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.     

微量陨石激光熔样稀有气体测定方法

微量陨石激光熔样稀有气体测定方法是一种可以在微米尺度上对几毫克陨石样品进行准确稀有气体同位素分析的方法,克服了传统全岩熔融法在测量时存在样品用量大、前处理过程复杂和样品稀有气体分布不均导致不同组分的宇宙射线暴露历史无法进一步区分等问题。但是由于该方法所用样品体积小和样品用量低,要求实验室具有超低本底的稀有气体提取系统,目前国内在微量陨石稀有气体分析技术方面尚处于起步阶段。本文采用金刚石激光样品窗成功研制了超低本底的气体提取系统,通过系统体积标定和天平称量误差、热本底、干扰元素、质量歧视及质谱灵敏度等参数的校正,在中国科学院地质与地球物理研究所建立了微量陨石激光熔样稀有气体测定方法,并对毫克级微量钙长辉长无球粒陨石Millbillillie粉末标样进行了稀有气体同位素含量和比值测定,计算获得准确一致的宇宙暴露年龄。该方法的建立,将为我国迅速发展的比较行星学和深空探测提供重要技术支撑。     

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.     

Chronology and shock history of the Bencubbin meteorite: A nitrogen, noble gas, and Ar-Ar investigation of silicates, metal and fluid inclusions

We have investigated the distribution and isotopic composition of nitrogen and noble gases, and the Ar-Ar chronology of the Bencubbin meteorite. Gases were extracted from different lithologies by both stepwise heating and vacuum crushing. Significant amounts of gases were found to be trapped within vesicles present in silicate clasts. Results indicate a global redistribution of volatile elements during a shock event caused by an impactor that collided with a planetary regolith. A transient atmosphere was created that interacted with partially or totally melted silicates and metal clasts. This atmosphere contained ¹⁵N-rich nitrogen with a pressure ?3 × 10⁵ hPa, noble gases, and probably, although not analyzed here, other volatile species. Nitrogen and noble gases were re-distributed among bubbles, metal, and partly or totally melted silicates, according to their partition coefficients among these different phases. The occurrence of N₂ trapped in vesicles and dissolved in silicates indicates that the oxygen fugacity (f_O2) was greater than the iron-wüstite buffer during the shock event. Ar-Ar dating of Bencubbin glass gives an age of 4.20 ± 0.05 Ga, which probably dates this impact event. The cosmic-ray exposure age is estimated at ∼40 Ma with two different methods. Noble gases present isotopic signatures similar to those of “phase Q” (the major host of noble gases trapped in chondrites) but elemental patterns enriched in light noble gases (He, Ne and Ar) relative to Kr and Xe, normalized to the phase Q composition. Nitrogen isotopic data together with ⁴⁰Ar/³⁶Ar ratios indicate mixing between a ¹⁵N-rich component (δ¹⁵N = +1000‰), terrestrial N, and an isotopically normal, chondritic N.Bencubbin and related ¹⁵N-rich meteorites of the CR clan do not show stable isotope (H and C) anomalies, precluding contribution of a nucleosynthetic component as the source of ¹⁵N enrichments. This leaves two possibilities, trapping of an ancient, highly fractionated atmosphere, or degassing of a primitive, isotopically unequilibrated, nitrogen component. Although the first possibility cannot be excluded, we favor the contribution of primitive material in the light of the recent finding of extremely ¹⁵N-rich anhydrous clasts in the CB/CH Isheyevo meteorite. This unequilibrated material, probably carried by the impactor, could have been insoluble organic matter extremely rich in ¹⁵N and hosting isotopically Q-like noble gases, possibly from the outer solar system.     

The Kaidun chondrite breccia: Petrology, oxygen isotopes, and trace element abundances

Oxygen isotope and trace element data for 13 samples of the Kaidun chondritic breccia reaffirm the complex polymict nature of this unique meteorite. Bulk Kaidun samples most closely resemble CR chondrites, but the matrix is CI-like. Two separated clasts are CR-like but have some properties that resemble CM, two clasts are enstatite chondrites (one EL and one EH), one clast is an aubrite-like metal-rich impact melt, and one clast is a unique layered olivine-bearing pyroxenite with the isotopic composition of an aubrite. Yet, although each clast resembles a known meteorite group, all deviate in some respect from the norms for those groups. Collectively, Kaidun has sampled materials not yet represented in the world meteorite collections and which greatly extend the definitions of known meteorite groups. Phyllosilicates in Kaidun span a very wide range in composition and vary from clast to clast, suggesting that the aqueous alteration experienced by the clasts predated assembly of the Kaidun parent body.     

Noble-gas-rich separates from ordinary chondrites

Acid-resistant residues were prepared by HCl-HF demineralization of three H-type ordinary chondrites: Brownfield 1937 (H3), Dimmitt (H3,4), and Estacado (H6). These residues were found to contain a large proportion of the planetary-type trapped Ar, Kr, and Xe in the meteorites. The similarity of these acid residues to those from carbonaceous chondrites and LL-type ordinary chondrites suggests that the same phase carries the trapped noble gases in all these diverse meteorite types. Because the H group represents a large fraction of all meteorites, this result indicates that the gas-rich carrier phase is as universal as the trapped noble-gas component itself. When treated with an oxidizing etchant, the acid residues lost almost all their complement of noble gases. In addition, the Xe in at least one oxidized residue, from Dimmitt, displayed isotopic anomalies of the type known as CCFX or DME-Xe, which is characterized by simultaneous excesses of both the lightest and heaviest isotopes. The anomaly in the Dimmitt sample differs from that observed in carbonaceous-chondrite samples, however, in the relative proportions of the light- and heavy-isotope excesses.The results of this study do not show an inverse correlation between trapped ${}^{20}\text{Ne}{}^{36}\text{Ar}$ and trapped ³⁶Ar abundance, as has been reported for acid-resistant residues from LL-chondrites. The results of this work therefore fail to support the hypothesis that meteoritic trapped noble gas abundances were established at the time of condensation.     

Neon and argon in the Allende meteorite

Trapped and cosmogenic Ne and Ar were measured in Ca,Al-rich aggregates and chondrules, mafic chondrules, and bulk and matrix samples from the Allende C3V chondritic meteorite to investigate the possible occurrence of anomalous isotopic compositions of noble gases that would correlate with oxygen or magnesium isotopic anomalies previously found in this meteorite.Large enrichments of both ²²Ne and ³⁶Ar were observed in low-temperature release fractions from several Ca,Al-rich inclusions, but the enrichments are consistent with galactic cosmic-ray production of ²²Ne by spallation from sodium and ³⁶Ar by neutron capture on chlorine. Trapped neon in matrix samples is comprised of two distinctive compositions, with (²⁰Ne/²²Ne)_t equal to 8.7 ± 0.1 and 10.4 ± 1.0, that appear to correlate with the two gas-rich trace phases chromite/carbon and ‘Q’ described by Lewis et al. (1975). Several Ca,Al-rich aggregates which have high contents of the volatile elements Na, Cl, K, and Rb also contain trapped neon. However, no neon-E has been identified in any of the samples studied, including samples of several inclusions known to contain isotopically anomalous oxygen and magnesium.     

Cosmic-ray exposure ages of four acapulcoites and two differentiated achondrites and evidence for a two-layer structure of the acapulcoite/lodranite parent asteroid

We determined the He, Ne, and Ar isotopic abundances in the four acapulcoites Dhofar (DHO) 125, DHO 290, DHO 312, and Graves Nunataks 98028, the metal-rich diogenite Northwest Africa (NWA) 1982, and a unique achondrite, NWA 1058, that resembles the acapulcoites in its chemical composition. The noble gases in these meteorites consist of three components: trapped gases, cosmic-ray produced nuclides, and nuclides produced by K, Th, and U decay. The four acapulcoites yield cosmic-ray exposure (CRE) ages in the range of 5.0-5.7 Ma and confirm earlier conclusions concerning break-up of all acapulcoites from a common S-type parent asteroid, possibly in three events 4.9, 5.9, and 14.8 Ma ago. We also discuss the other characteristics (mineralogy, chemistry, formation ages, and oxygen and trapped noble gas isotopes) of all other acapulcoites and their relatives, the lodranites. We propose that the acapulcoite/lodranite parent asteroid had a shell structure similar to that of the H chondrites: The less metamorphosed acapulcoites correspond to the H3 and H4 chondrites and originate from the exterior layers, whereas the more severely metamorphosed lodranites, similar to the H5 and H6 chondrites, represent the inner regions of their parent body. Ungrouped achondrite NWA 1982, probably a diogenite, shows a CRE age of 18.9 ± 2.0 Ma that falls on the major exposure age cluster of the diogenites. The unique achondrite NWA 1058 differs in cosmic-ray exposure age (38.9 ± 4.0 Ma) and in oxygen-isotopic composition from the acapulcoites and lodranites and is probably a winonaite.     

Origin of fossil meteorites from Ordovician limestone in Sweden

Based on the analysis of data in [1, 2] on the concentrations of noble gases and the cosmic ray exposure age (CREA) of chromite grains in fossil meteorites, it was demonstrated in [3] that the distributions of gas concentrations and cosmic ray exposure ages can be explained under the assumption of the fall of a single meteorite in the form of a meteorite shower in southern Sweden less than 0.2 Ma after the catastrophic destruction of the parental body (asteroid) of L chondrites in space at approximately 470 Ma. This assumption differs from the conclusion in [1, 2, 4] about the long-lasting (for 1–2 Ma) delivery of L chondrites to the Earth, with the intensity of the flux of this material one to two orders of magnitude greater than now. The analysis of newly obtained data on samples from the Brunflo fossil meteorite [5] corroborates the hypothesis of a meteorite shower produced by the fall of a single meteorite. The possible reason for the detected correlations between the cosmic ray exposure ages of meteorites and the masses of the samples with the ²⁰Ne concentrations can be the occurrence of Ne of anomalous isotopic composition in the meteorites.     

Adsorption of xenon ions onto defects in organic surfaces: Implications for the origin and the nature of organics in primitive meteorites

Noble gases trapped in primitive meteorites are quantitatively hosted by a poorly defined organic phase, labeled phase Q. Xenon is enriched in heavy isotopes by +1.30 ± 0.06% per atomic mass unit (amu, 1σ) in phase Q relative to solar. To understand the origin of this fractionation, we have performed adsorption experiments of xenon atoms and ions, ionized in a radiofrequency plasma. Within the reaction vessel, anthracite was heated and the resulting smoke deposited onto the walls of the vessel, resulting in carbon-rich films. Xenon was trapped in the carbon films either as ions in the ionization zone of the vessel, or as neutral atoms outside this zone. Xenon trapped as ionic Xe is tightly bound and is enriched by +1.36 ± 0.05%/amu (1σ) in heavy isotopes, reproducing the isotopic fractionation of xenon trapped in phase Q relative to solar. Neutral xenon is more loosely trapped, is in much lower concentration, and is not isotopically fractionated. Ionized conditions allow the constant xenon isotopic composition observed in meteorite during stepwise heating release to be reproduced. Furthermore, the trapping efficiency of Xe⁺ estimated from these experiments is consistent with the high xenon concentration measured in phase Q of primitives meteorites.Xenon was not trapped in the film by implantation because the energies of the incident Xe atoms and ions were far too low (<1 eV). From the difference of behavior between ionic and neutral forms, we propose that xenon ions were trapped via chemical bonding at the surface of the newly created C-rich film. The observed mass-dependent fractionation of xenon is unlikely to have occurred in the gas phase. It is more probably related to variations in chemical bonding strengths of Xe isotopes as chemical bonds involving heavy Xe isotopes are more stable than those involving light ones. For young stars, including the young Sun, photons emitted in the far UV energy range able to ionize noble gases (<100 nm) were orders of magnitude more abundant than for the Present-day Sun, allowing efficient ionization of gaseous species. A way to achieve Q-noble gas fractionation and trapping was UV irradiation by nearby young stars from O/B association of the surface of growing organic grains in the outer part of the solar system or by the young Sun at the edge of the disk.     

Cosmic ray exposure age and time of formation of a new meteorite,Dhofar 007 achondrite from Oman: A rock fragment from the asteroid Vesta

The isotopic composition of noble gases was investigated in the Dhofar 007 meteorite. Petrographic and mineralogical observations suggested that it is a brecciated cumulate eucrite with high contents of siderophile elements. The concentrations of noble gases in Dhofar 007 are identical to those of other eucrites. Its cosmic ray exposure age was estimated as 11.8 ± 0.8 Ma, which coincides with a maximum on the histogram of comic ray exposure ages of eucrite meteorites. It can be supposed that, similar to other eucrites, Dhofar 007 was ejected from the surface of their parent body (presumably, asteroid Vesta) about 12.0 Ma ago. The crystallization age of the Dhofar 007 eucrite was estimated from the ratio of plutonogenic Xe to Nd as 4476 ± 22 Ma. The potassium-argon age is much younger, 3.7–4.1 Ga, which indicates partial loss of radiogenic argon during the history of the meteorite, most likely related to impact metamorphic events.     

The influence of cosmic-ray production on extinct nuclide systems

Variations in the atomic abundances of ⁵³Cr, ⁹²Zr, ⁹⁸Ru, ⁹⁹Ru, and ¹⁸²W in meteorites and lunar samples relative to terrestrial values may imply the early decay of radioactive ⁵³Mn, ⁹²Nb, ⁹⁸Tc, ⁹⁹Tc and ¹⁸²Hf, respectively. From this one can deduce nucleosynthetic sites and early solar system timescales. Because these effects are very small, production and consumption of the respective isotopes by cosmic-ray interactions is a concern. It has recently been demonstrated that ¹⁸²W production by neutron capture reactions on ¹⁸¹Ta is crucial for most lunar samples (Leya et al., 2000a). In this study the neutron fluence of each sample was estimated from its nominal cosmic-ray exposure age as deduced from noble gas data. This approach overestimates the true cosmogenic isotopic shift for samples that might have been irradiated very close to the regolith surface. Here we therefore combine our model calculations with the neutron dose proxies ¹⁵⁷Gd/¹⁵⁸Gd and ¹⁴⁹Sm/¹⁵⁰Sm. This allows us to accurately correct the measured W isotopic data for cosmic-ray induced shifts without the explicit knowledge of the exposure age or the shielding depth of the sample simply by measuring ¹⁵⁷Gd/¹⁵⁸Gd and/or ¹⁴⁹Sm/¹⁵⁰Sm in an aliquot. In addition we present new model results for the GCR-induced effects on ⁵³Mn-⁵³Cr, ⁹²Nb-⁹²Zr and ⁹⁸Tc-⁹⁹Tc-⁹⁸Ru-⁹⁹Ru. For each of these systems, except Tc-Ru, a proper cosmic-ray dose proxy is given, permitting the accurate correction of measured isotopic ratios for cosmogenic contributions.     

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.     

Isotopic composition of silicon in meteorites

Samples of bulk meteorites show only mass-dependent fractionation of silicon isotopes. No isotopic anomalies were found. The variation of the ratios ²⁹Si/²⁸Si and ³⁰Si/²⁸Si over the meteorite classes is small; 1%. per mass unit difference. The average Si isotopic composition for each class of meteorites is identical, within analytical uncertainties. This is quite unlike O, whose anomalous isotopic abundances in bulk samples differentiate among the classes of meteorites. The overlapping abundance ranges of Si isotopes among many classes of meteorites suggest closed-system behavior for this element prior to meteorite accretion and allow calculation of an average solar system Si isotope composition.     

Fission-track ages of four meteorites

A method for selective annealing of cosmic-ray tracks has been developed, permitting determination of fission-track ages in the presence of a large background of cosmic-ray tracks. The mesosiderite Bondoc contains 41 fission tracks/cm², of which about 75% are due to neutron-induced fission of U²³⁵ during cosmic-ray exposure. Its net fission-track age is 140 ± 40 Myr, nearly identical to its cosmic-ray exposure age of 150 Myr. The mesosiderite Mincy has a fission-track age of 1500 ± 400 Myr.Nakhla (nakhlite) contains an excess of apparent fission tracks, which may be either genuine fission tracks from Pu²⁴⁴ or etch pits mimicking fission tracks in length, thermal stability, random orientation, and other characteristics. On the assumption that they are fission tracks, the Pu²⁴⁴/U²³⁸ ratio at the onset of track retention in Nakhla was (3.1 ± 1.3) × 10^?3, nearly an order of magnitude lower than the initial solar system ratio. This may reflect a chemical fractionation of Pu and U, or a late impact or magmatic event. Different minerals of the Washougal howardite have different Pu²⁴⁴/U²³⁸ ratios, from (24 ± 7) × 10^?3 to (2.3 ± 0.7) × 10^?3. This may imply a succession of impacts over a period of time. Additionally, Pu and U may have been chemically fractionated from each other in this meteorite.Shocked meteorites show no consistent pattern in the retentivity of fission tracks and of fissiogenic or radiogenic noble gases. Some meteorites, e.g. Bondoc, Serra de Magé, and Mincy, retain gases more completely than tracks; others, e.g. Nakhla and Allende, retain them less completely.Uranium was determined in feldspar and/or pyroxene from 19 Ca-rich achondrites and mesosiderites. For most, only upper limits of 0.01–0.03 ppb were obtained. Apparently the uranium in these meteorites resides almost exclusively in minor phases, as in terrestrial and lunar rocks.     

Helium,neon, and argon in the iron meteorites Dongling,Nantan and Ningbo

The light noble gases He, Ne and Ar have been measured in the iron meteorites Dongling, Nantan and Ningbo. Dongling and Ningbo show a deficit of cosmic-ray that produced³He of ca. 30% and 10%, respectively, which is argued to be caused by the loss of³H (tritium) from the meteoroids during the time of their exposure to the cosmic radiation. Nantan has the lowest content of noble gases as yet reported for any iron meteorite. Cosmogenic³He and³⁸Ar are only about 1/5000 of those in Dongling which has particularly interesting implications if the two meteorites belong to the same fall^[2]. In addition, Nantan contains nonspallogenic⁴He which we believe to be of radiogenic origin. This radiogenic⁴He, together with a U-content of 2.6×10⁻¹¹ g/g^[20] yields a⁴He retention age close to the cosmic-ray exposure age of Dongling. If Dongling and Nantan were part of the same meteoroid^[2], this result would indicate that He retention in the meteoroid age were 4,500 Ma, a U-content of less than 7.2×10⁻¹³ g/g is required to explain the non-cosmogenic₄He present. An upper limit to the number of transuranium or superheavy-element atoms which have decayed by α-emission in Nantan since onset of He retention is 2×10¹⁰ per gram.     

Formation of Pt-bearing Western Pana pluton on the Kola Peninsula: Fluid regime as deduced from helium and argon isotopic compositions

The distribution of He and Ar isotopes has been studied in 41 rock samples and seven monomineralic fractions from ore-bearing layered units and poorly differentiated host gabbronorite of the Western Pana mafic–ultramafic pluton on the Kola Peninsula. The gases assigned for mass-spectrometric analysis were released by means of whole-rock sample melting and by comminution mainly from fluid microinclusions. The data show that the present-day isotopic composition of noble gases in rocks from the pluton is caused by many factors: the degree of melt degassing, various concentrations and retention of the trapped isotopes, the contents of radioactive elements, and the generation and loss of radiogenic gases. The hypabyssal conditions of pluton formation facilitate the loss of primary mantle-derived volatile components and the dilution of magmatic fluid with near-surface paleometeoric waters containing air dissolved therein. The correlation of noble gas isotopes and ore-forming chemical elements does not suggest derivation of the latter from crustal material and evidences their mantle origin. Variations in the geochemical indices of the gas corroborate previously established or proposed multistage formation of the pluton, mainly, the autometamorphic character of postmagmatic processes and the participation of fluids in ore formation.     

Do lunar and meteoritic archives record temporal variations in the composition of solar wind noble gases and nitrogen? A reassessment in the light of Genesis data

Since about half a century samples from the lunar and asteroidal regoliths been used to derive information about elemental and isotopic composition and other properties of the present and past solar wind, predominantly for the noble gases and nitrogen. Secular changes of several important compositional parameters in the solar wind were proposed, as was a likely secular decrease of the solar wind flux. In 2004 NASA’s Genesis mission returned samples which had been exposed to the solar wind for almost 2.5 years. Their analyses resulted in an unprecendented accuracy for the isotopic and elemental composition of several elements in the solar wind, including noble gases, O and N. The Genesis data therefore also allow to re-evaluate the lunar and meteorite data, which is done here. In particular, claims for long-term changes of solar wind composition are reviewed.Outermost grain layers from relatively recently irradiated lunar regolith samples conserve the true isotopic ratios of implanted solar wind species. This conclusion had been made before Genesis based on the agreement of He and Ne isotopic data measured in the aluminum foils exposed to the solar wind on the Moon during the Apollo missions with data obtained in the first gas release fractions of stepwise in-vacuo etch experiments. Genesis data allowed to strengthen this conclusion and to extend it to all five noble gases. Minor variations in the isotopic compositions of implanted solar noble gases between relatively recently irradiated samples (<100 Ma) and samples irradiated billions of years ago are very likely the result of isotopic fractionation processes that happened after trapping of the gases rather than indicative of true secular changes in the solar wind composition. This is particularly important for the ³He/⁴He ratio, whose constancy over billions of years indicates that hardly any ³He produced as transient product of the pp-chains has been mixed from the solar interior into its outer convective zone. The He isotopic composition measured in the present-day solar wind therefore is identical to the (D + ³He)/⁴He ratio at the start of the suns’s main sequence phase and hence can be used to determine the protosolar D/H ratio.Genesis settled the long-standing controversy on the isotopic composition of nitrogen in lunar regolith samples. The ¹⁵N/¹⁴N ratio in the solar wind as measured by Genesis is lower than in any lunar sample. This proves that nitrogen in regolith samples is dominated by non-solar sources. A postulated secular increase of ¹⁵N/¹⁴N by some 30% over the past few Ga is not tenable any longer. Genesis also provided accurate data on the isotopic composition of oxygen in the solar wind, invaluable for cosmochemisty. These data superseded but essentially confirmed one value – and disproved a second one – derived from lunar regolith samples shortly prior to Genesis.Genesis also confirmed prior conclusions that lunar regolith samples essentially conserve the true elemental ratios of the heavy noble gases in the solar wind (Ar/Kr, Kr/Xe). Several secular changes of elemental abundances of noble gases in the solar wind had been proposed based on lunar and meteoritic data. I argue here that lunar data – in concert with Genesis – provide convincing evidence only for a long-term decrease of the Kr/Xe ratio by almost a factor of two over the past several Ga. It appears that the enhancement of abundances of elements with a low first ionisation potential in the solar wind (FIP effect) changed with time.Finally, Genesis allows a somewhat improved comparison of the present-day flux of solar wind Kr and Xe with the total amount of heavy solar wind noble gases in the lunar regolith. It remains unclear whether the past solar wind flux has been several times higher on average than it is today.     

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.