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.     

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.     

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.     

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.     

Coupled Cu and O excesses in chondrites

Recent developments in multiple-collector magnetic-sector ICP-MS (inductively coupled plasma-mass spectrometry) have permitted the relative abundances of the two isotopes 63 and 65 of copper to be measured with unprecedented precision (40 ppm). Here, we report Cu isotopic variations among eight carbonaceous chondrites (CCs) from the CI, CM, CO, and CV groups and the presently ungrouped Tagish Lake, and 10 ordinary chondrites (OCs) from the H, L, and LL groups. The widest isotopic range of ∼0.8‰ per a.m.u. is observed for the carbonaceous chondrites. Copper in carbonaceous chondrites becomes isotopically lighter with petrologic type in the order 1 to 3 but seems extremely homogeneous for each type. The Cu isotopic composition of Tagish Lake confirms its other characteristics that are intermediate between CI and CM. In three of the groups (CI-CM-CO), as well as for Tagish Lake, ⁶³Cu excess over terrestrial mantle abundances correlates well with ¹⁶O excess. For all four groups, ⁶³Cu excess also correlates remarkably well with elemental refractory/volatile ratios (e.g., Ca/Mn). For ordinary chondrites, small differences exist between the H, L, and LL groups, with Cu becoming isotopically heavier in that order. Equilibrated and unequilibrated samples, however, exhibit the same Cu isotopic signature within each group. Although the range of Cu isotopic compositions in ordinary chondrites is smaller than in carbonaceous chondrites, ⁶³Cu excesses still correlate with ¹⁶O excesses. The observed trends of isotopic variation seem incompatible with a single-stage fractionation process by either volatilization or low-temperature metamorphism. The correlations between ⁶³Cu excesses and ¹⁶O excesses suggest the presence of at least two and perhaps three isotopically distinct Cu reservoirs in the early Solar System: (1) an Earth-like reservoir common to the CI and LL probably representing the main Cu stock of the inner Solar System, (2) a reservoir present in all carbonaceous chondrites, but most abundant in CV, with large ⁶³Cu and ¹⁶O excesses (this reservoir is probably hosted in refractory material), and (3) possibly a third reservoir present in ordinary chondrites. The OC trend may also be explained as a mixture of the first two Cu reservoirs if its oxygen was first equilibrated with nebular gas. The coexistence of ⁶³Cu and ¹⁶O excesses in the same component raises the issue of how volatile Cu was preserved in refractory material. A strong correlation between ⁶³Cu/⁶⁵Cu and Ni/Cu ratios suggests that ⁶³Cu excess may have originated as more refractory ⁶³Ni (T_1/2 = 100 yr) upon irradiation of refractory grains by electromagnetic flares and particle bursts during the T-Tauri phase of the Sun.     

Xenon isotopes in size separated nanodiamonds from Efremovka: Xe*, Xe-P3, and Xe-P6

Xenon isotopic data were acquired by high resolution step pyrolysis and combined step pyrolysis/combustion of aliquots of size separated nanodiamonds. ¹²⁹Xe excess (¹²⁹Xe*) from in situ decay of ¹²⁹I is preferentially associated with the larger grain size separates. This observation rules out trapping by recoil from surrounding material. The releases of Xe-P3 and ¹²⁹Xe occur in the same low temperature pyrolysis steps and exhibit similar distributions among the size separates. These observations imply a common site for the components and, in consequence, suggest a common incorporation event.Whether one component or two, our observations require that ¹²⁹Xe* and Xe-P3 were incorporated into a subpopulation of nanodiamonds before nanodiamonds were mixed and incorporated into parent bodies. Their susceptibilities to loss during heating in the laboratory are similar, but the ratio of ¹²⁹Xe* to Xe-P3 varies among nanodiamond separates from different meteorites (literature data). We conclude that the ¹²⁹Xe* we observe today was present as ¹²⁹I during parent body processing. Furthermore, the range of ¹²⁹Xe*/¹³²Xe_P3 ratios across all the separates requires that even nanodiamonds from CI chondrites were at least 5-10× more rich in Xe-P3 during ¹²⁹I decay than they are today.We present a simple model involving one degassing event per parent body between incorporation of nanodiamonds and final decay of ¹²⁹I. The observed variations among parent bodies require degassing events separated by several ¹²⁹I half lives (∼50Ma), consistent with low-temperature processing on parent bodies but longer than expected for nebular processing. In this model, nanodiamonds from ALHA77307 degassed at an unusually early stage, suggesting they alone may retain the signature of processing in the nebula in their P3 and ¹²⁹Xe* abundances.The isotopic signature associated with Xe-P6 is also found only in the larger size separates. Concentration of Xe-HL increases with increasing grain size, but its relative abundance with respect to Xe-P3 and P6 is higher in smaller grain-size fractions. We argue that Xe-P6 is best seen as a variant of Xe-HL, and that they are both mixtures of a “normal” component akin to solar xenon and a slightly variable exotic component. We show that both current models of Xe-H formation can account for the observed variability, and propose a scenario according to which Xe-HL and P6 were implanted into separate diamond populations before incorporation of Xe-P3 and ¹²⁹I.     

Isotopic composition of xenon in petroleum from the shell bullwinkle field

We have measured the abundance and isotopic composition of xenon in petroleum samples from the Shell Bullwinkle Field off the coast of Louisiana. We used an oxidation and purification procedure designed to insure complete extraction and clean up of xenon from the petroleum. The xenon isotopic composition was found to be similar to the atmospheric value for one petroleum sample. While the results of the second sample suggest possible enrichment of the heavier isotopes, the errors associated with these excesses preclude a definitive statement to that effect. No monoisotopic enrichment in¹²⁹Xe was detected in either sample, the presence of which might have allowed us to deduce the petroleum age. Our results represent only the second xenon measurement from petroleum, and the concentrations are within the range of values published in the earlier report.     

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.     

Hydrogen Isotopes of Glassy and Phyllosilicate Spherules in AI Rais （CR） and Orgueil （CI） Chondrites

The hydroxyl in phyllosilicate minerals is the most common occurrence of water in primitive meteorites.Direct hydrogen isotopic analysis of this water component using an ion microprobe has been made in some glassy or phyllosilicate spherules from the A1 Rais (CR) and Orgueil (CI) chondrites. The spherules from A1 Rais show largedeuterium excesses (δD= 200- 800‰) relative to terrestrial standards, whereas deuterium-enrichments in the spherules from Orgueil are much smaller (δD= 40- 130‰). The phyllosilicate spherules are products of aqueous alteration of glassy precursors. In A1 Rais the phyllosilicate spherules have relatively higher δD values than the glassy ones, indicating that water introduced during aqueous alteration was deuterium-enriched. The deuterium-enrichments in the phyllosilicate spherules from Orgueil could result from isotopic exchange under thermodynamic conditions within the solar nebula. The much larger δD excesses of the A1 Rais spherules, however, cannot be attributed to the similar process;instead, an interstellar origin needs to be invoked.     

Hf-W isotope systematics of chondrites, eucrites, and martian meteorites: Chronology of core formation and early mantle differentiation in Vesta and Mars

The timescale of accretion and differentiation of asteroids and the terrestrial planets can be constrained using the extinct ¹⁸²Hf-¹⁸²W isotope system. We present new Hf-W data for seven carbonaceous chondrites, five eucrites, and three shergottites. The W isotope data for the carbonaceous chondrites agree with the previously revised ¹⁸²W/¹⁸⁴W of chondrites, and the combined chondrite data yield an improved ?_W value for chondrites of −1.9 ± 0.1 relative to the terrestrial standard. New Hf-W data for the eucrites, in combination with published results, indicate that mantle differentiation in the eucrite parent body (Vesta) occurred at 4563.2 ± 1.4 Ma and suggest that core formation took place 0.9 ± 0.3 Myr before mantle differentiation. Core formation in asteroids within the first ∼5 Myr of the solar system is consistent with the timescales deduced from W isotope data of iron meteorites. New W isotope data for the three basaltic shergottites EETA 79001, DaG 476, and SAU 051, in combination with published ¹⁸²W and ¹⁴²Nd data for Martian meteorites reveal the preservation of three early formed mantle reservoirs in Mars. One reservoir (Shergottite group), represented by Zagami, ALH77005, Shergotty, EETA 79001, and possibly SAU 051, is characterized by chondritic ¹⁴²Nd abundances and elevated ?_W values of ∼0.4. The ¹⁸²W excess of this mantle reservoir results from core formation. Another mantle reservoir (NC group) is sampled by Nakhla, Lafayette, and Chassigny and shows coupled ¹⁴²Nd-¹⁸²W excesses of 0.5-1 and 2-3 ? units, respectively. Formation of this mantle reservoir occurred 10-20 Myr after CAI condensation. Since the end of core formation is constrained to 7-15 Myr, a time difference between early silicate mantle differentiation and core formation is not resolvable for Mars. A third early formed mantle reservoir (DaG group) is represented by DaG 476 (and possibly SAU 051) and shows elevated ¹⁴²Nd/¹⁴⁴Nd ratios of 0.5-0.7 ? units and ?_W values that are indistinguishable from the Shergottite group. The time of separation of this third reservoir can be constrained to 50-150 Myr after the start of the solar system. Preservation of these early formed mantle reservoirs indicates limited convective mixing in the Martian mantle as early as ∼15 Myr after CAI condensation and suggests that since this time no giant impact occurred on Mars that could have led to mantle homogenization. Given that core formation in planetesimals was completed within the first ∼5 Myr of the solar system, it is most likely that Mars and Earth accreted from pre-differentiated planetesimals. The metal cores of Mars and Earth, however, cannot have formed by simply combining cores from these pre-differentiated planetesimals. The ¹⁸²W/¹⁸⁴W ratios of the Martian and terrestrial mantles require late effective removal of radiogenic ¹⁸²W, strongly suggesting the existence of magma oceans on both planets. Large impacts were probably the main heat source that generated magma oceans and led to the formation metallic cores in the terrestrial planets. In contrast, decay of short-lived ²⁶Al and ⁶⁰Fe were important heat sources for melting and core formation in asteroids.     

The sources of water in Martian meteorites: clues from hydrogen isotopes

H isotope measurements of carbonate, phosphate, feldspathic and mafic glasses, and post-stishovite silica phase in the shergottites Zagami, Shergotty, SaU 005, DaG 476, ALHA 77005 and EETA 79001, as well as in Chassigny and ALH 84001, show that all these phases contain deuterium-enriched water of extraterrestrial origin. The minerals and glasses analyzed may contain an initial primary hydrogen component, but their isotopic composition was modified to varying degrees by three different processes: interaction with a fractionated exchangeable water reservoir on Mars, hydrogen devolatilization by impact melting, and terrestrial contamination. Positive correlations between δD and water abundance in feldspathic glass and post-stishovite silica in Zagami, Shergotty, and SaU 005 is indicative of mixing of a high δD component (3000-4000‰) and a less abundant, low δD component (∼0‰). The high δD component is primarily derived from the Martian exchangable reservoir, but may also have been influenced by isotopic fractionation associated with shock-induced hydrogen loss. The low δD component is either a terrestrial contaminant or a primary “magmatic” component. The negative correlation between δD and water abundances in mafic and feldspathic glasses in ALH 84001, ALHA 77005, and EETA 79001 is consistent with the addition of a low δD terrestrial contaminant to a less abundant high-deuterium Martian component. The low δD of magmatic glass in melt inclusions suggests that the δD of Martian parent magma was low and that the initial H isotope signature of Mars may be similar to that of Earth.     

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.     

Heavily fractionated noble gases in an acid residue from the Klein Glacier 98300 EH3 chondrite

Noble gases were measured both in bulk samples (stepped pyrolysis and total extraction) and in a HF/HCl residue (stepped pyrolysis and combustion) from the Klein Glacier (KLE) 98300 EH3 chondrite. Like the bulk meteorite and as seen in previous studies of bulk type 3 E chondrites (“sub-Q”), the acid residue contains elementally fractionated primordial noble gases. As we show here, isotopically these are like those in phase-Q of primitive meteorites, but elementally they are heavily fractionated relative to these. The observed noble gases are different from “normal” Q noble gases also with respect to release patterns, which are similar to those of Ar-rich noble gases in anhydrous carbonaceous chondrites and unequilibrated ordinary chondrites (with also similar isotopic compositions). While we cannot completely rule out a role for parent body processes such as thermal and shock metamorphism (including a later thermal event) in creating the fractionated elemental compositions, parent body processes in general seem not be able to account for the distinct release patterns from those of normal Q noble gases. The fractionated gases may have originated from ion implantation from a nebular plasma as has been suggested for other types of primordial noble gases, including Q, Ar-rich, and ureilite noble gases. With solar starting composition, the corresponding effective electron temperature is about 5000 K. This is lower than inferred for other primordial noble gases (10,000-6000 K). Thus, if ion implantation from a solar composition reservoir was a common process for the acquisition of primordial gas, electron temperatures in the early solar system must have varied spatially or temporally between 10,000 and 5000 K.Neon and xenon isotopic ratios of the residue suggest the presence of presolar silicon carbide and diamond in abundances lower than in the Qingzhen EH3 and Indarch EH4 chondrites. Parent body processes including thermal and shock metamorphism and a late thermal event also cannot be responsible for the low abundances of presolar grains. KLE 98300 may have started out with smaller amounts of presolar grains than Qingzhen and Indarch.     

Water-extractable and exchangeable phosphate in Martian and carbonaceous chondrite meteorites and in planetary soil analogs

Aqueous extraction contributes to the formation and weathering of planetary materials and renders electrolytes such as phosphate available for biology. In this context, the solubility of phosphate is measured in planetary materials, represented by the Mars meteorites Nakhla, Dar al Gani 476 (DaG 476), Elephant Morraine 79001 (EETA 79001), and terrestrial analogs, and in the Murchison CM2 and Allende CV3 carbonaceous chondrites. The Mars meteorites contain high levels of phosphate that is readily extracted by water, up to 15 mg kg⁻¹ in Nakhla and DaG 476 and 38 mg kg⁻¹ in EETA 79001, while the terrestrial analogs and the carbonaceous chondrites contain 0.5 to 6 mg kg⁻¹. Correspondingly, high phosphate concentrations of 4 to >28 mg L⁻¹ are obtained in extracts of the Mars meteorites at high solid/solution ratios, exceeding the concentrations of 0.4 to 2.0 mg L⁻¹ in the extracts of the terrestrial analogs. A wide range of planetary conditions, including N₂ and CO₂ atmospheres, solid/solution ratios of 0.01 to 1.0 kg L⁻¹, extraction times of 1 to 21 d, and temperatures of 20 to 121°C affect the amounts of extractable phosphate by factors of only 2 to 5 in most materials. Phosphate-fixing capacity and exchangeable phosphate are assessed by the isotopic exchange kinetics (IEK) method, which quantifies the amount of P isotopically exchangeable within 1 min (E_1min) and between 1 min and 3 months (E_1min-3m) and the amount of P that cannot be exchanged within 3 months (E_>3m). The IEK results show that the DaG 476 Mars meteorite and terrestrial analogs have low P-fixing capacities, while the carbonaceous chondrites have high P-fixing capacities. Aqueous processing under early planetary CO₂ atmospheres has large effects on the available phosphate. For example, the fraction of total P that is exchangeable in 3 months increases from 1.6 to 11%, 13 to 51.6%, and 43.9 to 90.4% in the DaG 476 Mars meteorite, Allende, and Murchison, respectively. The results show that solutions with high phosphate concentrations can form in the pores of planetary lava ash and basalts and in carbonaceous asteroids and meteorites. These solutions can help prebiotic synthesis and early microbial nutrition. The Martian and carbonaceous chondrite materials contain sufficient phosphate for space-based agriculture.     

History and origin of aubrites

The cosmic ray exposure (CRE) ages of aubrites are among the longest of stone meteorites. New aubrites have been recovered in Antarctica, and these meteorites permit a substantial extension of the database on CRE ages, compositional characteristics, and regolith histories. We report He, Ne, and Ar isotopic abundances of nine aubrites and discuss the compositional data, the CRE ages, and regolith histories of this class of achondrites. A Ne three-isotope correlation reveals a solar-type ratio of ²⁰Ne/²²Ne = 12.1, which is distinct from the present solar wind composition and lower than most ratios observed on the lunar surface. For some aubrites, the cosmic ray-produced noble gas abundances include components produced on the surface of the parent object. The Kr isotopic systematics reveal significant neutron-capture-produced excesses in four aubrites, which is consistent with Sm and Gd isotopic anomalies previously documented in some aubrites. The nominal CRE ages confirm a non-uniform distribution of exposure times, but the evidence for a CRE age cluster appears doubtful. Six meteorites are regolith breccias with solar-type noble gases, and the observed neutron effects indicate a regolith history. ALH aubrites, which were recovered from the same location and are considered to represent a multiple fall, yield differing nominal CRE ages and, if paired, document distinct precompaction histories.     

High-precision osmium isotopes in enstatite and Rumuruti chondrites

Isotopic heterogeneity within the solar nebula has been a long-standing issue. Studies on primitive chondrites and chondrite components for Ba, Sm, Nd, Mo, Ru, Hf, Ti, and Os yielded conflicting results, with some studies suggesting large-scale heterogeneity. Low-grade enstatite and Rumuruti chondrites represent the most extreme ends of the chondrite meteorites in terms of oxidation state, and might thus also present extremes if there is significant isotopic heterogeneity across the region of chondrite formation. Osmium is an ideal tracer because of its multiple isotopes generated by a combination of p-, r-, and s-process and, as a refractory element; it records the earliest stages of condensation.Some grade 3-4 enstatite and Rumuruti chondrites show similar deficits of s-process components as revealed by high-precision Os isotope studies in some low-grade carbonaceous and ordinary chondrites. Enstatite chondrites of grades 5-6 have Os isotopic composition identical within error to terrestrial and solar composition. This supports the view of digestion-resistant presolar grains, most likely SiC, as the major carrier of these anomalies. Destruction of presolar grains during parent body processing, which all high-grade enstatite chondrites, but also some low-grade chondrites seemingly underwent, makes the isotopically anomalous Os accessible for analysis. The magnitude of the anomalies is consistent with the presence of a few ppm of presolar SiC with a highly unusual isotopic composition, produced in a different stellar environment like asymptotic giant branch stars (AGB) and injected into the solar nebula. The presence of similar Os isotopic anomalies throughout all major chondrite groups implies that carriers of Os isotopic anomalies were homogeneously distributed in the solar nebula, at least across the formation region of chondrites.     

The vanadium isotopic composition of L ordinary chondrites

Stable isotopic data of meteorites are critical for understanding the evolution of terrestrial planets. In this study, we report high-precision vanadium (V) isotopic compositions of 11 unequilibrated and equilibrated L chondrites. Our samples show an average δ⁵¹V of ??1.25‰?±?0.38‰ (2SD, n?=?11), which is ~?0.5‰ lighter than that of the bulk silicate Earth constrained by mantle peridotites. Isotopic fractionation in type 3 ordinary chondrites vary from ??1.76‰ to ??1.29‰, whereas the δ⁵¹V of equilibrated chondrites vary from ??1.37‰ to ??1.08‰. δ⁵¹V of L chondrites do not correlate with thermal metamorphism, shock stage, or weathering degree. Future studies are required to explore the reason for V isotope variation in the solar system.     

“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.     

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.     

Non-racemic amino acids in the Murray and Murchison meteorites.

Small (1.0-9.2%) L-enantiomer excesses were found in six alpha-methyl-alpha-amino alkanoic acids from the Murchison (2.8-9.2%) and Murray (1.0-6.0%) carbonaceous chondrites by gas chromatography-mass spectroscopy of their N-trifluoroacetyl or N-pentafluoropropyl isopropyl esters. These amino acids [2-amino-2,3-dimethylpentanoic acid (both diastereomers), isovaline, alpha-methyl norvaline, alpha-methyl valine, and alpha-methyl norleucine] are either unknown or rare in the terrestrial biosphere. Enantiomeric excesses were either not observed in the four alpha-H-alpha-amino alkanoic acids analyzed (alpha-amino-n-butyric acid, norvaline, alanine, and valine) or were attributed to terrestrial contamination. The substantial excess of L-alanine reported by others was not found in the alanine in fractionated extracts of either meteorite. The enantiomeric excesses reported for the alpha-methyl amino acids may be the result of partial photoresolution of racemic mixtures caused by ultraviolet circularly polarized light in the presolar cloud. The alpha-methyl-alpha-amino alkanoic acids could have been significant in the origin of terrestrial homochirality given their resistance to racemization and the possibility for amplification of their enantiomeric excesses suggested by the strong tendency of their polymers to form chiral secondary structure.