Rare gases and fossil particle tracks in the Kenna ureilite

Fossil particle tracks and spallation-produced He and Ne in the Kenna ureilite indicate that it existed in space as a small object for 23 m.y. In our study of Kenna, we found no evidence of trapped He or Ne. Large amounts of heavy rare gases occur in Kenna in concentrations typical of ureilites. In a step-wise release of gases, the isotopic compositions of Kr and Xe were found to be constant above 600°C, revealing the presence of a single retentively sited component. The Xe isotopic abundances are characterized by 124:126:128:129:130:131:132:134:136 = 0.471:0.414:8.280:103.61: 16.296:81.92:100:37.70:31.23. This isotopic composition is distinct from AVCC (average carbonaceous chondritic), but similar to compositions known for some time in certain temperature fractions of Renazzo, Murray and Murchison. Kenna-type Xe appears to be one of the several components found in carbonaceous chondrites.

Binz et al. (Geochim. Cosmochim. Acta 39, 1576–1579, 1975) have recently found that many volatile trace elements are strongly depleted in ureilites. Thus, the relatively large amounts of heavy rare gases present in ureilites did not result from a mixture of a volatile-rich component with the ureilite host. It appears that some material rich in carbon and heavy rare gases was incorporated into a differentiated ureilite host. All current hypotheses which purport to explain the origin of trapped gases in meteorites encounter difficulty in accounting for trapped gases in ureilites in a straightforward manner.     

Noble gas composition of the solar wind as collected by the Genesis mission

We present the elemental and isotopic composition of noble gases in the bulk solar wind collected by the NASA Genesis sample return mission. He, Ne, and Ar were analyzed in diamond-like carbon on a silicon substrate (DOS) and ^84,86Kr and ^129,132Xe in silicon targets by UV laser ablation noble gas mass spectrometry. Solar wind noble gases are quantitatively retained in DOS and with exception of He also in Si as shown by a stepwise heating experiment on a flown DOS target and analyses on other bulk solar wind collector materials. Solar wind data presented here are absolutely calibrated and the error of the standard gas composition is included in stated uncertainties. The isotopic composition of the light noble gases in the bulk solar wind is as follows: ³He/⁴He: (4.64 ± 0.09) × 10⁻⁴, ²⁰Ne/²²Ne: 13.78 ± 0.03, ²¹Ne/²²Ne: 0.0329 ± 0.0001, ³⁶Ar/³⁸Ar 5.47 ± 0.01. The elemental composition is: ⁴He/²⁰Ne: 656 ± 5, and ²⁰Ne/³⁶Ar 42.1 ± 0.3. Genesis provided the first Kr and Xe data on the contemporary bulk solar wind. The preliminary isotope and elemental composition is: ⁸⁶Kr/⁸⁴Kr: 0.302 ± 0.003, ¹²⁹Xe/¹³²Xe: 1.05 ± 0.02, ³⁶Ar/⁸⁴Kr 2390 ± 150, and ⁸⁴Kr/¹³²Xe 9.5 ± 1.0. The ³He/⁴He and the ⁴He/²⁰Ne ratios in the Genesis DOS target are the highest solar wind values measured in exposed natural and artificial targets. The isotopic composition of the other noble gases and the Kr/Xe ratio obtained in this work agree with data from lunar samples containing “young” (∼100 Ma) solar wind, indicating that solar wind composition has not changed within at least the last 100 Ma. Genesis could provide in many cases more precise data on solar wind composition than any previous experiment. Because of the controlled exposure conditions, Genesis data are also less prone to unrecognized systematic errors than, e.g., lunar sample analyses. The solar wind is the most authentic sample of the solar composition of noble gases, however, the derivation of solar noble gas abundances and isotopic composition using solar wind data requires a better understanding of fractionation processes acting upon solar wind formation.     

Nitrogen components in ureilites

Abundances and isotopic compositions of nitrogen and argon have been investigated in bulk samples as well as in acid-resistant C-rich residues of a suite of ureilites consisting of six monomict (Haverö, Kenna, Lahrauli, ALH81101, ALH82130, LEW85328), three polymict (Nilpena, EET87720, EET83309), and the diamond-free ureilite ALH78019. Nitrogen in bulk ureilites varies from 6.3 ppm (in ALH 78019) to ∼55 ppm (in ALH82130), whereas C-rich acid residues have ∼65 to ∼530 ppm N, showing approximately an order of magnitude enrichment, compared with the bulk ureilites, somewhat less than trapped noble gases. Unlike trapped noble gases that show uniform isotopic composition, nitrogen shows a wide variation in δ¹⁵N values within a given ureilite as well as among different ureilites. The variations observed in δ¹⁵N among the ureilites studied here suggest the presence of at least five nitrogen components. The characteristics of these five N components and their carrier phases have been identified through their release temperature during pyrolysis and combustion, their association with trapped noble gases, and their carbon (monitored as CO + CO₂ generated during combustion). Carrier phases are as follows: 1) Amorphous C, as found in diamond-free ureilite ALH78019, combusting at ≤500°C, with δ¹⁵N = -21‰ and accompanied by trapped noble gases. Amorphous C in all diamond-bearing ureilites has evolved from this primary component through almost complete loss of noble gases, but only partial N loss, leading to variable enrichments in ¹⁵N. 2) Amorphous C as found in EET83309, with similar release characteristics as component 1, δ¹⁵N ≥ 50‰ and associated with trapped noble gases. 3) Graphite, as clearly seen in ALH78019, combusting at ≥700°C, δ¹⁵N ≥ 19‰ and devoid of noble gases. 4) Diamond, combusting at 600-800°C, δ¹⁵N ≤ -100‰ and accompanied by trapped noble gases. 5) Acid-soluble phases (silicates and metal) as inferred from mass balance are expected to contain a large proportion of nitrogen (18 to 75%) with δ¹⁵N in the range -25‰ to 600‰. Each of the ureilites contains at least three N components carried by acid-resistant C phases (amorphous C of type 1 or 2, graphite, and diamond) and one acid-soluble phase in different proportions, resulting in the observed heterogeneity in δ¹⁵N. In addition to these five widespread components, EET83309 needs an additional sixth N component carried by a C phase, combusting at <700°C, with δ¹⁵N ≥ 153‰ and accompanied by noble gases. It could be either noble gas-bearing graphite or more likely cohenite. Some excursions in the δ¹⁵N release patterns of polymict ureilites are suggestive of contributions from foreign clasts that might be present in them.Nitrogen isotopic systematics of EET83309 clearly confirm the absence of diamond in this polymict ureilite, whereas the presence of diamond is clearly indicated for ALH82130. Amorphous C in ALH78019 exhibits close similarities to phase Q of chondrites.The uniform δ¹⁵N value of −113 ± 13 ‰ for diamond from both monomict and polymict ureilites and its independence from bulk ureilite δ¹⁵N, Δ¹⁷O, and %Fo clearly suggest that the occurrence of diamond in ureilites is not a consequence of parent body-related process. The large differences between the δ¹⁵N of diamond and other C phases among ureilites do not favor in situ shock conversion of graphite or amorphous C into diamond. A nebular origin for diamond as well as the other C phases is most favored by these data. Also the preservation of the nitrogen isotopic heterogeneity among the carbon phases and the silicates will be more consistent with ureilite formation models akin to “nebular sedimentation” than to “magmatic” type.     

Argon, krypton, and xenon in the bulk solar wind as collected by the Genesis mission

We present bulk solar wind isotopic and elemental ratios for Ar, Kr, and Xe averaged from up to 14 individual analyses on silicon targets exposed to the solar wind for ∼2.3 years during NASA’s Genesis mission. All averages are given with 1σ standard errors of the means and include the uncertainties of our absolute calibrations. The isotopic ratios ⁸⁶Kr/⁸⁴Kr and ¹²⁹Xe/¹³²Xe are 0.303 ± 0.001 and 1.06 ± 0.01, respectively. The elemental ratios ³⁶Ar/⁸⁴Kr and ⁸⁴Kr/¹³²Xe are 2390 ± 120 and 9.9 ± 0.3, respectively. Average fluxes of ⁸⁴Kr and ¹³²Xe in the bulk solar wind in atoms/(cm² s) are 0.166 ± 0.009 and 0.017 ± 0.001, respectively. The flux uncertainties also include a 2% uncertainty for the determination of the extracted areas. The bulk solar wind ³⁶Ar/³⁸Ar ratio of 5.50 ± 0.01 and the ³⁶Ar flux of 397 ± 11 atoms/(cm² s) determined from silicon targets agree well with the ³⁶Ar/³⁸Ar ratio and the ³⁶Ar flux determined earlier on a different type of target by Heber et al. (2009). A comparison of the solar wind noble gas/oxygen abundance ratios with those in the solar photosphere revealed a slight enrichment of Xe and, within uncertainties a roughly uniform depletion of Kr-He in the solar wind, possibly related to the first ionization potentials of the studied elements. Thus, the solar wind elemental abundances He-Kr display within uncertainties roughly photospheric compositions relative to each other. A comparison of the Genesis data with solar wind heavy noble gas data deduced from lunar regolith samples irradiated with solar wind at different times in the past reveals uniform ³⁶Ar/⁸⁴Kr ratios over the last 1-2 Ga but an increase of the ⁸⁴Kr/¹³²Xe ratio of about a factor of 2 during the same time span. The reason for this change in the solar wind composition remains unknown.     

Noble gas and carbon abundances of the Haverö, Dingo Pup Donga,and North Haig ureilites

Total carbon determinations on the Haverö, Dingo Pup Donga, and North Haig ureilites yield values of 2.07, 3.17, and 5.58 wt.%, respectively. Haverö and Dingo Pup Donga contain relatively large amounts of trapped Ar, Kr and Xe, which like the carbon content varies with grain size for Haverö. These two meteorites also contain dominant cosmic rayproduced He and Ne, and show ³He exposure ages of ~23 m.y. and ~7 m.y., respectively. North Haig contains much smaller amounts of trapped gases and spallogenic gases, which may result from loss due to terrestrial weathering. The isotopic composition of Xe in five grain size analyses of Haverö and a whole rock analysis of Dingo Pup Donga shows the presence of a major solar-like Xe component. The presence of this solar component adds an additional complication to the concept of forming ureilites from carbonaceous chondrites.     

The noble gas systematics of late-orogenic H2O-CO2 fluids, Mt Isa, Australia

The noble gases (He, Ne, Ar, Kr and Xe) are powerful geochemical tracers because they have distinctive isotopic compositions in the atmosphere, crust and mantle. This study illustrates how noble gases can be used to trace fluid origins in high-temperature metamorphic and mineralising environments; and at the same time provides new information on the composition of noble gases in deeper parts of the crust than have been sampled previously.We report data for H₂O and CO₂ fluid inclusions trapped at greenschist to amphibolite facies metamorphic conditions associated with three different styles of mineralisation and alteration in the Proterozoic Mt Isa Inlier of Australia. Sulphide fluid inclusions are dominated by crustal ⁴He. However, co-variations in fluid inclusion ²⁰Ne/²²Ne, ²¹Ne/²²Ne, ⁴⁰Ar/³⁶Ar and ¹³⁶Xe/¹³⁰Xe indicate noble gases were derived from three or more reservoirs. In most cases, the fluid inclusions elemental noble gas ratios (e.g. Ne/Xe) are close to the ranges expected in sedimentary and crystalline rocks. However, the elemental ratios have been modified in some of the samples providing evidence for independent pulses of CO_2, and interaction of CO₂ with high-salinity aqueous fluids.Compositional variation is attributed to mixing of: (i) magmatic fluids (or deeply sourced metamorphic fluids) characterised by basement-derived noble gases with ²⁰Ne/²²Ne ∼ 8.4, ²¹Ne/²²Ne ∼ 0.4, ⁴⁰Ar/³⁶Ar ∼ 40,000 and ¹³⁶Xe/¹³⁰Xe ∼ 8; (ii) basinal-metamorphic fluids with a narrow range of compositions including near-atmospheric values and (iii) noble gases derived from the meta-sedimentary host-rocks with ²⁰Ne/²²Ne ∼ 8-9.8, ²¹Ne/²²Ne < 0.1, ⁴⁰Ar/³⁶Ar < 2500 and ¹³⁶Xe/¹³⁰Xe ∼ 2.2.These data provide the strongest geochemical evidence available for the involvement of fluids from two distinct geochemical reservoirs in Mt Isa’s largest ore deposits. In addition the data show how noble gases in fluid inclusions can provide information on fluid origins, the composition of the crust’s major lithologies, fluid-rock interactions and fluid-fluid mixing or immiscibility processes.     

Origin of isotopically light nitrogen in meteorites

Bulk meteorite samples of various chemical classes and petrologic types (mainly carbonaceous chondrites) were systematically investigated by the stepped combustion method with the simultaneous isotopic analysis of carbon, nitrogen, and noble gases. A correlation was revealed between planetary noble gases associating with the Q phase and isotopically light nitrogen (δ¹⁵N up to –150‰). The analysis of this correlation showed that the isotopically light nitrogen (ILN) is carried by Q. In most meteorites, isotopically heavy nitrogen (IHN) of organic compounds (macromolecular material) is dominant. The ILN of presolar grains (diamond and SiC) and Q can be detected after separation from dominant IHN. Such a separation of nitrogen from Q and macromolecular material occurs under natural conditions and during laboratory stepped combustion owing to Q shielding from direct contact with oxygen, which results in Q oxidation at temperatures higher than the temperatures of the release of most IHN. There are arguments that ILN released at high temperature cannot be related to nanodiamond and SiC. The separation effect allowed us to constrain the contents of noble gases in Q, assuming that this phase is carbon-dominated. The directly measured ³⁶Ar/C and ¹³²Xe/C ratios in ILN-rich temperature fractions are up to 0.1 and 1 × 10^–4 cm³/g, respectively. These are only lower constraints on the contents. The analysis of the obtained data on the three-isotope diagram δ¹⁵N–³⁶Ar/¹⁴N showed that Q noble gases were lost to a large extent from most meteorites during the metamorphism of their parent bodies. Hence, the initial contents of noble gases in Q could be more than an order of magnitude higher than those directly measured. Compared with other carbon phases, Q was predominantly transformed to diamond in ureilites affected by shock metamorphism. The analysis of their Ar–N systematics showed that, similar to carbonaceous chondrites, noble gases were lost from Q probably before its transformation to diamond.     

Solubilities of noble gases in magnetite: implications for planetary gases in meteorites

Solubilities of noble gases in magnetite were determined by growing magnetite in a noble-gas atmosphere between 450 and 700°K. Henry's law is obeyed at pressures up to 10^?2 atm for He, Ne, Ar and up to 10^?5 atm for Kr, Xe, with the following distribution coefficients at 500° (cc STP g^?1 atm^?5): He 0.042, Ne 0.016, Ar 3.6, Kr 1.3, Xe 0.88, some 10²–10⁵ times higher than previous determinations on silicate and fluoride melts. Apparent heats of solution in kcal/mole are: He ?2.42 ±0.12, Ne ?2.20 ±0.10, Ar ?15.25 ±0.25, Kr ?13.0 ±0.3, Xe ?12-5 ± 0.5. These values, too, stand in sharp contrast with earlier determinations on melts which were small and positive, but are comparable to the values for clathrates. Presumably the gases are held in anion vacancies.Extrapolation of the magnetite data to the formation temperature of C1 chondrites, 360°K, shows that the Ar_p³⁶ content of Orgueil magnetite could be acquired by equilibrium solubility at a total nebular pressure of 4 × 10^?6 atm. In the absence of data for silicates (the principal host phase of planetary gas), an attempt is made to estimate the solubilities required to account for planetary gases in meteorites. These values do not appear grossly unreasonable in the light of the magnetite data, when structural differences between the two minerals are taken into account. It seems that equilibrium solubility may be able to account for four features of planetary gas: elemental ratios, amounts, correlations with other volatiles and retentive siting. It cannot account for the isotopic fractionation of planetary gas, however.     

Noble gases,nitrogen and cosmic ray exposure age of the Sulagiri chondrite

The Sulagiri meteorite fell in India on 12 September 2008,LL6 chondrite class is the largest among all the Indian meteorites.Isotopic compositions of noble gases(He,Ne,Ar,Kr and Xe) and nitrogen in the Sulagiri meteorite and cosmic ray exposure history are discussed.Low cosmogenic(~(22)Ne/~(21)Ne)_c ratio is consistent with irradiation in a large body.Cosmogenic noble gases indicate that Sulagiri has a 4πcosmic-ray exposure(CRE) age of 27.9 ± 3.4 Ma and is a member of the peak of CRE age distribution of IX chondrites.Radiogenic ~4He and ~(40)Ar concentrations in Sulagiri yields the radiogenic ages as 2.29 and4.56 Ca,indicating the loss of He from the meteorite.Xenon and krypton are mixture of Q and spallogenic components.     

Planetary and pre-solar noble gases in meteorites

Noble gases are not rare in the Universe, but they are rare in rocks. As a consequence, it has been possible to identify in detailed analyses a variety of components whose existence is barely visible in other elements: radiogenic and cosmogenic gases produced in situ, as well as a variety of “trapped” components – both of solar (solar wind) origin and the “planetary” noble gases. The latter are most abundant in the most primitive chondritic meteorites and are distinct in elemental and isotopic abundance patterns from planetary noble gases sensu strictu, e.g., those in the atmospheres of Earth and Mars, having in common only the strong relative depletion of light relative to heavy elements when compared to the solar abundance pattern. In themselves, the “planetary” noble gases in meteorites constitute again a complex mixture of components including such hosted by pre-solar stardust grains.The pre-solar components bear witness of the processes of nucleosynthesis in stars. In particular, krypton and xenon isotopes in pre-solar silicon carbide and graphite grains keep a record of physical conditions of the slow-neutron capture process (s-process) in asymptotic giant branch (AGB) stars. The more abundant Kr and Xe in the nanodiamonds, on the other hand, show a more enigmatic pattern, which, however, may be related to variants of the other two processes of heavy element nucleosynthesis, the rapid neutron capture process (r-process) and the p-process producing the proton-rich isotopes.“Q-type” noble gases of probably “local” origin dominate the inventory of the heavy noble gases (Ar, Kr, Xe). They are hosted by “phase Q”, a still ill-characterized carbonaceous phase that is concentrated in the acid-insoluble residue left after digestion of the main meteorite minerals in HF and HCl acids. While negligible in planetary-gas-rich primitive meteorites, the fraction carried by “solubles” becomes more important in chondrites of higher petrologic type. While apparently isotopically similar to Q gas, the elemental abundances are somewhat less fractionated relative to the solar pattern, and they deserve further study. Similar “planetary” gases occur in high abundance in the ureilite achondrites, while small amounts of Q-type noble gases may be present in some other achondrites. A “subsolar” component, possibly a mixture of Q and solar noble gases, is found in enstatite chondrites. While no definite mechanism has been identified for the introduction of the planetary noble gases into their meteoritic host phases, there are strong indications that ion implantation has played a major role.The planetary noble gases are concentrated in the meteorite matrix. Ca-Al-rich inclusions (CAIs) are largely planetary-gas-free, however, some trapped gases have been found in chondrules. Micrometeorites (MMs) and interplanetary dust particles (IDPs) often contain abundant solar wind He and Ne, but they are challenging objects for the analysis of the heavier noble gases that are characteristic for the planetary component. The few existing data for Xe point to a Q-like isotopic composition. Isotopically Q-Kr and Q-Xe show a mass dependent fractionation relative to solar wind, with small radiogenic/nuclear additions. They may be closer to “bulk solar” Kr and Xe than Kr and Xe in the solar wind, but for a firm conclusion it is necessary to gain a better understanding of mass fractionation during solar wind acceleration.     

Low-pressure adsorption of Ar, Kr, and Xe on carbonaceous materials (kerogen and carbon blacks), ferrihydrite, and montmorillonite: Implications for the trapping of noble gases onto meteoritic matter

Noble gases trapped in meteorites are tightly bound in a carbonaceous carrier labeled “phase Q.” Mechanisms having led to their retention in this phase or in its precursors are poorly understood. To test physical adsorption as a way of retaining noble gases into precursors of meteoritic materials, we have performed adsorption experiments for Ar, Kr, and Xe at low pressures (10⁻⁴ mbar to 500 mbar) encompassing pressures proposed for the evolving solar nebula. Low-pressure adsorption isotherms were obtained for ferrihydrite and montmorillonite, both phases being present in Orgueil (CI), for terrestrial type III kerogen, the best chemical analog of phase Q studied so far, and for carbon blacks, which are present in phase Q and can be considered as possible precursors.Based on adsorption data obtained at low pressures relevant to the protosolar nebula, we propose that the amount of noble gases that can be adsorbed onto primitive materials is much higher than previously inferred from experiments carried out at higher pressures. The adsorption capacity increases from kerogen, carbon blacks, montmorillonite to ferrihydrite. Because of its low specific surface area, kerogen can hardly account for the noble gas inventory of Q. Carbon blacks in the temperature range 75 K-100 K can adsorb up to two orders of magnitude more noble gases than those found in Q. Irreversible trapping of a few percent of noble gases adsorbed on such materials could represent a viable process for incorporating noble gases in phase Q precursors. This temperature range cannot be ruled out for the zone of accretion of the meteorite precursors according to recent astrophysical models and observations, although it is near the lower end of the temperatures proposed for the evolving solar nebula.     

Noble gases in the Allende and Abee meteorites and a gas-rich mineral fraction: investigation by stepwise heating

Noble gases in three meteoritic samples were examined by stepwise heating, in an attempt to relate peaks in the outgassing curves to specific minerals: NeKrXe in Allende (C3V) and an Allende residue insoluble in HF-HCl, and Xe in Abee (E4). In Allende, chromite and carbon contain most of the trapped Ne (²⁰Ne/²²Ne ≈ 8.7) and anomalous Xe enriched in light and heavy isotopes, and release it at ~850°C (bulk meteorite) or 1000°C (residue). Mineral Q, containing most of the trapped Ar, Kr, Xe as well as some Ne (²⁰Ne/²²Ne ≈ 10.4), releases its gases mainly between 1200 and 1600°C, well above the release temperatures of organic polymers (300–500°) or amorphous carbon (800–1000°). The high noble-gas release temperature, ready solubility in oxidizing acids, and correlation with acid-soluble Fe and Cr all point to an inorganic rather than carbonaceous nature of Q.All the radiogenic ¹²⁹Xe is contained in HCl, HF-soluble minerals, and is distributed as follows over the peaks in the release curve: Attend 1000° (75%), 1300° (25%); Abee (data of Hohenberg and Reynolds, 1969) ~850° (15%), 1100° (60%), 1300° (25%). No conclusive identifications of host phases can yet be given; possible candidates are troilite and silicates for Allende, and djerfisherite, troilite and silicates for Abee.Mineral Q strongly absorbs air xenon, and releases some of it only at 800–1000°C. Dilution by air Xe from Q and other minerals may explain why temperature fractions from bulk meteorites often contain less ^124–130Xe for a given enrichment in heavy isotopes than does xenon from etched chromitecarbon samples, although chromite-carbon is the source of the anomalous xenon in either case. Air xenon contamination thus is an important source of error in the derivation of fission xenon spectra.     

Noble gas evidence for two fluids in the Baca (Valles Caldera) geothermal reservoir

Noble gas elemental and isotopic abundances were measured in steam from four wells in the Baca geothermal reservoir located in the Valles Caldera, New Mexico. The ${}^{40}\text{Ar}{}^{36}\text{Ar}$ ratio and noble gas elemental abundances relative to ³⁶Ar are all strongly correlated with 1/³⁶Ar, the inverse of the argon content. Ratios of (α,n)-produced ²¹Ne1 and radiogenic ⁴⁰Ar1 to total ⁴He (dominantly radiogenic) are nearly constant at 2.1 × 10?8 and 0.20, respectively. The ${}^3\text{He}{}^4\text{He}$ ratio covers a restricted range of 3.9 to 4.8 times atmospheric. The high ³He content of the gas indicates the presence of a helium component ultimately derived from the mantle. Kr and Xe isotopic compositions are close to atmospheric; excess ¹²⁹Xe1 is <0.25% of the total ¹²⁹Xe.The high degree of linear correlation among the various noble gas results strongly suggests that the Baca reservoir contains two distinct fluids that are produced in varying proportions from individual wells. The noble gases in fluid A (~2900 mg/1 C1) are air-like, but with lighter gases and isotopes preferentially enriched. The fluid A ³⁶Ar content is low, only 13% that of 10°C air-saturated water (ASW). The second fluid, B (~ 1700 mg/1 C1), is the dominant carrier of the radiogenic and mantle-derived gases. The heavier non-radiogenic gases are preferentially enriched in fluid B, and its ³⁶Ar content is very low, only 5–7% ASW. The source of the noble gases in fluid A is tentatively ascribed to leaching of the relatively young (<1.4 m.y.) volcanic Bandelier Tuff. The radiogenic gases and mantle-derived helium in fluid B suggest a deeper source, possibly including gases escaping from a magma.     

Helium and Argon Isotopic Composition of Cenozoic Alkali Basalts and Mantle-Derived Xenoliths from Kuandian, Liaoning Province, China

The noble gas isotopic composition and content data of 2 alkali basalts, 3 Iherzolite xenoliths and one clinopyroxene megacryst from the Kuandian region have confirmed the occurrence of a fractionation of noble gases during magmatism. Light noble gases such as He and Ne are high in mobility and appear to be incompatible as compared with heavy ones ( such as Kr and Xe). Therefore, light noble gases are abundant in volcanics, especially in the volcanics with bubbles; lherzolite xenoliths have relatively high heavy noble gases. The clinopyroxene megacryst has the lowest abundance of noble gases, probably due to its high P-T origin. Noble gas isotopic composition of the clinopyroxene megacryst reveals that the mantle source beneath the Kuandian area has an MORB-like reservoir with^3 He/^4He ratio of—10 Ra(Ra: atmospheric^3 He/^4He ratio) and^40 Ar/^36 Ar ratio of 345.6. The Iherzolite xenoliths possess moderate^3 He/^4He ratios of 2.59 -4.53 Ra, reflecting the loss of primary helium during rock deformation or metasomatism caused by enriched mantle fluids during the up-lifting. The alkali volcanics have very low^3 He/^4 He ratios(0.47—0.61 Ra),indicating a contribution of radiogenic^4 He, probably having resulted from crust contamination. Most of the samples have excess^21 Ne and^22 Ne as compared with atmospheric neon, but Kr and Xe isotopic compositions are indistinguishable from atmospheric values within uncertainties with only individual samples having excess^129Xe,^134Xeand^136 Xe.     

Noble gases and nitrogen in Martian meteorites Dar al Gani 476, Sayh al Uhaymir 005 and Lewis Cliff 88516: EFA and extra neon

Meteorite “finds” from the terrestrial hot deserts have become a major contributor to the inventory of Martian meteorites. In order to understand their nitrogen and noble gas components, we have carried out stepped heating experiments on samples from two Martian meteorites collected from hot deserts. We measured interior and surface bulk samples, glassy and non-glassy portions of Dar al Gani 476 and Sayh al Uhaymir 005. We have also analyzed noble gases released from the Antarctic shergottite Lewis Cliff 88516 by crushing and stepped heating. For the hot desert meteorites significant terrestrial Ar, Kr, Xe contamination is observed, with an elementally fractionated air (EFA) component dominating the low temperature releases. The extremely low Ar/Kr/Xe ratios of EFA may be the result of multiple episodes of trapping/loss during terrestrial alteration involving aqueous fluids. We suggest fractionation processes similar to those in hot deserts to have acted on Mars, with acidic weathering on the latter possibly even more effective in producing elementally fractionated components. Addition from fission xenon is apparent in DaG 476 and SaU 005. The Ar-Kr-Xe patterns for LEW 88516 show trends as typically observed in shergottites - including evidence for a crush-released component similar to that observed in EETA 79001. A trapped Ne component most prominent in the surface sample of DaG 476 may represent air contamination. It is accompanied by little trapped Ar (²⁰Ne/³⁶Ar > 50) and literature data suggest its presence also in some Antarctic finds. Data for LEW 88516 and literature data, on the other hand, suggest the presence of two trapped Ne components of Martian origin characterized by different ²⁰Ne/²²Ne, possibly related to the atmosphere and the interior. Caution is recommended in interpreting nitrogen and noble gas isotopic signatures of Martian meteorites from hot deserts in terms of extraterrestrial sources and processes. Nevertheless our results provide hope that vice-versa, via noble gases and nitrogen in meteorites and other relevant samples from terrestrial deserts, Martian secondary processes can be studied.     

The origin of rare gases on Earth: The noble gas ‘subduction barrier’ revisited

The origin of the Earth's atmosphere can be constrained by the study of noble gases in oceanic basalts. If it is clear that the mantle is degassed and formed part of the present atmosphere, it has been proposed that an important subduction of atmospheric noble gases in the mantle occurred during Earth's history, altering the primordial signature of the solid Earth. This subduction process has been suggested on the basis of the measurements of light xenon isotopes in CO₂ well gases. Moreover, the fact that the ³⁸Ar/³⁶Ar ratio is atmospheric in all oceanic basalts, even for uncontaminated samples (e.g. with high ²⁰Ne/²²Ne), may also suggest that a massive subduction of atmospheric argon occurred, if the primitive Earth had a solar-like ³⁸Ar/³⁶Ar. This also implies that the atmosphere suffered a massive gas loss accompanied by mass fractionation (e.g. hydrodynamic escape) after mantle degassing or that a late veneer with an atmospheric composition occurred. Such a hypothesis is explored for rare gases, by developing a model in which degassing and subduction of atmospheric noble gases started ∼4.4 Ga ago. In the model, both radiogenic and non-radiogenic isotopic ratios are used (e.g. ³⁸Ar/³⁶Ar and ⁴⁰Ar/³⁶Ar; ¹²⁴Xe/¹³⁰Xe and ¹²⁹Xe/¹³⁰Xe) to constrain the subduction flux and the degassing parameters. It is shown that subduction and massive contamination of the entire mantle is possible, but implies that the ⁴⁰Ar/³⁶Ar and the ¹²⁹Xe/¹³⁰Xe ratios were higher in the past than today, which is not observed in Archean samples. It also implies that the sediments and the altered oceanic crust did not loose their noble gases during subduction or that the contaminated mantle wedge is mixed by the convective mantle. Moreover, such a model has to apply to the oceanic island source, since this later shows the same signature of argon and xenon non-radiogenic isotopic ratios. A scenario where the isotopic compositions of the argon and xenon were settled before or during accretion is therefore preferred to the subduction.     

Noble gases in ultramafic xenoliths from San Carlos,Arizona

This work reports the results of noble gas (Ne, Ar, Kr, Xe) analyses of accidental mantle xenoliths from San Carlos, Arizona. Except for the addition of radiogenic ⁴⁰Ar and mass fractionation effects, the isotopic structures of these gases are indistinguishable from atmospheric composition. The absence of ¹²⁹Xe excesses in these rocks may reflect indirect mixing of atmospheric gases with the source region of the xenoliths. The dominant influence on the noble gas abundances in the San Carlos xenoliths appears to have been diffusive gas loss, which may have occurred in a mantle metamorphic event or during contact with the host basanite magma. Evidence is presented for the partitioning of significant amounts of the heavy noble gases into fluid inclusions in the xenolith minerals; the proportion of each gas in the inclusions increases with increasing atomic weight of the gas, possibly reflecting solubility effects. The noble gases are present in greater concentration in pyroxenes than in olivine, similar to the behavior of other incompatible elements.     

Thermal metamorphism of primitive meteorites—VIII. Noble gases,carbon and sulfur in Allende (C3) meteorite heated at 400–1000°C

Noble gases, C and S are lost from Allende samples heated for 1 week at temperatures of 400–1000°C in a low pressure environment. In the extreme, losses of ³He and ⁴He are ~ 100 × while for C. S and Ne, Ar and Kr isotopes and ¹³²Xe. these are ≤10 ×. Except for He, these losses are less severe than those of Bi or Tl from samples heated in the same runs. Significant He. Ne and Ar isotopic fractionation during heating indicates preferential outgassing of specific reservoirs. Apparent activation energies for all species generally indicate loss controlled by a diffusive process. Next to He, ⁴⁰Ar is the most labile of those species considered here but still less so than Bi or Tl. L-group (but not H- or LL-group) chondrites may have lost mobile elements like Tl while being outgassed after late impact-associated heating. A less likely alternative possibility involving a collateral relation between condensation conditions and depth in a parent object may also explain the L-group trend.     

Dating ultra-deep mine waters with noble gases and Cl, Witwatersrand Basin, South Africa

Concentrations and isotopic ratios of dissolved noble gases, ³⁶Cl, δD and δ¹⁸O in water samples from the ultra-deep gold mines (0.718 to 3.3 km below the surface) in the Witwatersrand Basin, South Africa, were investigated to quantify the dynamics of these ultra deep crustal fluids. The mining activity has a significant impact on the concentrations of dissolved gases, as the associated pressure release causes the degassing of the fissure water. The observed under saturation of the atmospheric noble gases in the fissure water samples (70-98%, normalized to ASW at 20°C and 1013 mbar) is reproduced by a model that considers diffusive degassing and solubility equilibration with a gas phase at sampling temperature. Corrections for degassing result in ⁴He concentrations as high as 1.55 · 10⁻¹cm³STP⁴He g⁻¹, ⁴⁰Ar/³⁶Ar ranging between 806 and 10331, and ¹³⁴Xe/¹³²Xe and ¹³⁶Xe/¹³²Xe ratios above 0.46 and 0.44, respectively. Corrected ^134(136)Xe/¹³²Xe and ^134(136)Xe/⁴He-ratios are consistent with their production ratios, whereas the nucleogenic ⁴He/⁴⁰Ar, and ^134(136)Xe/⁴⁰Ar ratios generally indicate that these gases are produced in an environment with an average [U + Th]/K-content 2-3 times above that of crustal average. In two scenarios, one considering only accumulation of in situ produced noble gases, the other additionally crustal flux components, the model ages for 14 individual water samples range from 13 to 168 Ma and from 1 to 23 Ma, respectively.The low ³⁶Cl-ratios of (4-37) · 10⁻¹⁵ and comparatively high ³⁶Cl-concentrations of (8-350) · 10⁻¹⁵ atoms ³⁶Cl l⁻¹ reflect subsurface production in secular equilibrium indicating an age in excess of 1.5 Ma or 5 times the half-life of ³⁶Cl.In combination, the results suggest residence times of the fluids in fissures in this region (up to 3.3 km depth) are of the order of 1-100 Ma. We cannot exclude the possibility of mixing and that small quantities of younger water have been mixed with the very old bulk.     

Noble gas tracing of groundwater/coalbed methane interaction in the San Juan Basin, USA

The San Juan Basin natural gas field, located in northwestern New Mexico and southwestern Colorado in the USA, is a case-type coalbed methane system. Groundwater is thought to play a key role in both biogenic methane generation and the CO₂ sequestration potential of coalbed systems. We show here how noble gases can be used to construct a physical model that describes the interaction between the groundwater system and the produced gas. We collected 28 gas samples from producing wells in the artesian overpressured high production region of the basin together with 8 gas samples from the underpressured low production zone as a control. Stable isotope and major species determination clearly characterize the gas in the high production region as dominantly biogenic in origin, and the underpressured low producing region as having a significant admix of thermogenic coal gas. ³He/⁴He ratios increase from 0.0836R_a at the basin margin to 0.318R_a towards the center, indicating a clear but small mantle He signature in all gases. Coherent fractionation of water-derived ²⁰Ne/³⁶Ar and crustal ⁴He/⁴⁰Ar* are explained by a simple Rayleigh fractionation model of open system groundwater degassing. Low ²⁰Ne concentrations compared to the model predicted values are accounted for by dilution of the groundwater-associated gas by desorbed coalbed methane. This Rayleigh fractionation and dilution model together with the gas production history allows us to quantify the amount of water involved in gas production at each well. The quantified water volumes in both underpressured and overpressured zones range from 1.7 × 10³ m³ to 4.2 × 10⁵ m³, with no clear distinction between over- and underpressured production zones. These results conclusively show that the volume of groundwater seen by coal does not play a role in determining the volume of methane produced by secondary biodegradation of these coalbeds. There is no requirement of continuous groundwater flow for renewing the microbes or nutrient components. We furthermore observe strong mass related isotopic fractionation of ²⁰Ne/²²Ne and ³⁸Ar/³⁶Ar isotopic ratios. This can be explained by a noble gas concentration gradient in the groundwater during gas production, which causes diffusive partial re-equilibration of the noble gas isotopes. It is important for the study of other systems in which extensive groundwater degassing may have occurred to recognize that severe isotopic fractionation of air-derived noble gases can occur when such concentration gradients are established during gas production. Excess air-derived Xe and Kr in our samples are shown to be related to the diluting coalbed methane and can only be accounted for if Xe and Kr are preferentially and volumetrically trapped within the coal matrix and released during biodegradation to form CH₄.