Atmospheric and juvenile noble gases in the Skaergaard layered igneous intrusion

Gabbro and diorite from the Skaergaard layered igneous intrusion contain noble gases which are mixtures of atmospheric and juvenile components. Atmospheric noble gases predominate in samples that have undergone extensive oxygen isotope exchange with meteoric-hydrothermal water. The source of the atmospheric noble gas component is inferred to be the hydrothermal circulation system. A juvenile component with ${}^{40}\text{Ar}{}^{36}\text{Ar}\text{≥ 6100}$ and containing fission xenon is also present This component predominates in samples showing unaltered magmatic oxygen isotope compositions. Neon of atmospheric isotopic composition is associated with the juvenile radiogenic ⁴⁰Ar and fission xenon. The source of this second noble gas component may be either the crustal country rock or the upper mantle. If the neon is juvenile primordial neon from a mantle source region, terrestrial primordial ${}^{20}\text{Ne}{}^{22}\text{Ne}$ is the same as atmospheric to within 4%. However, subduction of atmospheric noble gases into the upper mantle may provide an alternate source of neon and other noble gases in the mantle.     

Isotopic anomalies of noble gases in meteorites and their origins—VII. C3V carbonaceous chondrites

Noble gases were measured in bulk samples of the C3V chondrites Grosnaja, Vigarano, and Leoville, and in HF,HCl-insoluble residues before and after etching with HNO₃. The residues were characterized by INAA and SEM. Gas components were determined, directly or by subtraction, for the following fractions: HF,HCl-solubles (?98% of the meteorite), ‘sphase Q’, a poorly characterized trace mineral that is insoluble in HCl-HF but soluble in HNO₃, and an insoluble residue, consisting of ferrichromite, carbonaceous matter, and spinel.Bulk meteorites show some correlation of the noble-gas pattern with McSween's subclasses: two ‘oxidized’ C3V's—Allende (LEWIS et al, 1975) and Grosnaja— have lower Ar/Xe but higher Ne/Xe ratios than the ‘reduced’ C3V's—Vigarano and Leoville—which are transitional to LL3's and C3O chondrites in both respects. An HCl-soluble mineral of high Ar/Xr ratio seems to be responsible. In other respects, the 3 C3V's of this study resemble Allende, with only moderate differences. Phase Q contains most of the Ar, Kr, Xe, but only small amounts of Ne; the etched residues contain planetary Ne ($\text{Ne}{}^{20}\text{Ne}{}^{22}\text{? 8.5}$) and the controversial CCFXe component, enriched in the heavy Xe isotopes ($\text{Xe136}\text{Xe132 ? 0.4–0.5}$). The CCFXe is accompanied by an ‘L-Xe’ component that is enriched in the light Xe isotopes. The proportion of the two is virtually constant in C3V's. as in all other C-chondrites. in contrast to the ~ 2-fold variation in ordinary chondrites.C3V's have systematically higher $\text{Xe}{}^{136}\text{Xe}{}^{132}$ ratios, and hence higher ratios of CCFXe to planetary Xe, than do other chondrite classes. This may reflect some peculiarity in their formation conditions, favoring uptake of CCFXe.     

Sorption of noble gases by solids,with reference to meteorites. III. Sulfides,spinels, and other substances; on the origin of planetary gases

To simulate trapping of noble gases by meteorites, we reacted 15 FeCr or FeCrNi alloy samples with CO, H₂O or H₂S at 350–720 K, in the presence of noble gases. The reaction products, including (Fe,Cr)₂O₃, FeCr₂S₄, FeS, C, and Fe₃C, were analyzed by mass spectrometry, usually after chemical separation by selective solvents. Three carbon samples were prepared by catalytic decomposition of CO or by dehydration of carbohydrates with H₂SO₄.The spinel and carbon samples were similar to those of earlier studies (Yang et al., 1982 and Yang and Anders, 1982), with only minor effects attributable to the presence of Ni. All samples sorted substantial amounts of noble gases, with distribution coefficients of 10^?1–10^?2 cm³ STP/g atm for Xe. On the basis of release temperature three gas components were distinguished: a generally dominant physisorbed component (20–80% of total), and two more strongly bound, chemisorbed and trapped components. Judging from the elemental pattern, the adsorbed components were acquired at the highest noble gas partial pressure encountered by the sample—atmosphere or synthesis vessel.Sulfides, particularly daubréelite, showed three distinctive trends relative to chromite or magnetite: the high-T component was larger, 30–70% of the total; $\text{Ne}\text{Xe}$ ratios were higher, by up to 10², possibly due to preferential diffusion of Ne during synthesis. In one synthesis, at relatively high P, the gases were sorbed with only minimal elemental fractionation, presumably by occlusion.Most of the features of primordial noble gases can be explained in terms of the data and concepts presented in the three papers of this series. The elemental fractionation pattern of Ar, Kr, Xe in meteorites, terrestrial rocks, and planets resembles the adsorption pattern on the solids studied: carbon, spinels, Sulfides, etc. The variation in $\text{Ne}\text{Ar}$ ratio may be explained by preferential diffusion of Ne. The high release temperature of meteoritic noble gases may be explained by transformation of physisorbed to chemisorbed gas, as observed in some experiments. The ready loss of meteoritic heavy gases on surficial oxidation (“Phase Q”) is consistent with adsorption, as is the high abundance. Extrapolation of the limited laboratory data suggests that the observed amounts of noble gases could have been adsorbed from a solar gas at 160–170 K and 10^?6–10^?5 atm, i.e. in the early contraction stages of the solar nebula. The principal unsolved problem is the origin of isotopically anomalous, apparently mass-fractionated noble gases in the Earth's atmosphere and in meteoritic carbon and chromite.     

Titanium isotopic anomalies in meteorites

High-precision analyses of Ti are reported for samples from a variety of meteorite classes. The expanded data base for Allende inclusions still shows Ti isotopic anomalies in every inclusion. All the coarse-grained inclusions give quite similar patterns, but fine-grained inclusions show more variable, and sometimes larger, anomalies. One inclusion, 3675A, was analyzed because others identified it as a possible “FUN” inclusion due to its mass-fractionated Mg. This designation is supported by the significantly more complex Ti isotopic pattern for 3675A compared to all our other Allende inclusions. Available data fail to suggest that any particular Allende mineral phase, including a chromite-carbon fraction from an acid residue, is especially rich in anomalous Ti. We also find anomalous Ti in a bulk sample of a Cl chondrite and in matrix separates from C2 chondrites. The excesses of ⁵⁰Ti are smaller than for Allende inclusions, and subtle differences in Ti isotopic patterns tentatively suggest that parent materials for C1-C2 matrix and Allende inclusions are not directly related. Analyses of chondrules from unequilibrated ordinary chondrites did not yield clear evidence for anomalous Ti, but some “larger than usual” deficits at $\text{50}\text{46}$ give encouragement for future work in this direction. Comparing the magnitude of isotopic shifts at ⁵⁰Ti and ¹⁶O for all these meteorite samples indicates that they are not correlated, but the data do not preclude a correlation between concentrations of “exotic” ⁵⁰Ti and ¹⁶O atoms.Whether or not Allende “FUN” inclusions are considered, at least 4 distinct isotopic components of Ti are required to account for the observed isotopic variations. The Ti data cannot be plausibly explained in terms of an early solar-system particle irradiation; instead, neutron-rich hydrostatic burning within a star is probably responsible for the dominant ⁵⁰Ti anomalies, while s-process mechanisms are viable sources for some of the more subtle Ti variations. We suggest that the Ti anomalies are linked to a diversity of nucleosynthetic sources and the highly refractory behavior of Ti. Therefore, some form of “chemical memory” from the ISM, rather than “late stage supernova injection”, is most likely responsible for the preservation of observed isotopic heterogeneities.     

A 33S Anomaly in the allende meteorite

The isotope ratios ³³S/³²S and ³⁴S/³²S have been measured in sulphur fractions extracted from samples of the meteorites Allende and Eagle Station by leaching at successively greater acid concentrations and higher temperatures. On a three isotope plot of δ³³S$\text{vs}$δ³⁴S most of the data lie on or close to the mass fractionation line. The last fraction of sulphur extracted from a bulk Allende sample lies off the line and has an approximately 1%. excess in the ³³/³²S ratio.Previous searches for anomalous abundance patterns of ³²S, ³³S, ³⁴S and ³⁶S have been reported by HULSTON and THODE (1965a,b), THODE and REES (1971), and REES and THODE (1972). No isotope abundance variations were found, in the meteorite and lunar samples studied, which could not be explained on the basis of either mass dependent isotope fractionation or, in the special case of iron meteorites, cosmic ray production of ³³S and ³⁶S. We report here preliminary results of a renewed search for isotopically anomalous sulphur in which we are concentrating on the Allende and Eagle Station meteorites, both of which contain anomalous oxygen (CLAYTON $\text{et}$$\text{al}$., 1973, 1976). In a first attempt to distinguish between normal sulphur and any possible anomalous sulphur, we have leached both bulk samples and hand separated components of these meteorites with hydrochloric acid.CLAYTON and RAMADURAI (1977) suggested that the presence of isotopically anomalous sulphur would be evidence for the existence of presolar grains which are relics of nucleosynthesis in certain zones of supernova expansion. In particular they suggested that sulphides of titanium are good candidates for isotopic analysis. These are not expected to exist in conventional solar equilibrium condensation sequences, but might be abundant in condensates from silicon burning shells of supernovae. Our chemical procedures were already completed when CLAYTON and RAMADURAI'S suggestions came to our attention and it must be stressed that so far, in all cases but one we have examined only sulphur from sulphides which are decomposed by HC1. Thus we may not have sampled sulphides of the type suggested by CLAYTON and RAMADURAI.All samples of the Allende meteorite were ground finer than 50μm before acid extraction of sulphur. Samples of sulphur were extracted from the various phases of the meteorites by using successively stronger hydrochloric acid leaches, longer times and higher temperatures of reaction. Sulphur initially released as H₂S was successively converted to CdS, Ag₂S and SF₆, this latter compound being analysed mass spectrometrically (THODE and REES, 1971). Analyses of nine SF₆ samples prepared from Ag₂S originally derived from Canyon Diablo troilite were also performed in order to monitor fluorination and mass spectrometry precision and to establish the zero points ofthe isotope variation scales. The results are shown in Table 1. The sulphur contents of the various samples were determined gravimetrically as Ag₂S. The bulk and matrix samples are probably a few percent low because of mechanical losses. The percentages of sulphur in each fraction of a sample extracted during each leaching stage are given in the table. The total sulphur content in the bulk and matrix samples of the Allende meteorite i.e., the sum of the sulphur contents of the individual fractions, varies from 1.8 to 2.08%, the highest percentage being in the matrix. These values compare with about 2 to 2.1% obtained by CLARKE $\text{et}$$\text{al}$. (1970).     

I-Xe studies of individual Allende chondrules

Iodine-xenon studies have been performed on nine Allende chondrules and a sample of oxidized Allende matrix material. The chondrules are all very rich in radiogenic xenon relative to trapped xenon, making it possible to determine a relatively precise model initial iodine composition for each temperature extraction. These model compositions show a total range in variation of about 20 percent, spanning the compositions seen in Bjurbole chondrules. One of the chondrules (chondrule 6) gives a well-defined isochron, with an apparent age .53 ±. 15 m.y. later than Bjurbole whole rock. The rest of the chondrules show a pattern of increasing apparent antiquity with increasing extraction temperature, which could be interpreted as relatively slow cooling (100–200°C/m.y.). Alternatively, poorly-defined plateaus in composition can be seen, perhaps indicative of a few phases with distinct initial iodine compositions (but also temperature-ordered), as has been previously suggested for Allende inclusions. Possible consequences of these interpretations are discussed. Elemental abundances were determined for some elements several months after the irradiation by INAA, and suggest that all the chondrules except chondrule 6 might be pyroxene- or mesostasis-rich. The oxidized matrix sample gives a well-defined isochron with an initial ${}^{129}\text{I}{}^{127}$I ratio higher than any plateaus seen in the chondrules, suggesting that, if this sample is representative of matrix, the matrix pre-dates the chondrules. The initial ${}^{244}\text{Pu}{}^{238}\text{U}$ ratios of the Allende chondrules and 10 Bjurbole chondrules irradiated earlier appear to be consistent with. 004–.007 values quoted for unfractionated material in the early solar nebula.     

26Al, 244Pu, 50Ti,REE, and trace element abundances in hibonite grains from CM and CV meteorites

The ion microprobe was used to measure Ti and Mg isotopes as well as rare earth and other trace elements in ten hibonites from the CM carbonaceous chondrites Murchison, Murray, and Cold Bokkeveld and in two hibonites and Ti-rich pyroxene from the CV chondrite Allende. In hibonites from Murchison and Murray fission track densities were also measured, as were Th and U concentrations. Eight of the hibonites, from all four meteorites, exhibit large Ti isotopic anomalies, particularly in ⁵⁰Ti. Two grains from Murray have ⁵⁰Ti excesses of ~ 10%. At least four nucleosynthetic components are required to account for all the Ti isotopic data. Neutron-rich nuclear statistical equilibrium nucleosynthesis is the most likely process to account for a ⁵⁰Ti-rich component (with ${}^{50}\text{Ti}{}^{49}\text{Ti}\text{\$}\text{̆}\text{20}$). The ion probe Ti isotopic measurements confirm that the solar nebula was isotopically heterogeneous on a small spatial scale and argue for a chemical memory origin of the Ti isotopic anomalies which were probably carried into the solar system in the form of refractory dust grains. However, there is no experimental evidence that such interstellar grains survived the formation of the hibonites. The REE and trace element patterns of the hibonites are similar to those seen in CAIs and can be interpreted in terms of fractionation effects during condensation from a gas of solar composition, thus arguing for a solar system origin of the hibonites. Additional evidence for such an origin is provided by the $\text{Pu}\text{Th}$ ratios, which are ~ 10⁻⁴, and by the Mg isotopic compositions which are normal except for ²⁶Mg1 due to ²⁶Al.Only three out of ten hibonites exhibit ²⁶Mg1, consistent with previous studies which demonstrated the paucity of ²⁶Mg1 in hibonites. Because of the refractory nature of hibonite and the presence of large Ti isotopic effects, we conclude that a heterogeneous distribution of ²⁶Al in the early solar system is the most likely reason. In particular, our observations of δ⁵⁰Ti = 15%. and of an isochron with (${}^{26}\text{Al}{}^{27}\text{Al}\text{)}{}_0\text{= 5 × 10}{}^{\mathrm{-8}}$ in the FUN inclusion HAL are evidence against both late formation and Mg redistribution to explain the lack of ²⁶Al in hibonites.There are no obvious correlations between the Ti isotopic compositions, the presence of ²⁶Mg1, the presence of ²⁴⁴Pu, and the REE and trace element patterns in individual hibonites. This indicates that the anomalous ⁵⁰Ti, as well as ²⁶A1 and ²⁴⁴Pu, were not co-produced in a single astrophysical source, and/or that these nuclides were introduced into the solar nebula by different carriers before being incorporated into the hibonites.     

Isotopic anomalies of noble gases in meteorites and their origins—IV. C3 (Ornans) carbonaceous chondrites

The C3O chondrites Kainsaz, Lancé and Ornans were studied by an acid dissolution technique, to characterize the noble-gas components in 3 mineral fractions: HF, HCl-solubles (99% of the meteorite), chromite and carbon (0.3–0.9%), and ‘phase Q’, a poorly characterized trace mineral (0.05–0.4%) containing most of the Ar, Kr, Xe. For all fractions, gas contents decline in the order Kainsaz > Lancé > Ornans; this trend parallels volatile contents but not heterogeneity of olivine composition or degree of metamorphism and seems to reflect progressively higher condensation temperatures from the solar nebula.Solubles contain nearly unfractionated Xe, and show ${}^{136}\text{Ar}{}^{132}\text{Xe}$ ratios up to 850. Hence the high $\text{Ar}\text{Xe}$ ratios (200–400) of bulk C3O chondrites must be due to an HF-soluble mineral (possibly magnetite). Phase Q contains ordinary planetary gases and a Ne component of ${}^{20}\text{Ne}{}^{22}\text{Ne}\text{= 10.3 ± 0.4.}$Chromite and carbon contain Ne of ${}^{20}\text{Ne}{}^{22}\text{Ne}\text{= 8.6 ± 0.1}$ and ‘CCF’ xenon (a peculiar component of possibly fissiogenic origin, enriched in the heavy isotopes but accompanied by a component enriched in the light isotopes).In all primitive chondrites, both the amount and the chemical separability of CCFXe parallel the abundance of promordial noble gases and other volatiles, such as C, N, Tl, Bi and In. The close correlation of CCFXe with various properties of undoubtedly local origin (volatile content, petrologic type, presence of ferrichromite and carbon, etc.) is more consistent with a local than with an extrasolar origin of this component. A volatile superheavy element seems to be the most plausible source, but the evidence is not conclusive.     

Foreign inclusions in stony meteorites—III. Rare gases and oxygen isotopes in a carbonaceous chondritic xenolith in the Plainview gas-rich chondrite

Measurements of oxygen and rare gas isotopes in a carbonaceous xenolithic inclusion in the Plainview H5 chondrite indicate that the xenolith and Plainview host are of two distinct meteorite types, and that no isotopic exchange has taken place between the two materials since their juxtaposition. The oxygen isotope analysis of the xenolith yields δ-¹⁸O value of 6.5 ± 0.1 % relative to SMOW, a value similar to that of carbonaceous chondrites (C2). Rare gas contents of the xenolith are also similar to those of carbonaceous chondrites. The radiation ages of the xenolith ($\text{2.9 ± 0.4}\text{Myr}$) and the host ($\text{2.8 ± 0.4}\text{Myr}$) are identical.Analyses of the rare gases in a sample of the host material adjacent to the xenolith show that Plainview is gas-rich, i.e., it contains large amounts (52,300 ± 10^?8 cm³ STP/g ⁴He) of solar-type trapped gases.We speculate that carbonaceous chondritic material may be more prevalent in the asteroid belt than previously suspected.     

Rare-gas-rich separates from carbonaceous chondrites

Samples studied were residual, carbonaceous /Alates—a coined word to designate colloids prepared sometimes before and sometimes after acid demineralization—from Murray, Murchison, Cold Bokkeveld (type C2s) and Allende (type CV3) meteorites. Characterization: C2 /Alates, comprising 0.5% of the bulk meteorite are fine-grained (< 100 Å), amorphous, sulfide-free, oxidizable, 95% carbonaceous materials which pyrolyze bimodally at 200–700 and 800–1200°C. Allende /Alates are similar but with traces of inferred spinel and chromite and of sulfur, Rare gas results: Elemental: Release from stepwise heated Murray is bimodal with maximum release and upper temperature peak at 1000°C, probably accompanying chemical reaction. All /Alates studied had very nearly the same elemental concentrations, distinctly planetary in pattern. Isotopic: Trapped neon compositions are unprecedentedly close to Pepin's neon-A corner but nevertheless show signs of complexity, as if accompanied by neon-E. The trapped ³He/⁴He ratio is essentially constant at (1.42 ± 0.2 × 10^?4. The isotopically anomalous heavy noble gases, easily detected in the residues of oxidized /Alates, were not conspicuous in this particular study. Comparison and Chicago results: Concentrations of heavy rare gases in our /Alates agree with concentrations measured directly (as opposed to inferred by difference) in acid resistant residues at Chicago. Alone, our results support the idea of a carbonaceous gas-carrier uniformly present in meteorites of various types, but Chicago characterizations of the samples can apply to both their samples and ours provided that the right amount of gas was lost in the Berkeley procedures to make the uniform gas contents in various samples a coincidence.     

Mineralogy and petrography of HAL,an isotopically-unusual Allende inclusion

A detailed mineralogical study of HAL was initiated to elucidate the origin of this inclusion because Leeet al. (1979) had found large mass fractionation effects and small nuclear effects in its Ca isotopic composition, but no ²⁶Mg excesses in samples of it with very high ${}^{27}\text{Al}{}^{24}\text{Mg}$ ratios. HAL's 1.0 mm radius interior consists almost entirely of three hibonite crystals and is surrounded by a 2.0 mm thick, multi-layered rim. The first layer, called the black rim, is black and compact, resembles a devitrified glass and contains an anisotropic Al-Fe-oxide similar to hercynite in composition. This is followed by a friable rim sequence, layer I of which is predominantly feldspathoids with minor anorthite, Ti-Fe-oxide and Al-Fe-oxide. Layer II contains abundant perovskite, plus grossular, andradite and pyroxene in addition to the minerals of layer I. Layer III is mostly Ca-phosphate, possibly hydroxy-apatite and perovskite. Layer IV is rich in hibonite, Al-Fe-oxide, perovskite, nepheline and the two garnets, lacks Ca-phosphate but contains traces of a Ti-Sc-Zr-oxide. Layer V is rich in Al-Fe-oxide, pyroxene, nepheline, the two garnets and olivine whose crystals display peculiar rectangular cross-sections. The black rim does not completely surround the hibonite core. Sectors of the friable rim exist where layer I is missing and where the mineralogy of adjacent layers is no different from that of the same layers in other sectors. Pentlandite, nickel-iron and barrel-shaped olivine crystals, minerals typical of the matrix of Allende and found nowhere else in HAL, are found in layer V and increase in abundance toward its exterior, as if grains of these phases accreted together with the other minerals of layer V. This layer also contains alternating olivine-rich and garnet-, pyroxene-rich bands, resembling rhythmic layering. For these reasons, we conclude that each of the layers of the friable rim formed by the accretion of an assemblage of condensate grains rather than by complete reaction of a precursor to HAL with a nebular gas. Thus, the unusual isotopic characteristics of HAL are thought to have been inherited from a nebular reservoir which was isotopically distinct from that which gave rise to the bulk of the material in Allende. HAL's mineralogical peculiarities indicate that its formation reservoir was also chemically distinct from the latter one.     

Noble gases in E-chondrites

Noble gas data are reported for 12 E-chondrites. Combined with literature data, they show that K-Ar ages are >4 Æ for 14 out of 18 meteorites, yet U, Th-He ages are often shorter, perhaps due to late, mild reheating. Cosmic-ray exposure ages differ systematically between types 4 and 6, with E4's mostly below 16 Myr and E6's above 30 Myr. This may mean that the E-chondrite parent body contains predominantly a single petrologic type on the (~ 1 km) scale of individual impacts, in contrast to the more thoroughly mixed parent bodies of the ordinary chondrites.The heavy noble gases consist of at least two primordial components: the usual planetary component (${}^{36}\text{Ar}{}^{132}\text{Xe}\text{~ 80}$) and a less fractionated, ‘subsolar’ component ($\text{2700 ≤}{}^{36}\text{Ar}{}^{132}\text{Xe}\text{≤ 3800}$). The latter is found in highest concentration in the E4 chondrite South Oman (³⁶Ar = 760 × 10^?8cc/g, ${}^{36}\text{Ar}{}^{132}\text{Xe}\text{= 2700}$). The isotopic compositions of both components are similar to typical planetary values, indicating that some factor other than mass controlled the noble gas elemental ratios. The heavy Xe isotopes occasionally show some of the lowest ${}^{134}\text{Xe}{}^{132}\text{Xe}$ and ${}^{136}\text{Xe}{}^{132}\text{Xe}$ ratios measured in bulk chondrites, suggestive of nearly fission-free Xe (e.g. ${}^{136}\text{Xe}{}^{132}\text{Xe}\text{= 0.3095 ± 0.0020}$). Amounts of planetary gas in E4 E6 chondrites fall in the range for ordinary chondrites of types 4–6, but, in contrast to the ordinary chondrites. fail to correlate with petrologic type or volatile trace element contents. Another unusual feature of E-chondrites is that primordial Ne is present even in most 4's and 5's (²⁰Ne_p ~ 1 to 7 × 10^?8cc/g). with an isotopic composition consistent with planetary Ne.Analyses of mineral separates show that the planetary gases are concentrated in an HF- and HCl-insoluble mineral similar to phase Q, the poorly characterized, HNO₃-soluble carrier of primordial gases in carbonaceous and ordinary chondrites. The subsolar gases, on the other hand, are located in an HCl- and HNO₃-resistant phase, possibly enstatite or a minor phase included in enstatite. Much of the ¹²⁹Xe_r (50% for E4's, > 70% for E6's) is in HCl-resistant but HF-soluble sites, suggestive of a silicate.A similar subsolar component may be responsible for the high ${}^{36}\text{Ar}{}^{132}\text{Xe}$ ratios of some C3's, unequilibrated ordinary chondrites, and the unique aubrite Shallowater. The planet Venus also has a high $\text{Ar}\text{Kr}$ ratio, well above the planetary range, and hence may have acquired its noble gases from an E-chondrite-like material, similar to South Oman.     

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.     

Carbonaceous chondrites—II. Carbonaceous chondrite phyllosilicates and light element geochemistry as indicators of parent body processes and surface conditions

Petrographic observations and analyses of CM matrices are consistent with their origin as in situ low temperature (<400°K) aqueous alteration products in a parent body regolith. At least four different phyllosilicates were tentatively characterized in Murray and Murchison meteorites, in addition to Fe- and Mg-serpentines in Nogoya. In comparison with bulk meteorite compositions, all phyllosilicates and bulk matrices show enrichment of K relative to Na. Possible loss of Na and possibly some Cl, with addition of H₂O and CO₂ and water-soluble organic compounds during alteration, indicates a partially open system during alteration. Poorly characterized phases (PCP) are fine-grained (< 1 μm) admixtures of variable proportions of phyllosilicates, carbonaceous matter and opaque oxides of sulfur with high Fe, Ni and Cr contents. Calcite and some magnetite show paragenetic overlap with PCP and phyllosilicates. Carbonaceous matter is largely associated with PCP in altered CM matrices. In the unaltered CV Allende, carbonaceous matter is concentrated on olivine surfaces as a micromounded coating, particularly in the dark haloes that surround some chondrules and aggregates. Precursive alteration material may have been analogous to similarly coated olivine mixed with smaller amounts of metal and sulfides.Synthesis of the water soluble organic compounds found in CM matrices may have occurred prior to or in the same environment as did aqueous alteration of the precursive phases. Preservation or partial preservation of this organic matter may reflect the degree of overlap in episodes of synthesis and alteration.Nogoya is 95% altered and has a bulk carbon content of 5.2 wt%, which is higher than any meteorite. In addition, it has the lowest measured ${}^{13}\text{C}{}^{12}\text{C}$ ratio of any other carbonaceous chondrite, except for Karoonda.     

Sulphur isotope effects in the dissociation and evaporation of troilite: A possible mechanism for 34S enrichment in lunar soils

Both the dissociation and evaporation of troilite. heated to its melting point in vacuo, are isotopically selective. The elemental sulphur from the dissociation of troilite has a ${}^{34}\text{S}{}^{32}\text{S}$ ratio which is 13.0‰ less than that of the undissociated material while the ${}^{34}\text{S}{}^{32}\text{S}$ ratio in evaporated troilite is 5.4‰ less than that of the residual material. The two processes occur simultaneously and the isotopic variations during the course of the reaction are in accord with those for a branched reaction where the unreacted material remains isotopically well-mixed, as in a Rayleigh distillation process. This isotopic selectivity must be taken into account, along with that in other lunar surface processes, when considering the heavy isotope enrichment of sulphur in lunar soils.     

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.     

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.