Noble Gas Components Research Articles

In situ measurement of atmospheric krypton and xenon on Mars with Mars Science Laboratory

Mars Science Laboratory's Sample Analysis at Mars (SAM) investigation has measured all of the stable isotopes of the heavy noble gases krypton and xenon in the martian atmosphere, in situ, from the Curiosity Rover at Gale Crater, Mars. Previous knowledge of martian atmospheric krypton and xenon isotope ratios has been based upon a combination of the Viking mission's krypton and xenon detections and measurements of noble gas isotope ratios in martian meteorites. However, the meteorite measurements reveal an impure mixture of atmospheric, mantle, and spallation contributions. The xenon and krypton isotopic measurements reported here include the complete set of stable isotopes, unmeasured by Viking. The new results generally agree with Mars meteorite measurements but also provide a unique opportunity to identify various non-atmospheric heavy noble gas components in the meteorites. Kr isotopic measurements define a solar-like atmospheric composition, but deviating from the solar wind pattern at 80Kr and 82Kr in a manner consistent with contributions originating from neutron capture in Br. The Xe measurements suggest an intriguing possibility that isotopes lighter than 132Xe have been enriched to varying degrees by spallation and neutron capture products degassed to the atmosphere from the regolith, and a model is constructed to explore this possibility. Such a spallation component, however, is not apparent in atmospheric Xe trapped in the glassy phases of martian meteorites.

Noble gas composition of subcontinental lithospheric mantle: An extensively degassed reservoir beneath Southern Patagonia

Patagonia, in the Southern Andes, is one of the few locations where interactions between the oceanic and continental lithosphere can be studied due to subduction of an active spreading ridge beneath the continent. In order to characterize the noble gas composition of Patagonian subcontinental lithospheric mantle (SCLM), we present the first noble gas data alongside new lithophile (Sr–Nd–Pb) isotopic data for mantle xenoliths from Pali-Aike Volcanic Field and Gobernador Gregores, Southern Patagonia. Based on noble gas isotopic compositions, Pali-Aike mantle xenoliths represent intrinsic SCLM with higher (U+Th+K)/(3He, 22Ne, 36Ar) ratios than the mid-ocean ridge basalt (MORB) source. This reservoir shows slightly radiogenic helium (3He/4He = 6.84–6.90 RA), coupled with a strongly nucleogenic neon signature (mantle source 21Ne/22Ne = 0.085–0.094). The 40Ar/36Ar ratios vary from a near-atmospheric ratio of 510 up to 17700, with mantle source 40Ar/36Ar between 31100−6800+9400 and 54000−9600+14200. In addition, the 3He/22Ne ratios for the local SCLM endmember, at 12.03±0.15 to 13.66±0.37, are higher than depleted MORBs, at 3He/22Ne = 8.31–9.75. Although asthenospheric mantle upwelling through the Patagonian slab window would result in a MORB-like metasomatism after collision of the South Chile Ridge with the Chile trench ca. 14 Ma, this mantle reservoir could have remained unhomogenized after rapid passage and northward migration of the Chile Triple Junction. The mantle endmember xenon isotopic ratios of Pali-Aike mantle xenoliths, which is first defined for any SCLM-derived samples, show values indistinguishable from the MORB source (129Xe/132Xe=1.0833−0.0053+0.0216 and 136Xe/132Xe=0.3761−0.0034+0.0246).The noble gas component observed in Gobernador Gregores mantle xenoliths is characterized by isotopic compositions in the MORB range in terms of helium (3He/4He = 7.17–7.37 RA), but with slightly nucleogenic neon (mantle source 21Ne/22Ne = 0.065–0.079). We suggest that this MORB-like metasomatism was capable of overprinting the noble gas composition of Gobernador Gregores due to recent metasomatism of the SCLM because of asthenospheric mantle upwelling in response to opening of the Patagonian slab window. The 40Ar/36Ar ratios vary from a near-atmospheric ratio of 380 up to 6560, with mantle source 40Ar/36Ar between 8100−700+1400 and 17700−3100+4400. The lower 40Ar/36Ar ratio of the Gobernador Gregores mantle source, compared with that of Pali-Aike, attests that the Patagonia SCLM was affected significantly by atmospheric contamination associated with the recycled oceanic lithosphere.

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.

The tritium-helium-3 method and its application to groundwater dating by the example of the Kirovsk mine region, Murmansk oblast

The measurement of 3H, 3He, 4He, and 20Ne concentrations in waters at the Tsentralny pumping station (southern Khibiny massif, Kola Peninsula) showed that they are a mixture of young (>90%) and old (<10%) waters. The excess noble gas component from the young water is caused by the dissolution of air bubbles trapped during recharge in the unsaturated zone. The 3H-3He(3H) age of the young water is 21 ± 1.5 yr. The U-Th-4He age of the old water is about 50 ka. The high concentrations of helium and some toxic elements (e.g., aluminum) in this old water are caused by dissolution of the alkaline rocks of the Khibiny massif as a result of water-rock interaction.

The quest for regolithic howardites. Part 2: Surface origins highlighted by noble gases

We report noble gas data of helium (He), neon (Ne), argon (Ar), krypton (Kr) and xenon (Xe), cosmic ray exposure (CRE) ages and nominal gas retention (K–Ar, U–Th–He) ages for seven howardites (CRE 01400, EET 87513, EET 87518, EET 99400, GRO 95535, GRO 95602, SAN 03472), in continuing research to identify regolithic samples, and better understand the vestan regolith. In our previous work, we found little correlation between suggested regolith parameters of Ni>300μg/g, Al2O3 8–9wt% and eucrite/diogenite (E:D) ratio of 2:1 (Warren et al., 2009), and trapped solar wind (SW), fractionated solar wind (FSW) or planetary noble gas components (from impacted material) – noble gas indicators of a regolithic origin. Here, we have expanded our data set to include samples outside of these parameters to further explore composition, and the differences in Ni content as indicators for the presence of non-Vesta material. In addition, our sample set includes two potentially paired meteorites from the GRO suite. Finally, in our petrographic studies, the samples selected showed no evidence for carbonaceous chondrite fragments, which should reduce the effect of “contamination” by planetary noble gas components, and will allow us to better identify SW/FSW components, where present.Of the samples studied here, three howardites GRO 95535, GRO 95602 and EET 87513 show evidence for a regolithic origin, with both isotopic and element noble gas ratios clearly pointing to the presence of trapped components similar to SW/FSW or planetary. The two GRO howardites, GRO 95535 and GRO 95602, show similar noble gas ratios to our previously defined SW/FSW dominated regolithic group (LEW 85313 and MET 00423), suggesting a surface origin for these samples. However, interestingly, the GRO samples show vastly different cosmogenic noble gas abundances, and thus different CRE ages, which suggests that they are not paired. For howardite EET 87513, the data hint to the presence of CM-material, with a neon release pattern similar to our defined planetary/FSW dominated regolithic group (CM-rich samples PRA 04401, SCO 06040). Our petrological investigations found no evidence for CM fragments within EET 87513, though a single clast was reported previously (Buchanan et al., 1993). Aside from the Ne release pattern, the remaining noble gas data show more similarity with SW/FSW components. The remaining four howardites CRE 01400, EET 87518, EET 99400, and SAN 03472 and are dominated by cosmogenic noble gases, and show no evidence for a regolithic origin. Our data suggest that a CM-composition is likely present in all samples to some degree, but that this can be overprinted by SW components or cosmogenic components obtained in situ on the vestan surface or during transit to Earth respectively.The presence of CM material is an important parameter for understanding the evolution of Vesta’s surface. While we have uncovered three further regolithic howardites (∼13 regolithic total, of ∼41 analysed), further noble gas analysis of HED meteorites is needed to not only determine regolithic origins, but to better characterise the abundance of carbonaceous chondrite material and its effect on the noble gas signatures of such samples.

Abundances of presolar silicon carbide grains in primitive meteorites determined by NanoSIMS

It has been suggested that the matrices of all chondrites are dominated by a common material with Ivuna-like (CI) abundances of volatiles, presolar grains and insoluble organic matter (IOM) (e.g., Alexander, 2005). However, matrix-normalized abundances of presolar silicon carbide (SiC) grains estimated from their noble gas components show significant variations in even the most primitive chondrites (Huss and Lewis, 1995; Huss et al., 2003), in contradiction to there being a common chondrite matrix material. Here we report presolar SiC abundances determined by NanoSIMS raster ion imaging of IOM extracted from primitive members of different meteorite groups. We show that presolar SiC abundance determinations are comparable between NanoSIMS instruments located at three different institutes, between residues prepared by different demineralization techniques, and between microtomed and non-microtomed samples. Our derived SiC abundances in CR chondrites are comparable to those found in the CI chondrites (∼30ppm) and are much higher than previously determined by noble gas analyses. The revised higher CR SiC abundances are consistent with the CRs being amongst the most primitive chondrites in terms of the isotopic compositions and disordered nature of their organic matter. Similar abundances between CR1, CR2, and CR3 chondrites indicate aqueous alteration on the CR chondrite parent body has not progressively destroyed SiC grains in them. A low SiC abundance for the reduced CV3 RBT 04133 can be explained by parent body thermal metamorphism at an estimated temperature of ∼440°C. Minor differences between primitive members of other meteorite classes, which did not experience such high temperatures, may be explained by prolonged oxidation at lower temperatures under which SiC grains formed outer layers of SiO2 that were not thermodynamically stable, leading to progressive degassing/destruction of SiC.

Phenocryst He–Ar isotopic and whole-rock geochemical constraints on the origin of crustal components in the mantle source of Cenozoic continental basalt in eastern China

Continental basalts commonly exhibit similar geochemical compositions to oceanic island basalts, but their origin is still enigmatic in chemical geodynamics. This involves a resolution to the nature of crustal components in their mantle sources. For this purpose, we have studied the He and Ar isotopic compositions of mineral phenocrysts from Cenozoic continental basalts in eastern China. The results are combined with existing data for whole-rock geochemistry, yielding two trends between noble gas isotopic and other geochemical indicators. First is high 3He/4He ratios of 6.6 to 7.5RA and low 4He/40Ar* ratios of 0.07 to 1.39 in association with varying (La/Yb)N values from 10.4 to 31.8. Second is low 3He/4He ratios of 0.6 to 2.4RA and variable 4He/40Ar* ratios from 0.68 to 15.47 in association with low (La/Yb)N values of 11.3 to 12.0. Phenocryst 40Ar/36Ar ratios vary from 331.0 to 1677.4, in which the low ratios are associated with the low (La/Yb)N values. In combination with whole-rock Ba/Th and Sr/Y ratios as well as initial Sr and Nd isotopic ratios, we suggest three-component mixing between enriched MORB mantle, altered oceanic basalt and seafloor sediment to generate the mantle sources. The two kinds of crustal components would be incorporated into the mantle sources in the form of felsic melts. One is adakitic melt deriving from the altered oceanic basalt and thus low in Ba/Th ratios but high in Sr/Y, (La/Yb)N and εNd(t) values. The other is sialic melt originating from the seafloor sediment and thus high in Ba/Th ratios but low in Sr/Y, (La/Yb)N and εNd(t) values. The atmospheric Ar and crustal He noble gas components would be carried by the both seawater–hydrothermally altered basalt and seafloor sediment on the oceanic crust. These oceanic crust-derived melts would serve as a metasomatic agent to transfer the supracrustal He and Ar isotopic signatures to the mantle sources. The felsic melts would react with the mantle wedge peridotite during slab–mantle interaction in oceanic subduction channel. Therefore, the noble gas isotopic compositions of mantle sources for intraplate basalts are primarily determined by the budget between the mantle and crustal components during the melt–peridotite in oceanic subduction factory.

Unique chemistry of a diamond-bearing pebble from the Libyan Desert Glass strewnfield, SW Egypt: Evidence for a shocked comet fragment

We have studied a small, very unusual stone, here named “Hypatia”, found in the area of southwest Egypt where an extreme surface heating event produced the Libyan Desert Glass 28.5 million years ago. It is angular, black, shiny, extremely hard and intensely fractured. We report on exploratory work including X-ray diffraction, Raman spectroscopy, transmission electron microscopy, scanning electron microscopy with EDS analysis, deuteron nuclear reaction analysis, C-isotope and noble gas analyses. Carbon is the dominant element in Hypatia, with heterogeneous O/C and N/C ratios ranging from 0.3 to 0.5 and from 0.007 to 0.02, respectively. The major cations of silicates add up to less than 5%. The stone consists chiefly of apparently amorphous, but very hard carbonaceous matter, in which patches of sub-μm diamonds occur. δ13C values (ca. 0‰) exclude an origin from shocked terrestrial coal or any variety of terrestrial diamond. They are also higher than the values for carbonaceous chondrites but fall within the wide range for interplanetary dust particles and comet 81P/Wild2 dust. In step heating, 40Ar/36Ar ratios vary from 40 to the air value (298), interpreted as a variable mixture of extraterrestrial and atmospheric Ar. Isotope data of Ne, Kr and Xe reveal the exotic noble gas components G and P3 that are normally hosted in presolar SiC and nanodiamonds, while the most common trapped noble gas component of chondritic meteorites, Q, appears to be absent. An origin remote from the asteroid belt can account for these features.We propose that the Hypatia stone is a remnant of a cometary nucleus fragment that impacted after incorporating gases from the atmosphere. Its co-occurrence with Libyan Desert Glass suggests that this fragment could have been part of a bolide that broke up and exploded in the airburst that formed the Glass. Its extraordinary preservation would be due to its shock-transformation into a weathering-resistant assemblage.

Effects of atmospheric entry heating on the noble gas and nitrogen content of micrometeorites

Fragments of the carbonaceous chondrite Orgueil were subjected to pulse-heating sequences in order to simulate the heating conditions experienced by micrometeorites (MMs) upon entry into Earthʼs atmosphere. By increasing the experimental run times from 2 to 120 s at a fixed temperature of 1350 °C, the different textures of natural MMs (from non-vesicular fine-grained particles to melted cosmic spherules) were reproduced, and the noble gas (He, Ne, Ar) and nitrogen abundances and isotope ratios of the MM analogues were subsequently determined by CO2 laser extraction-static mass spectrometry analysis. The starting material shows a heterogeneous He–Ne–Ar–N signature, consistent with the mineralogical heterogeneity of CI chondrites and the inhomogeneous distribution of various noble gas and nitrogen components among meteoritic minerals. Nonetheless, our experiments demonstrate that moderately to strongly heated Orgueil fragments retain only a few percent of their initial noble gas and nitrogen inventories, indicating that atmospheric entry heating results in extensive degassing of meteoritic dust particles. The evolution of the noble gas and nitrogen isotope ratios may, in part, be explained by equilibration with the atmosphere; however, the decreasing δ15N values may also indicate preferential degradation of a 15N-rich component by thermal processing of chondritic matter. Furthermore, the efficient loss of helium and cosmogenic neon during heating will lead to an underestimate of the 3He and 21Ne exposure ages of MMs, as well as to large uncertainties for cosmic dust accretion rates derived from extraterrestrial 3He abundances in deep-sea sediments or polar ice cores. While the relative proportions of infalling cometary and asteroidal dust on Earth are unknown, the contribution of noble gases, nitrogen, and water from cosmic dust to the terrestrial volatile inventory appears negligible.

The quest for regolithic howardites. Part 1: Two trends uncovered using noble gases

We report noble gas data (helium (He), neon (Ne), argon (Ar), krypton (Kr) and xenon (Xe)), nominal gas retention ages (K–Ar, U–Th–He) and cosmic ray exposure (CRE) ages for the ten howardites EET 83376, EET 99408, LEW 85313, MET 00423, MET 96500, PCA 02066, PRA 04401, QUE 94200, QUE 97002, and SCO 06040, in research to better understand the regolith of the HED parent body – Vesta – through a combined petrological, compositional and noble gas study. Our main aim is to determine which howardites are truly regolithic – as defined by the presence of solar noble gas components (e.g. solar wind (SW), fractionated solar wind (FSW)) and/or by the presence of planetary components (e.g. Q, HL) associated with foreign clasts of carbonaceous chondrite material within the breccias.Of our ten howardites, four (LEW 85313, MET 00423, PRA 04401 and SCO 06040) show evidence for a regolithic origin, with noble gas ratios indicating the presence of trapped components. Howardites PRA 04401 and SCO 06040 contain significant amounts of CM type carbonaceous chondrite material, and these samples are dominated by a planetary component similar to that observed in CM meteorites Murchison and Maribo. Overall, we find evidence for two regolithic groups with different release trends: (1) SW/FSW component dominated howardites (LEW 85313 and MET 00423), where SW/FSW is dominant at low temperature releases, and less pronounced at higher temperatures; (2) Planetary component dominated howardites (PRA 04401 and SCO 06040) that also contain SW/FSW – the planetary component is associated with incorporated carbonaceous chondrite material, and is dominant at the mid-temperature release. The remaining six howardites EET 83376, EET 99408, MET 96500, PCA 02066, QUE 94200, and QUE 97002, are dominated by cosmogenic noble gases, and are not considered regolithic.Previous work by Warren et al. (2009) suggested that high siderophile element contents (specifically nickel (Ni)>300μg/g) were a regolith indicator for howardites, in addition to restricted Al2O3 contents (8–9wt.%) representing a eucrite/diogenite mixing ratio of 2:1 as indicative of an ancient well-mixed regolith. These parameters were based on five ‘gas-rich’ howardites. However, we find no obvious correlation between these parameters and SW/FSW or planetary noble gas content in our howardite samples. We conclude that howardite regolith parameters are not as simple as those defined by Warren et al. (2009), where three of the five howardites used contained foreign CM material, which may have caused a bias in their defined parameters. We conclude that sideophile abundances alone cannot be used to determine the regolithic nature of a sample: noble gas analysis remains a key parameter, where it is important to distinguish between planetary-dominated and SW-dominated regolithic howardites.

Modeling Noble Gas Transport and Detection for The Comprehensive Nuclear-Test-Ban Treaty

Detonation gases released by an underground nuclear test include trace amounts of 133Xe and 37Ar. In the context of the Comprehensive Nuclear Test Ban Treaty, On Site Inspection Protocol, such gases released from or sampled at the soil surface could be used to indicate the occurrence of an explosion in violation of the treaty. To better estimate the levels of detectability from an underground nuclear test (UNE), we developed mathematical models to evaluate the processes of 133Xe and 37Ar transport in fractured rock. Two models are developed respectively for representing thermal and isothermal transport. When the thermal process becomes minor under the condition of low temperature and low liquid saturation, the subsurface system is described using an isothermal and single-gas-phase transport model and barometric pumping becomes the major driving force to deliver 133Xe and 37Ar to the ground surface. A thermal test is simulated using a nonisothermal and two-phase transport model. In the model, steam production and bubble expansion are the major processes driving noble gas components to ground surface. After the temperature in the chimney drops below boiling, barometric pumping takes over the role as the major transport process.

Determination of Holocene cave temperatures from Kr and Xe concentrations in stalagmite fluid inclusions

From the concentrations of dissolved atmospheric noble gases in water, a so-called “noble gas temperature” (NGT) can be determined that corresponds to the temperature of the water when it was last in contact with the atmosphere. Here we demonstrate that the NGT concept is applicable to water inclusions in cave stalagmites, and yields NGTs that are in good agreement with the ambient air temperatures in the caves. We analysed samples from two Holocene and one undated stalagmite. The three stalagmites originate from three caves located in different climatic regions having modern mean annual air temperatures of 27°C, 12°C and 8°C, respectively. In about half of the samples analysed Kr and Xe concentrations originated entirely from the two well-defined noble gas components air-saturated water and atmospheric air, which allowed NGTs to be determined successfully from Kr and Xe concentrations. One stalagmite seems to be particularly suitable for NGT determination, as almost all of its samples yielded the modern cave temperature. Notably, this stalagmite contains a high proportion of primary water inclusions, which seem to preserve the temperature-dependent signature well in their Kr and Xe concentrations. In future work on stalagmites detailed microscopic inspection of the fluid inclusions prior to noble gas analysis is therefore likely to be crucial in increasing the number of successful NGT determinations.

Production of anomalous Xe in nanodiamond in chondrites during the last supernova explosion predating the origin of the Solar System

Anomalous Xe enriched in both heavy and light isotopes (Xe-HL) was identified in the high-temperature Xe fraction in relict nanodiamond grains from chondrites, whereas the low-temperature Xe fraction (Xe-P3) typically has the normal isotopic composition. The paper presents a concise review of current models put forth to account for the genesis of nanodiamond with anomalous noble gas components and specifies a real process and major regularities during the generation of the isotopic relations of the anomalous Xe-HL component in relict nanodiamond grains. This component is demonstrated to be formed and captured simultaneously with the synthesis of nanodiamond, when shock waves induced by supernova explosions propagated. It is important that diamond synthesis during the passage of shock waves and the enrichment of this diamond in Xe-HL are also possible in the wave forefront region under extremal P-T conditions, in the pressure drop region behind the wave front (by means of nucleation), and by means of irradiation of carbonic grains with high-energy particles. The isotopic composition of Xe-HL results from an increase in the hardness of the spectrum of nuclear-active particles and its enrichment in heavy ions at acceleration in shock waves. Arguments are presented in support of the hypothesis that the nanodiamond population found in chondrites was produced during the latest supernova explosion before the development of the Solar System, with the supernova likely being a SnIa carbon detonation supernova. This furnishes evidence in support of recently advanced hypotheses that the nanodiamond population of chondrites is not presolar.

A reappraisal of the metamorphic history of EH3 and EL3 enstatite chondrites

The thermal history of a series of EH3 and EL3 chondrites has been investigated by studying the degree of structural order of the organic matter (OM) located and characterized in matrix areas by Raman micro-spectroscopy. By comparison with unequilibrated ordinary chondrites (UOCs) and CO and CV carbonaceous chondrites, the following petrologic types have been assigned to various E chondrites: Sahara 97096 and Allan Hills 84206: 3.1–3.4; Allan Hills 85170 and Parsa: 3.5; Allan Hills 85119: 3.7; Qingzhen, MacAlpine Hills 88136 and MacAlpine Hills 88184: 3.6–3.7. The petrologic type of Qingzhen is consistent with the abundance of the P3 noble gas component, a sensitive tracer of the grade of thermal metamorphism. The petrologic types are qualitatively consistent with the abundance of fine-grained matrix for the whole series. No significant effects of shock processes on the structure of OM were observed. However such processes certainly compete with thermal metamorphism and the possibility of an effect cannot be fully discarded, in particular in the less metamorphosed objects. The OM precursors accreted by the EH3 and EL3 parent bodies appear to be fairly similar to those of UOCs and CO and CV carbonaceous chondrites. Raman data however show some slight structural differences that could be partly accounted for by shock processes. The metamorphic history of EH3 and EL3 chondrites has often been described as complex, in particular regarding the combined action of shock and thermal metamorphism. Because OM maturity is mostly controlled by the temperature of peak metamorphism, it is possible to distinguish between the contributions of long duration thermal processes and that of shock processes. Comparison of the petrologic types with the closure temperatures previously derived from opaque mineral assemblages has revealed that the thermal history of EH3 and EL3 chondrites is consistent with a simple asteroidal onion shell model. Thermal metamorphism in enstatite chondrites appears to be fairly similar to that which takes place in other chondrite classes. The complex features recorded by mineralogy and petrology and widely reported in the literature appear to be mostly controlled by shock processes.

Noble gases in anhydrous mantle xenoliths from Tasmania in comparison with other localities from eastern Australia: Implications for the tectonic evolution

Ultramafic xenoliths from Tasmanian basalts were analysed for elemental and isotopic compositions of noble gases, for greater understanding of the evolution of the underlying subcontinental lithosphere. The noble gas isotopic compositions indicate contributions of radiogenic and MORB-like components to the xenoliths. The MORB-like component is characterized by 3He/ 4He ratios between 7 and 9 Ra while the radiogenic component shows lower 3He/ 4He ratios than those in MORB (8.75 ± 2.14 Ra, Graham, 2002). The identified radiogenic component in xenoliths from Tasmania may stem from subduction events, during which the mantle wedge and subcontinental lithospheric mantle were metasomatised by U- and Th-rich fluids. As subduction processes have played important role in the evolution of Eastern Australia during the Paleozoic, the radiogenic component is probably associated with this event. Incorporation of MORB-like noble gases in the subcontinental lithospheric mantle beneath Tasmania is likely related to extensional rifting and associated opening of the Tasman Sea in the Late Mesozoic and Cenozoic. The identified noble gas components of the xenoliths are consistent with the geochemical character of the host basalt based on the radiogenic isotope and trace element systematics. This agreement and the petrographic observations (e.g. fluid inclusion trails connected with the reaction rim of the minerals close to the host basalt, spongy texture) indicate that fluids (noble gases, CO 2) most likely propagated from the host basalts to the xenoliths forming fluid inclusions. The observed noble gas isotopic heterogeneity in mantle-derived xenoliths from Tasmanian to North Queensland reflects isotopic heterogeneity at regional scale in the subcontinental lithospheric mantle beneath eastern Australia.

Accurate analysis of noble gas concentrations in small water samples and its application to fluid inclusions in stalagmites

The concentrations of dissolved noble gases in water are widely used as a climate proxy to determine noble gas temperatures (NGTs); i.e., the temperature of the water when gas exchange last occurred. In this paper we make a step forward to apply this principle to fluid inclusions in stalagmites in order to reconstruct the cave temperature prevailing at the time when the inclusion was formed. We present an analytical protocol that allows us accurately to determine noble gas concentrations and isotope ratios in stalagmites, and which includes a precise manometrical determination of the mass of water liberated from fluid inclusions. Most important for NGT determination is to reduce the amount of noble gases liberated from air inclusions, as they mask the temperature-dependent noble gas signal from the water inclusions. We demonstrate that offline pre-crushing in air to subsequently extract noble gases and water from the samples by heating is appropriate to separate gases released from air and water inclusions. Although a large fraction of recent samples analysed by this technique yields NGTs close to present-day cave temperatures, the interpretation of measured noble gas concentrations in terms of NGTs is not yet feasible using the available least squares fitting models. This is because the noble gas concentrations in stalagmites are not only composed of the two components air and air saturated water (ASW), which these models are able to account for. The observed enrichments in heavy noble gases are interpreted as being due to adsorption during sample preparation in air, whereas the excess in He and Ne is interpreted as an additional noble gas component that is bound in voids in the crystallographic structure of the calcite crystals. As a consequence of our study's findings, NGTs will have to be determined in the future using the concentrations of Ar, Kr and Xe only. This needs to be achieved by further optimizing the sample preparation to minimize atmospheric contamination and to further reduce the amount of noble gases released from air inclusions.

“Planetary” noble gas components and the nucleosynthetic history of solar system material

Models capable of explaining the differences between the isotopic compositions of the planetary noble gas components “Q” and “P3” (widespread in primitive meteorites) and average solar system material as sampled by the solar wind are presented, and their implications discussed. Small, variable amounts of known presolar components and 129Xe from 129I decay are present in Q gases alongside a solar composition that has been mass fractionated. These most likely arise either from mixing during parent body processing or co-release from poorly retentive phases during analysis. Thus the heavy noble gas budget of primitive meteorites is dominated by a component derived from material with the average composition of the solar system. In contrast, P3 seems best explained as a presolar component, consistent with isolation from bulk material that subsequently evolved to the solar composition as newly synthesised material was added. Examination of Kr-P3 identifies the addition as having had the signature of the weak s-process, and demonstrates that a second process that contributes the isotopes of krypton not produced in the s-process (residual isotopes) must also have added material to the reservoir as it evolved to the solar composition. Total s-process contributions required of 132Xe and 84Kr are at least ∼1% of the present budget, as is that of the residual krypton “component”. While concentrations of P3 vary with extents of parent body processing, concentrations of 129Xe excess from 129I decay associated with P3 are roughly constant in those least processed meteorites that retain a P3 signature (apart from ALH77307). This has a natural explanation in the different chemical behaviours of iodine and xenon if 129I was alive in P3 in the early solar system. The presence of live 129I in P3 in the early solar system imposes a loose constraint that the P3 component was isolated from a parent reservoir less than ∼100 Myr before the formation of the solar system. The model of evolution from P3 gases to the solar composition requires that residual krypton isotopes are not products of a conventional r-process that also synthesises 129I. Separate sites for synthesis of residual isotopes of krypton and the heavy element r-process are consistent with observations of metal poor stars, but do not correspond to the two r-processes invoked to account for variations between the 182Hf and 129I systems. Since the weak s-process is implicated as the source of the s-process material contributed as the P3 reservoir evolved to a solar composition, the massive stars that host it may also host the process that synthesises residual krypton isotopes. The recent presence of nearby massive stars is consistent with an emerging picture of the environment of solar system formation.

Crustal noble gases in deep brines as natural tracers of vertical transport processes in the Michigan Basin

Noble gas concentrations and isotopic ratios are presented for 38 deep (∼0.5–3.6 km) brine samples in the Michigan Basin. These brine samples clearly show the presence of an important crustal component of 4He, 21Ne, 40Ar, and 136Xe. Both 40Arcrust and 136Xecrust display the presence of a strong vertical gradient along the sedimentary strata of the basin. We show that the in situ production for these two gases within the sedimentary strata is insufficient to account for the observed crustal component in the Michigan brines. These point to the presence of a deep, external source for crustal noble gases, likely the Precambrian crystalline basement beneath the Michigan Basin. Furthermore, observed elemental ratios of crustal noble gases (4He/40Ar, 21Ne/40Ar, 4He/136Xe, and 21Ne/136Xe) in these brines vary over several orders of magnitude with respect to the expected production ratios from the crystalline basement rocks and display a systematic pattern within the basin. Specifically, samples above the Salina Group (shallow formations) are relatively enriched in 4Hecrust and 21Necrust with respect to 40Arcrust and 136Xecrust, as opposed to those below the massive Salina evaporite layer (deeper formations) which exhibit complementary patterns. We show that such a general trend is best explained by a Rayleigh‐type elemental fractionation model involving upward transport of crustal noble gases and associated elemental fractionation processes, controlled by both diffusion‐ and solubility‐related mechanisms. As previously indicated by the mantle and atmospheric noble gas signatures in these same Michigan brine samples, release of deep crustal noble gases into the basin is yet another independent indicator pointing to the occurrence of a past thermal event in the basin. We suggest that recent reactivation of the ancient midcontinent rift system underneath the Michigan Basin is likely responsible for the upward transport of heat and loss of the atmospheric noble gas component, as well as release of crustal (still ongoing) and mantle noble gases into the basin via deep‐seated faults and fracture zones. Such a model also supports an internal heat source hypothesis as being largely responsible for the existence of past high temperatures in the basin without involvement of large‐scale brine migration from peripheral forming orogenic fold belts.

Noble gas and nitrogen isotopic components in Oceanic Island Basalts

We present helium, argon, xenon and nitrogen isotopic data from Oceanic Island Basalts (OIBs), obtained from stepped heating and vacuum crushing experiments. Signatures of 3He/ 4He in the present samples, except for those from the Canary Islands, are significantly higher (up to 20 × the air ratio) than the MORB signature (8.5 × air ratio). The argon ( 40Ar/ 36Ar) and xenon ( 129Xe/ 132Xe and 136Xe/ 132Xe) isotopic data are consistent with a two-component mixture of gases from the mantle (either MORB or OIB source) and air contamination. In the stepwise heating data, δ 15N varies from − 20‰ to + 15‰ in the different heating steps. The vacuum crushing data show a narrower range (− 5‰ to + 8‰) of δ 15N, which, except for one Réunion sample, is somewhat heavier than the totals from the stepped heating experiments. Simultaneous argon and nitrogen isotopic systematics of the present data suggest contributions from mantle (somewhat different from MORB), recycled materials and air contamination. This is also consistent with the 36Ar/ 132Xe elemental ratio. The present stepped heating data are consistent with a nitrogen isotopic component with δ 15N ~ − 25‰ in the OIB mantle. In line with the oxygen isotopic composition of the bulk Earth, this would be consistent with a contribution from enstatite chondrite-like volatiles to the planet's accretion.

SODIUM-22 FROM SUPERNOVAE: A METEORITE CONNECTION

There are several meteoritic noble gas components whose isotopic abundances are distinctly different from the solar abundance. One of these components, Ne-E(L), is a 22Ne-rich component carried by presolar graphite. Neon-22 is dominantly from the radiogenic decay of 22Na (T 1/2 = 2.6 a), but it also contains 22Ne produced by 14N(α, γ)18F(e +ν)18O(α, γ)22Ne. The proportions of 22Ne from the two different origins vary with graphite density. Many low-density graphite grains (1.65-1.72 g cm–3) exhibit 18O and 28Si excesses, signatures of supernova origin. We revisited noble gas data on bulk (=aggregates) and single-grain analyses of presolar graphite to better understand the origin of Ne-E(L). We conclude that essentially all 22Ne in low-density graphite grains originated from 22Na produced in the O/Ne zone in supernovae. The initial presence of 22Na in these grains indicates that grains formed within a few years after the supernova explosion. The absence of implanted 22Ne can be explained if the grains and the gas in the ejecta became decoupled when they encountered the reverse shock and sputtering eroded the grains in the outer H-rich zone and in the interstellar medium.