotope ratios, but this can be ambiguous in some cases. A geochemical method that provides clear-cut proof of the cryogenic origin of individual crystals has been lacking so far.We examined the formation process of cryogenic cave calcites using water and noble gases extracted from inclusions in these crystals. Based on their δ13C and δ18O values, these calcite crystals could have also formed as ‘normal’, i.e. non-cryogenic, speleothems. Noble gas concentrations derived from fluid inclusions in these cryogenic calcites, however, deviate significantly from commonly observed concentrations in atmospheric air, surface water, groundwater, and stalagmites. These concentrations cannot be explained simply by a solubility component nor by the addition of various amounts of excess-air to a solubility component. The data, however, are consistent with the scenario of a slowly freezing water body lacking exchange with the cave atmosphere. The gradual freezing process leads to a partitioning of the noble gases between ice and remaining water and thereby to a pronounced over-abundance of heavy noble gases in the liquid phase recorded in the fluid inclusions of the cryogenic calcite crystals.

Atmospheric noble gases as tracers of biogenic gas dynamics in a shallow unconfined aquifer

Atmospheric noble gases (NGs) were used to investigate biogenic gas dynamics in a shallow unconfined aquifer impacted by a crude oil spill, near Bemidji, MN. Concentrations of 3,4He, 20,22Ne, 36,40Ar, Kr, and Xe were determined for gas- and aqueous-phase samples collected from the vadose and saturated zones, respectively. Systematic elemental fractionation of Ne, Ar, Kr, and Xe with respect to air was observed in both of these hydrogeologic zones. Within the vadose zone, relative ratios of Ne and Ar to Kr and Xe revealed distinct process-related trends when compared to corresponding ratios for air. The degree of NG deviation from atmospheric concentrations generally increased with greater atomic mass (i.e., ΔXe>ΔKr>ΔAr>ΔNe), indicating that Kr and Xe are the most sensitive NG tracers in the vadose zone. Reactive transport modeling of the gas data confirms that elemental fractionation can be explained by mass-dependent variations in diffusive fluxes of NGs opposite to a total pressure gradient established between different biogeochemical process zones. Depletion of atmospheric NGs was also observed within a methanogenic zone of petroleum hydrocarbon degradation located below the water table. Solubility normalized NG abundances followed the order Xe>Kr>Ar>Ne, which is indicative of dissolved NG partitioning into the gas phase in response to bubble formation and possibly ebullition. Observed elemental NG ratios of Ne/Kr, Ne/Xe, Ar/Xe, and Kr/Xe and a modeling analysis provide strong evidence that CH4 generation below the water table caused gas exsolution and possibly ebullition and carbon transfer from groundwater to the vadose zone. These results suggest that noble gases provide sensitive tracers in biologically active unconfined aquifers and can assist in identifying carbon cycling and transfer within the vadose zone, the capillary fringe, and below the water table.

Quantifying brine assimilation by submarine magmas: Examples from the Galápagos Spreading Centre and Lau Basin

Volatiles are critically important in controlling the chemical and physical properties of the mantle. However, determining mantle volatile abundances via the preferred proxy of submarine volcanic glass can be hampered by seawater assimilation. This study shows how combined Cl, Br, I, K and H2O abundances can be used to unambiguously constrain the dominant mechanism by which melts assimilate seawater-derived components, and provide an improved method for determining mantle H2O and Cl abundances. We demonstrate that melts from the northwest part of the Lau Basin, the Galápagos Spreading Centre and melts from other locations previously shown to have anomalously high Cl contents, all assimilated excess Cl and H2O from ultra-saline brines with estimated salinities of 55±15wt.% salts. Assimilation probably occurs at depths of ∼3–6km in the crust when seawater-derived fluids come into direct contact with deep magmas. In addition to their ultra-high salinity, the brines are characterised by K/Cl of <0.2, I/Cl of close to the seawater value (∼3×10−6) and distinctive Br/Cl ratios of 3.7–3.9×10−3, that are higher than both the seawater value of 3.5×10−3 and the range of Br/Cl in 43 pristine E-MORB and OIB glasses that are considered representative of diverse mantle reservoirs [Br/Clmantle=(2.8±0.6)×10−3 and I/Clmantle=(60±30)×10−6 (2σ)]. The ultra-saline brines, with characteristically elevated Br/Cl ratios, are produced by a combination of fluid-rock reactions during crustal hydration and hydrothermal boiling. The relative importance of these processes is unknown; however, it is envisaged that a vapour phase will be boiled off when crustal fluids are heated to magmatic temperatures during assimilation. Furthermore, the ultra-high salinity of the residual brine that is assimilated may be partly determined by the relative solubilities of H2O and Cl in basaltic melts. The most contaminated glasses from the Galápagos Spreading Centre and Lau Basin have assimilated ∼95% of their total Cl and up to 35–40% of their total H2O, equivalent to the melts assimilating 1000–2000ppm brine at an early stage of their evolution. Dacite glasses from Galapagos contain even higher concentrations of brine components (e.g. 12,000ppm), but the H2O and Cl in these melts was probably concentrated by fractional crystallisation after assimilation. The Cl, Br, I and K data presented here confirm the proportion of seawater-derived volatiles assimilated by submarine magmas can vary from zero to nearly 100%, and that assimilation is closely related to hydrothermal activity. Assimilation of seawater components has previously been recognised as a possible source of atmospheric noble gases in basalt glasses. However, hydrothermal brines have metal and helium concentrations up to hundreds of times greater than seawater, and brine assimilation could also influence the helium isotope systematics of some submarine glasses.

A combined vacuum crushing and sieving (CVCS) system designed to determine noble gas paleotemperatures from stalagmite samples

This paper presents a novel extraction device for water and noble gases from speleothem samples for noble gas paleotemperature determination. The “combined vacuum crushing and sieving (CVCS) system” was designed to reduce the atmospheric noble gas contents from air inclusions in speleothem samples by up to 2 orders of magnitude without adsorbing atmospheric noble gases onto the freshly produced grain surfaces, a process that had often hampered noble gas temperature (NGT) determination in the past. We also present the results from first performance tests of the CVCS system processing stalagmite samples grown at a known temperature. This temperature is reliably reproduced by the NGTs derived from Ar, Kr, and Xe extracted from the samples. The CVCS system is, therefore, suitable for routine determinations of accurate NGTs. In combination with stalagmite dating, these NGTs will allow reconstructing past regional temperature evolutions, and also support the interpretation of the often complex stable isotope records preserved in the stalagmites' calcite.

Large atmospheric noble gas excesses in a shallow aquifer in the Michigan Basin as indicators of a past mantle thermal event

Significant atmospheric noble gas excesses in aquifer systems have systematically been linked to increased hydrostatic pressure, either due to increased water table levels or due to the development of ice cover. Measured noble gases (Ne, Ar, Kr, and Xe) in the shallow Saginaw aquifer in the Michigan Basin display both moderate (∼20–60% Ne excess) and large (∼80−>120% Ne excess) excesses of atmospheric noble gases with respect to air saturated water for modern recharge conditions. All large atmospheric noble gas excesses are located in the main discharge area of the Michigan Basin, in the Saginaw Lowlands region.Here, through a step-by-step analysis, we first show that large atmospheric noble gas excesses in the Saginaw aquifer do not result from increased hydrostatic pressure but, instead, are the result of vertical transport of atmospheric noble gases that are believed to have escaped from deep Michigan Basin brines following a past thermal event of mantle origin. Subsequently, we show that the atmospheric noble gas pattern of the entire Michigan Basin strata appears to result from two distinct end-members: (a) an end-member represented by the deepest, most depleted brines from which most of the atmospheric noble gases escaped; and (b) an end-member with excess atmospheric noble gas values above those displayed by the Saginaw samples. The latter is unconstrained due to the dilution effect exerted by recharge water. Using a Rayleigh distillation model we further show that the greater enrichment of lighter relative to heavier noble gases in the Saginaw aquifer in the Saginaw Lowlands area is compatible with either diffusion or solubility related mechanisms. These findings reinforce the notion that a past thermal event is indeed responsible for the atmospheric noble gas excesses found in the Saginaw aquifer in the Saginaw Lowlands area. They are also consistent with and reinforce previous findings with respect to the occurrence of a thermal event of mantle origin in the Michigan Basin.

Concentrations and isotope ratios of helium and other noble gases in the Earth's atmosphere during 1978–2011

The evolution of the atmospheric noble gas composition during the past few decades has hardly been studied because, in contrast to many other atmospheric gases, systematic time-series measurements have not been available. Based on theoretical considerations, the atmospheric noble gas isotope composition is assumed to be stable on time scales of up to about 106yrs, with the potential exception of anthropogenic changes predicted for the He concentration and the 3He/4He ratio. However, experimental assessments of the predicted changes in the atmospheric He isotope composition are controversial. To empirically test these assumptions and predictions, we analysed the noble gas isotope composition in samples of the Cape Grim Air Archive, a well-defined archive of marine boundary layer air in the southern hemisphere. The resulting time series of the 20Ne, 40Ar, 86Kr and 136Xe concentrations and 20Ne/22Ne and 40Ar/36Ar ratios during 1978–2011 demonstrate the stability of the atmospheric Ne, Ar, Kr and Xe composition during this time interval. The He isotope data indicate a decrease in the 3He/4He during the same time interval at a mean rate of 0.23–0.30‰ per yr. This result is consistent with most model predictions of the rate of decrease in the atmospheric 3He/4He ratio associated with mining and burning of fossil fuels.

Subduction zone fluxes of halogens and noble gases in seafloor and forearc serpentinites

Serpentinites form by hydration of ultramafic lithologies in a range of seafloor and shallow subduction zone settings. Serpentinites are recognised as major reservoirs of fluid mobile elements and H2O in subducting oceanic lithosphere, and together with forearc serpentinites formed in the mantle wedge, provide critical information about shallow-level volatile fluxes during subduction. The current study provides new Cl, as well as the first comprehensive Br, I and noble gas analyses reported for seafloor and forearc chrysotile–lizardite serpentinites. The samples were recovered from IODP drilling campaigns of mid-ocean ridge, passive margin and forearc settings (n=17), and ophiolites in the Italian Alps and Apennines (n=10). The aims of this study were to determine the compositional variability of noble gases and halogens in serpentinites entering subduction zones and evaluate the efficiency of gas loss during the early stages of serpentinite subduction.The chrysotile–lizardite serpentinites and serpentised peridotites contain 43–2300ppm Cl and 3×10−13–2×10−11molg−136Ar, with the concentrations of these elements broadly related to the estimated degree of serpentinisation. The serpentinites have extremely variable Br/Cl and I/Cl ratios with many samples preserving compositions similar to organic-rich sedimentary marine pore fluids. Serpentinites from the Marianas Forearc have very high I concentrations of up to 45ppm I and I/Cl ratios of ∼14,000 times the seawater value that is even higher than the maximum I/Cl enrichment observed in sedimentary marine pore fluids. The serpentinites have 130Xe/36Ar and 84Kr/36Ar ratios that are mostly close to or above seawater values, and 20Ne/36Ar ratios that range from seawater to lower values. The serpentinites contain <10–270ppm K and, irrespective of age (0Ma to ∼160Ma), are characterised by 40Ar/36Ar ratios of 300–340 that are slightly higher than the seawater value of 296, thus indicating the presence of minor excess 40Ar*. Three of six serpentinites analysed for helium also have measurable excess 4He contents that cannot be explained by in situ production. The data show that serpentinites trap noble gases and halogens that originate from seawater, organic matter and diverse crustal lithologies.Combined with previous analyses of metamorphosed serpentinites, the new data suggest that approximately 60–70% of the 36Ar entering subduction zones in serpentinites is lost from chrysotile and/or antigorite and could potentially escape through the forearc. An additional, ∼20–30% of the 36Ar entering subduction zones in serpentinites is lost during antigorite breakdown and may be cycled through the arc or back-arc, and ∼1–10% of the 36Ar entering subduction zones in serpentinites may be subducted into the deeper mantle. The data demonstrate decoupling of noble gases, halogens and water during subduction and suggest that subduction-zone fluid fluxes can produce especially high concentrations of noble gases and iodine in newly formed forearc serpentinites. The distinctive I/Cl enrichment of forearc serpentinites suggest that halogen abundance ratios provide a plausible means for inferring the geotectonic setting of serpentinisation in ophiolite samples. The exceptional Cl, Br, I and noble gas concentrations of serpentinites, the potential subduction of the forearc serpentinites and the stability of serpentine minerals to mantle depths of >200km, imply that serpentinites could dominate the deep recycling budgets of both the heavy halogens and atmospheric noble gases.

Environmental isotopes and noble gases in the deep aquifer system of Kazan Trona Ore Field, Ankara, central Turkey and links to paleoclimate

Environmental isotopes and noble gases in groundwater samples from the Kazan Trona Ore Field are studied to establish the temperature change between the Holocene and the late Pleistocene. Noble gas temperatures (NGTs) presented in this study add an important facet to the global paleotemperature map in the region between Europe and North Africa. The groundwater system under investigation consists of three different aquifers named shallow, middle and deep in which δ18O and δ2H vary from −8.10‰ to −12.80‰ and from −60.89‰ to −92.60‰ VSMOW, respectively. The average isotopic depletion between unconfined and confined parts of the system is −2.5‰ in δ18O and −20‰ in δ2H. It is not possible to explain this depletion solely with the elevation effect. Recharge temperatures derived from dissolved atmospheric noble gases reflect the current average yearly ground temperatures (13°C) for samples collected near the recharge area but are 3 to 8°C lower than today's temperatures in the deep aquifer system. Low 14C activities and high He excesses in the confined parts of the aquifer system suggest that the water in the deep aquifer was recharged during the last Pleistocene under considerably cooler climatic conditions.

Noble gas constraints on the origin and evolution of Earth’s volatiles

This issue of Geochemical Perspectives examines the noble gas geochemistry of meteorites and the Earth to provide essential constraints on the origin of volatiles on our own and other terrestrial planets. Noble gases (He, Ne, Ar, Kr, Xe and Rn) belong to the last column of the Mendeleev’s table, implying they are chemically inert in contrast to the other highly volatile elements. This important feature allows their primordial elemental and isotopic compositions on Earth to be determined without having to consider the additional complexities of chemical or biological influences. Any variations of elemental or isotopic ratios of the noble gases reflects either physical processes such as diffusion, adsorption, degassing, or solubilisation or the effects of natural radioactivity. Moreover, among the highly volatile elements, the noble gases are the only ones that are able to provide constraints on the timing of geochemical fractionations that have occurred since Earth’s accretion, thanks to the natural radioactivity of several parent nuclides with a range of different half-lives, 235,238U, 232Th, 40K, 244Pu, 129I. In this issue, I describe the distribution and isotopic compositions of noble gases in meteorites, mantle-derived rocks and the atmosphere, from both a historical point of view and using some major, new discoveries in that field that have recently changed opinions on mantle/atmosphere evolution and on the origin of volatiles on terrestrial planets. In particular, I discuss the nature of the parent bodies and of the noble gas carriers, the existence and location of a reservoir rich in primordial noble gases sampled by mantle plumes, the subduction of atmospheric noble gas into the mantle and the evolution of the atmosphere evolution since the Earth’s accretion. Of course, this contribution does not have the ambition of addressing all the issues of noble gas geochemistry, but it raises some key questions and contemplates the potential future direction of research into the origin of noble gases and other volatiles in terrestrial planets in the coming years.

The origins of volatiles in the terrestrial planets

The origins of volatiles in the terrestrial planets

Heterogeneous upper mantle Ne, Ar and Xe isotopic compositions and a possible Dupal noble gas signature recorded in basalts from the Southwest Indian Ridge

Variations in heavy noble gas (Ne, Ar, Xe) isotopic compositions provide unique insights into the nature of heterogeneities in the mantle. However, few precise constraints on mantle source heavy noble gas isotopic compositions are available due to ubiquitous shallow-level atmospheric contamination. As a result, the extent of heterogeneity in mid-ocean ridge basalt (MORB) mantle source Ne, Ar and Xe isotopic compositions is unknown. Basalts from the ultra-slow spreading Southwest Indian Ridge (SWIR) between 7°E and 25°E exhibit remarkable variability in He isotopic composition: SWIR 4He/3He spans half the total range observed in all mantle-derived basalts. Therefore, basalts from the SWIR provide a unique window into upper mantle heterogeneity and present an ideal opportunity to characterize variations in upper mantle heavy noble gas isotopic composition. Here we present new high-precision Ne, Ar and Xe isotopic compositions as well as He, CO2, Ne, Ar and Xe abundances measured in basalt glasses from the SWIR. After correcting the measured values for shallow-level atmospheric contamination, significant and systematic variations in mantle source Ne, Ar and Xe compositions are observed. We note that large variations in source 40Ar/36Ar and 129Xe/130Xe are observed in basalts removed from the influence of known hotspots, indicating a heterogeneous mid-ocean ridge basalt source. Thus, SWIR heavy noble gas data reveal a greater degree of source heterogeneity than is evident in the 4He/3He systematics alone. The observed heavy noble gas isotopic heterogeneities imply that the average MORB source 40Ar/36Ar and 129Xe/130Xe ratios are not yet well-determined.Variation in MORB source 40Ar/36Ar and 129Xe/130Xe at a given 4He/3He and 21Ne/22Ne may reflect heterogeneous recycling of atmospheric Ar and Xe. In particular, we find low mantle source 40Ar/36Ar and 129Xe/130Xe ratios in the eastern region of the study area, which may reflect the noble gas signature of the Dupal mantle domain. Our observations require that the sampled mantle domain either is very ancient (>4.45Ga) or has been metasomatized by subduction zone fluids carrying recycled atmospheric Ar and Xe. However, our Xe isotopic measurements indicate that differences between MORB and ocean island basalt (OIB) source noble gas compositions cannot be explained by recycling of atmospheric noble gases alone. Instead, a relatively undegassed mantle reservoir is required to account for OIB noble gases. The SWIR data demonstrate that the reservoir supplying primordial noble gases to mantle plumes differentiated from the MORB source early in Earth history, and the two reservoirs have not been homogenized over 4.45Ga of mantle convection.

Recharge and source‐water insights from the Galapagos Islands using noble gases and stable isotopes

Through a combined noble gas and stable isotope study carried out in the Galapagos Islands of Santa Cruz and San Cristobal, we demonstrate the utility of atmospheric noble gases in identifying recharge areas and timing of recharge in fractured, basaltic systems. Timing of recharge obtained through noble gas temperatures (NGTs) for all samples is corroborated by stable isotopes. Except for one sample, combined NGTs and stable isotope analyses point to recharge during the hot season for all low‐altitude (&lt;∼420 m) spring samples from San Cristobal and all basal aquifer samples in Santa Cruz. Stable isotope comparisons also indicate that San Cristobal springs located at high altitudes (&gt;420 m above sea level) are recharged during both the “garúa” and hot seasons. Preservation of seasonality independently recorded by NGTs and stable isotopes is further reinforced by estimated young water ages. Samples located at high‐altitude display systematic deviations of dissolved noble gases from expected air saturated water values and lead to inconsistent recharge altitudes and temperatures using standard NGT models. Existing degassing models are unable to account for the observed noble gas pattern for most samples. We explore various mechanisms to assess their potential at reproducing the observed noble gas signature. In particular, the potential impact of fog droplets during the cooler “garúa” season on dissolved noble gas concentrations in groundwater and the effect of mixing high‐altitude (≥1500 m) rainwater with low‐altitude (∼400 m) fog droplets is explored. This mixing hypothesis is capable of explaining Ne and Xe concentrations for most high‐altitude samples.

Noble gases as proxies of mean ocean temperature: sensitivity studies using a climate model of reduced complexity

Past global mean ocean temperature may be reconstructed from measurements of atmospheric noble gas concentrations in ice core bubbles. Assuming conservation of noble gases in the atmosphere-ocean system, the total concentration within the ocean mostly depends on solubility which itself is temperature dependent. Therefore, the colder the ocean, the more gas can be dissolved and the less remains in the atmosphere. Here, the characteristics of this novel paleoclimatic proxy are explored by implementing krypton, xenon, argon, and N 2 into a reduced-complexity climate model. The relationship between noble gas concentrations and global mean ocean temperature is investigated and their sensitivities to changes in ocean volume, ocean salinity, sea-level pressure and geothermal heat flux are quantified. We conclude that atmospheric noble gas concentrations are suitable proxies of global mean ocean temperature. Changes in ocean volume need to be considered when reconstructing ocean temperatures from noble gases. Calibration curves are provided to translate ice-core measurements of krypton, xenon, and argon into a global mean ocean temperature change. Simulated noble gas-to-nitrogen ratios for the last glacial maximum are δKr atm = −1.10‰, δXe atm = −3.25‰, and δAr atm = −0.29‰. The uncertainty of the krypton calibration curve due to uncertainties of the ocean saturation concentrations is estimated to be ±0.3 °C. An additional ±0.3 °C uncertainty must be added for the last deglaciation and up to ±0.4 °C for earlier transitions due to age-scale uncertainties in the sea-level reconstructions. Finally, the fingerprint of idealized Dansgaard-Oeschger events in the atmospheric krypton-to-nitrogen ratio is presented. A δKr atm change of up to 0.34‰ is simulated for a 2 kyr Dansgaard-Oeschger event, and a change of up to 0.48‰ is simulated for a 4 kyr event.

High abundances of noble gas and chlorine delivered to the mantle by serpentinite subduction

The Earth’s mantle contains non-radiogenic noble gas isotopes that imply transfer of noble gases from the atmosphere into the mantle through subduction. Hydrated serpentinite rocks within subducting oceanic lithosphere are recognized as key carriers of water and chlorine, but the pathways for noble gas subduction have been poorly constrained. Here we analyse the concentration of noble gas isotopes and halogens in rocks from the Ligurian Alps, Italy and the Betic Cordillera, Spain. These rocks and the fluid inclusions trapped within them preserve a record of serpentinite dehydration during progressively deeper stages of subduction. We find that the noble gas and halogen signature of serpentinites reflects that of sea water and sediment pore fluids. The fluids released become progressively depleted in noble gases and chlorine is subducted to greater depths than bromine or iodine. After complete breakdown of the serpentinites at mantle depths of around 70 km, the dehydrated rock residues still retain a seawater-derived noble gas signature and significant chlorine. We suggest that these samples are proxies for serpentinite dehydration in cold slabs at mantle depths of 200 km or greater. We conclude that atmospheric noble gases are readily incorporated into hydrous minerals formed close to the sea floor, and incompletely removed by subduction zone metamorphism. This implies that noble gases can be subducted to great depths in the Earth’s mantle. Noble gases from the atmosphere are carried into Earth’s mantle through subduction. Geochemical analyses of rocks that record slab dehydration during progressively deeper stages of subduction indicate that noble gases incorporated into hydrous minerals close to the sea floor are efficiently transported to mantle depths of at least 200 km.