Search for solar-type nitrogen in the gas-rich Pesyanoe meteorite

Abstract— We report nitrogen isotopic data obtained from a stepwise gas release of two grain-size fractions of the gas-rich meteorite Pesyanoe. Cosmic-ray-produced ¹⁵N_c may be present in all temperature steps ≥600 °C, and we correct this component using spallation ²¹Ne data. The resulting ratios reveal the presence of more than one trapped N component. Indigenous N is released above 1000 °C with an isotopic signature of δ¹⁵N = ?33‰. This is consistent with the rather uniform signatures of indigenous nitrogen in enstatite meteorites. There is no evidence for the presence of “very light” N of δ¹⁵N ? ?200‰. On the other hand, a “heavy” nitrogen component appears in the temperature range 700–800 °C, and coincides with a major release of solar-type noble gases. For a two-component mixture, the isotopic shifts in this temperature range define a lower limit δ¹⁵N_corr = ?6‰ for the second component (e.g., solar-type nitrogen). However, for the case of a solar-type component, the calculated δ¹⁵N signature depends on the adopted elemental abundances. For example, adoption of the relative abundances of ¹⁴N and noble gases in lunar ilmenite 71501 yields δ¹⁵N ? +170, which is in the range of the heavier nitrogen signatures observed on the lunar surface.     

Microtextures and crystal chemistry of pigeonite in the ureilites ALHA77257, RKPA80239, Y‐791538, and ALHA81101

Abstract— The microtextures of pigeonite in four ureilites, Allan Hills (ALH) 77257, Reckling Peak (RKP) A80239, Yamato (Y‐) 791538, and Allan Hills A81101, chosen to span a range of composition and shock level, were investigated by transmission electron microscopy (TEM); two of the samples were also investigated by single crystal X‐ray diffraction to determine Fe²⁺‐Mg cation site partitioning. The low‐shock and compositionally homogeneous pigeonites in ALHA77257 and RKPA80329 (Wo 6.4 for both, mg 86.3 and 84.3 respectively) display irregularly spaced, shock‐induced stacking faults oriented parallel to (100), and large antiphase domains (50–100 nm). Antiphase domains have no preferential orientation. No evidence of exsolution was observed. The low‐shock Y‐791538 pigeonite is homogeneous and has higher Ca and mg (Wo 9.4, mg 91.2). TEM investigation showed spinodal decomposition, indicative of incipient exsolution; small antiphase domains were observed (～5 nm). Single crystal refinement yielded R_4s? = 5.71%, with Fe²⁺‐Mg partitioning coefficient k_d = 0.077(8) and T_c = 658(35) °C. ALHA81101 has compositionally heterogeneous pyroxenes, with large local variations in Wo and mg (Wo = 4–13, mg = 86–68). No compositional gradients from core to rim of grains were observed, and the heterogeneity is interpreted as related to cation migration during shock. In one relatively Ca‐rich region (Wo～12), TEM analysis showed augite‐pigeonite exsolution lamellae, with spacing 145(20) nm. Results for ALHA77257, RKPA80239, and Y‐791538 support a model of rapid cooling following breakup of the ureilite parent body. The presence of exsolution lamellae in ALHA81101 can be related to a local shock‐induced Ca enrichment and provides no constraint on the late cooling history.     

Isotopic composition of carbon and nitrogen in ureilitic fragments of the Almahata Sitta meteorite

This study characterizes carbon and nitrogen abundances and isotopic compositions in ureilitic fragments of Almahata Sitta. Ureilites are carbon‐rich (containing up to 7 wt% C) and were formed early in solar system history, thus the origin of carbon in ureilites has significance for the origin of solar system carbon. These samples were collected soon after they fell, so they are among the freshest ureilite samples available and were analyzed using stepped combustion mass spectrometry. They contained 1.2–2.3 wt% carbon; most showed the major carbon release at temperatures of 600–700 °C with peak values of δ¹³C from ?7.3 to +0.4‰, similar to literature values for unbrecciated (“monomict”) ureilites. They also contained a minor low temperature (≤500 °C) component (δ¹³C = ca ?25‰). Bulk nitrogen contents (9.4–27 ppm) resemble those of unbrecciated ureilites, with major releases mostly occurring at 600–750 °C. A significant lower temperature release of nitrogen occurred in all samples. Main release δ¹⁵N values of ?53 to ?94‰ fall within the range reported for diamond separates and acid residues from ureilites, and identify an isotopically primordial nitrogen component. However, they differ from common polymict ureilites which are more nitrogen‐rich and isotopically heavier. Thus, although the parent asteroid 2008TC₃ was undoubtedly a polymict ureilite breccia, this cannot be deduced from an isotopic study of individual ureilite fragments. The combined main release δ¹³C and δ¹⁵N values do not overlap the fields for carbonaceous or enstatite chondrites, suggesting that carbon in ureilites was not derived from these sources.     

Nitrogen isotopic composition of CK chondrites

Abstract— Nitrogen abundances and isotopic compositions of four CK chondrites (ALH85002, EET92002, Yamato6903 and Karoonda) were measured by a stepped-combustion method. Neon and Ar were also measured for the same samples. Two types of isotopically light N were observed. One of them is labile N released at low temperatures (～300 °C). This N is observed only in ALH85002. The other N is extracted at high temperatures (900?1200 °C) from all CK chondrites; although, the isotopic compositions are somewhat variable. There is a fair correlation between the excess ¹⁵N values and the abundance of trapped ³⁶Ar for the high-temperature component, suggesting presolar origin of these species. The light N (δ¹⁵N = ?106.8‰) observed in Karoonda is one of the lightest N components ever reported for bulk chondrites.     

History of lunar meteorites Queen Alexandra Range 93069, Asuka 881757, and Yamato 793169 based on noble gas isotopic abundances,radionuclide concentrations,and chemical composition

Abstract— We investigated the characteristics and history of lunar meteorites Queen Alexandra Range 93069, Yamato 793169 and Asuka 881757 based on the abundances of all stable noble gas isotopes, the concentrations of the radionuclides ¹⁰Be, ²⁶Al, ³⁶Cl, and ⁸¹Kr, and the abundances of Mg, Al, K, Ca, Fe, Cl, Sr, Y, Zr, Ba, and La. Based on the solar wind and cosmic-ray irradiations, QUE 93069 is the most mature lunar meteorite studied up to now. The ⁴⁰Ar/³⁶Ar ratio of the trapped component is 1.87 ± 0.16. This ratio corresponds to a time when the material was exposed to solar and lunar atmospheric volatiles ～400 Ma ago. On the other hand, Yamato 793169 and Asuka 881757 contain very little or no solar noble gases, which indicates that these materials resided in the top layer of the lunar regolith only briefly or not at all. For all lunar meteorites, we observe a positive correlation of the concentrations of cosmic-ray produced with trapped solar noble gases. The duration of lunar regolith residence for the lunar meteorites was calculated based on cosmic-ray produced ²¹Ne, ³⁸Ar, ⁷⁸Kr, ⁸³Kr, and ¹²⁶Xe and appropriate production rates that were derived based on the target element abundances and the shielding indicator ¹³¹Xe/¹²⁶Xe. For QUE 93069, Yamato 793169, and Asuka 881757, we obtained 1000 ± 400 Ma, 50 ± 10 Ma, and <1 Ma, respectively. Both Asuka 881757 and Yamato 793169 show losses of radiogenic ⁴He from U and Th decay and Yamato 793169 also ⁴⁰Ar loss from K-decay. For Asuka 881757, we calculate a K-Ar gas retention age of 3100 ± 600 Ma and a ²⁴⁴Pu-¹³⁶Xe fission age of 4240 ± 170 Ma. This age is one of the oldest formation ages ever observed for a lunar basalt. The exposure history of QUE 93069 after ejection from the Moon was derived from the radionuclide concentrations: ejection 0.16 ± 0.03 Ma ago, duration of Moon-Earth transit 0.15 ± 0.02 Ma and fall on Earth <0.015 Ma ago. This ejection event is distinguished temporally from those which produced the other lunar meteorites. We conclude that six to eight events are necessary to eject all the known lunar meteorites.     

Nitrogen in diamond‐free ureilite Allan Hills 78019: Clues to the origin of diamond in ureilites

Abstract— Nitrogen and noble gases were measured in a bulk sample and in acid‐resistant carbon‐rich residues of the ureilite Allan Hills (ALH) 78019 which has experienced low shock and is free of diamond. A small amount of amorphous carbon combusting at ≤500 °C carries most of the noble gases, while the major carbon phase consisting of large crystals of graphite combusts at ≥800 °C, and is almost noble‐gas free. Nitrogen on the other hand is present in both amorphous carbon and graphite, with different δ¹⁵N signatures of ?21%_o and +19%_o, respectively, distinctly different from the very light nitrogen (about ?100%_o) of ureilite diamond. Amorphous carbon in ALH 78019 behaves similar to phase Q of chondrites with respect to noble gas release pattern, behavior towards oxidizing acids as well as nitrogen isotopic composition. In situ conversion of amorphous carbon or graphite to diamond through shock would require an isotopic fractionation of 8 to 12% for nitrogen favoring the light isotope, an unlikely proposition, posing a severe problem for the widely accepted shock origin of ureilite diamond.     

A carbon and nitrogen isotope study of diamond from primitive chondrites

Abstract Diamonds isolated from primitive chondrites of the carbonaceous, ordinary and enstatite groups have been analysed by high-resolution stepped combustion, followed by measurement of their C and N isotopes using a newly adapted technique that allows quantitative measurements of C/N ratios. The δ¹³C of the diamond is shown to vary between meteorite groups from ?32 to ?38%0, and the measured C/N ratios suggest that the N concentration of diamond ranges over a factor of 7 from 1800 ppm (Tieschitz) to 13,000 ppm (Adrar 003). The δ¹⁵N of N released from diamond is constrained to ?348 ± 7%. The complexity of the C release pattern and C/N ratio during combustion implies the presence of more than one component, which suggests that either more than one type of diamond is present in the samples, or unidentified additional phases are located in the acid-resistant residue. The components are present in varying proportions between meteorite groups. The data are compatible with a model of a mix of different diamond populations (some probably presolar and some possibly solar) existing in the early solar nebula, where each population originally contributed a roughly equal amount to chondrites of every class. Subsequent metamorphism has resulted in overall variations in δ¹³C and C/N ratios in diamond isolated from meteorites of differing petrologic grade without significantly altering the N isotopic composition. Possible ways for this to be achieved are explored.     

Compound‐specific carbon,nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

Abstract– Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ¹³C, and δ¹⁵N) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound‐specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ¹³C and increasing δD with increasing carbon number in the α‐H, α‐NH₂ amino acids that correspond to predictions made for formation via Strecker‐cyanohydrin synthesis. We also observe light δ¹³C signatures for β‐alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight‐chain, amine‐terminal amino acids (n‐ω‐amino acids). Higher deuterium enrichments are observed in α‐methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent‐body chemistry.     

The origin of chondritic macromolecular organic matter: A carbon and nitrogen isotope study

Abstract— The N and C abundances and isotopic compositions of acid-insoluble carbonaceous material in thirteen primitive chondrites (five unequilibrated ordinary chondrites, three CM chondrites, three enstatite chondrites, a CI chondrite and a CR chondrite) have been measured by stepped combustion. While the range of C isotopic compositions observed is only ～δ¹³C = 30%, the N isotopes range from δ¹⁵N ' -40 to 260%. After correction for metamorphism, presolar nanodiamonds appear to have made up a fairly constant 3–4 wt% of the insoluble C in all the chondrites studied. The apparently similar initial presolar nanodiamond to organic C ratios, and the correlations of elemental and isotopic compositions with metamorphic indicators in the ordinary and enstatite chondrites, suggest that the chondrites all accreted similar organic material. This original material probably most closely resembles that now found in Renazzo and Semarkona. These two meteorites have almost M-shaped N isotope release profiles that can be explained most simply by the superposition of two components, one with a composition between δ¹⁵N = -20 and -40% and a narrow combustion interval, the other having a broader release profile and a composition of δ¹⁵N ～ 260%. Although isotopically more subdued, the CI and the three CM chondrites all appear to show vestiges of this M-shaped profile. How and where the components in the acid-insoluble organics formed remains poorly constrained. The small variation in nanodiamond to organic C ratio between the chondrite groups limits the local synthesis of organic matter in the various chondrite formation regions to at most 30%. The most ¹⁵N-rich material probably formed in the interstellar medium, and the fraction of organic N in Renazzo in this material ranges from 40 to 70%. The isotopically light component may have formed in the solar system, but the limited range in nanodiamond to total organic C ratios in the chondrite groups is consistent with most of the organic material being presolar.     

Raman spectroscopic study of diamond and graphite in ureilites and the origin of diamonds

Abstract– We performed micro‐Raman spectroscopic analyses of the carbon vein in five ureilites: Allan Hills (ALH) A77257, Northwest Africa (NWA) 3140, Shi?r 007, Yamato 790981 (Y‐790981), and Yamato 791538 (Y‐791538). The graphite peaks showed that the graphite structure in ureilite is well developed, especially compared with the carbonaceous material in carbonaceous chondrite. The domain sizes of the graphite were 45–110 Å. We observed shifts in the diamond peak positions to higher wave numbers with a large full width at half maximum (FWHM), especially for NWA 3140. Although the FWHM of a diamond peak is not a crucial diagnostic test for a chemical vapor deposition (CVD) origin of diamond, the shift of the diamond peaks to higher wave numbers could be a strong indicator that supports the CVD origin as these shifts have only been observed in CVD diamonds. We discuss the origin of diamond from various aspects, and confirm that the CVD model is the most plausible. We conclude that all carbon material (graphite, amorphous carbon, diamond, etc.) condensed on the early condensates in the primitive solar nebula.     

Mineralogical evidence for the origin of diamond in ureilites

Abstract— The x‐ray powder diffraction patterns of 50–100 μm C‐rich grains from five ureilitic meteorites—Kenna, Allan Hills (ALH) 78019, Yamato (Y)‐82100, Y‐791538, and ALH 77257—were obtained by using a Gandolfi camera. The results reveal that the basal spacing of part of the graphite coexisting with diamond is slightly smaller compared to the normal spacing. Compressed graphite is experimentally known to occur at the initial stage of the direct transformation from graphite to diamond structures at high pressures and temperatures. The presence of the compressed graphite in ureilites, therefore, gives clear evidence that the diamond formed by high‐pressure conversion of graphite. The modes of occurrence of C minerals observed with reflected light through an optical microscope reveal that graphite coexisted with olivine and pyroxene during igneous or metamorphic processes and, furthermore, that part of the graphite was converted to diamond by impact. The relative x‐ray intensity of diamond to graphite increases in the following order: ALH 78019 and Y‐82100 < Y‐791538 < Kenna < ALH 77257. This correlates with the shock level that is estimated mainly on the basis of the shock features of silicates. Therefore, the relative amounts of diamond to graphite suggested by x‐ray intensities may be useful as a measure of the degree of shock.     

Nitrogen and noble gases in a glass sample from the LEW88516 shergottite

Abstract— A glass separate from the LEW88516 shergottite was analyzed by step-wise combustion for N and noble gases to determine whether it contained trapped gas similar in composition to the martian atmosphere-like component previously observed in lithology C of EETA79001. Excesses of ⁴⁰Ar and ¹²⁹Xe were in fact observed in this glass, although the amounts of these excesses are ≤20% of those seen in the latter meteorite, and are comparable to the amounts seen in whole-rock analyses of LEW88516. The isotopic composition of N in LEW88516 does not show an enrichment in ¹⁵N commensurate with the amount of isotopically-heavy N expected from the noble gases excesses. One must posit some extreme assumptions about the nature of the N components present in LEW88516 in order to allow the presence of the trapped nitrogen component. Alternatively, the N has somehow been decoupled from the noble gases, and was either never present or has been lost.     

Populations of nanodiamond grains in meteorites from the data on isotopic composition and content of nitrogen

The present study has shown that the dependence of the isotopic composition of nitrogen on the N/C ratio, revealed from the data for bulk samples of meteoritic nanodiamond, can be obtained within the framework of the following model of the composition of populations of nanodiamond grains: (a) initial nanodiamond, i.e., the nanodiamond in the protoplanetary cloud before the accretion of the meteorite parent bodies, was composed mainly of grains of two populations (denoted as C_N and C_F), the ratio of which changed in meteorites depending on the degree of hydrothermal metamorphism; (b) only the grains of one of these populations (C_N) contain volume-bound nitrogen with δ¹⁵N = ?350‰; (c) the grains of both populations contain surface-bound nitrogen (δ¹⁵N ≡ 0). The calculations revealed the following properties of population grains in this model. (1) The grains of the C_N and C_F populations are most likely the same in isotopic composition of carbon and heterogeneous in distribution of its isotopes: the central part of grains is enriched with the δ¹²C isotope relative to the remainder of the grain. While the value of δ¹³C is ?37.3 ± 1.1‰ for carbon in the central part, it is ?32.8 ± 1.5‰ for the whole volume of the grains. (2) The noble gases of the HL component, specifically Xe-HL, are anomalous in isotopic composition and are most likely contained in the third population of nanodiamond grains (denoted as C_HL), the mass fraction of which is negligible relative to that for other grain populations. Only the grains of the C_HL population have an undoubtedly presolar origin, while the grains of the other nanodiamond populations could have formed at the early stages of the evolution of the protoplanetary cloud material before the accretion of the meteoritic parent bodies.     

Noble gases and nitrogen in Muong Nong tektites

Abstract— Three samples of Muong Nong tektites have been studied for N and noble gases. The isotopic composition of noble gases is airlike. The noble gas amounts are much higher in Muong Nong tektites than in splash-form tektites. As compared to air, He and Ne have been enriched, most likely due to inward diffuion from ambient air, subsequent to glass formation. Nitrogen contents range from 0.3 to 1.34 ppm, with a non-atmospheric δ¹⁵N ranging from 8 to 17%. The release pattern of δ¹⁵N clearly shows the presence of two N components. Higher N/³⁶Ar values than those of air, together with positive δ¹⁵N, show that a major portion of N in Muong Nong tektites is a remnant from the sedimentary source material.     

Carbon,Nitrogen, and Noble Gases in the Diamond Fractions of the Novo Urei Ureilite

We measured the contents and isotopic compositions for C, N, and noble gases in the diamond fractions separated in a heavy liquid ( = 2.9 g/cm³) from a sample enriched with diamond from the Novo Urei ureilite. The results show that the concentrations of nitrogen and noble gases in the diamond fraction isolated from the supernatant (the fraction is named DNU-1) are more than a factor of 1.5 higher than those in the diamond fraction from the residue (DNU-2). This difference is probably caused by smaller sizes of grains and (or) clusters of smaller grains as well as by larger defectiveness of the crystal lattice of the diamond in the DNU-1 fraction as compared to DNU-2. Both fractions are similar in the isotopic composition of C and N and in the ratios of trapped chemical elements. The results obtained and the published data concerning C, N, and noble gases in different fractions of other ureilites allow us to conclude the following. (1) The ureilite diamond was most likely formed from graphite and the fine-grained crystalline (or semiamorphous) carbonaceous phase as a result of shock transformation in the parent bodies. (2) The negative result in the search for the isotopically light component of nitrogen (¹⁵N is about –100) in the Antarctic unshocked ureilite ALH 78019 (Rai et al., 2002), which introduced serious difficulties for explaining the origin of the ureilite diamond in the parent bodies during the impact, is most likely caused by the absorption of atmospheric nitrogen by the carbonaceous material in the processes of terrestrial weathering. (3) The source of light nitrogen (¹⁵N –100) in the ureilite diamond was probably the presolar diamond in the initial carbonaceous material of the ureilite parent bodies, because the impurity elements, including nitrogen (¹⁵N < –350), in this diamond could be trapped in the magmatic processes by the carbonaceous material, which became a precursor of the ureilite diamond in the shock event.     

Noble gases in ureilites released by crushing

Abstract— Noble gases in two ureilites, Kenna and Allan Hills (ALH) 78019, were measured with two extraction methods: mechanical crushing in a vacuum and heating. Large amounts of noble gases were released by crushing, up to 26.5% of ¹³²Xe from ALH 78019 relative to the bulk concentration. Isotopic ratios of the crush‐released Ne of ALH 78019 resemble those of the trapped Ne components determined for some ureilites or terrestrial atmosphere, while the crush‐released He and Ne from Kenna are mostly cosmogenic. The crush‐released Xe of ALH 78019 and Kenna is similar in isotopic composition to Q gas, which indicates that the crush‐released noble gases are indigenous and not caused by contamination from terrestrial atmosphere. In contrast to the similarities in isotopic composition with the bulk samples, light elements in the crush‐released noble gases are depleted relative to Xe and distinct from those of each bulk sample. This depletion is prominent especially in the ²⁰Ne/¹³²Xe ratio of ALH 78019 and the ³⁶Ar/¹³²Xe ratio of Kenna. The values of measured ³He/²¹Ne for the gases released by crushing are significantly higher than those for heating‐released gases. This suggests that host phases of the crush‐released gases might be carbonaceous because cosmogenic Ne is produced mainly from elements with a mass number larger than Ne. Based on our optical microscopic observation, tabular‐foliated graphite is the major carbon mineral in ALH 78019, while Kenna contains abundant polycrystalline graphite aggregates and diamonds along with minor foliated graphite. There are many inclusions at the edge and within the interior of olivine grains that are reduced by carbonaceous material. Gaps can be seen at the boundary between carbonaceous material and silicates. Considering these petrologic and noble gas features, we infer that possible host phases of crush‐released noble gases are graphite, inclusions in reduction rims, and gaps between carbonaceous materials and silicates. The elemental ratios of noble gases released by crushing can be explained by fractionation, assuming that the starting noble gas composition is the same as that of amorphous carbon in ALH 78019. The crush‐released noble gases are the minor part of trapped noble gases in ureilites but could be an important clue to the thermal history of the ureilite parent body. Further investigation is needed to identify the host phases of the crush‐released noble gases.     

Presolar silicon carbide from the Indarch (EH4) meteorite: Comparison with silicon carbide populations from other meteorite classes

Abstract— Presolar SiC from the Indarch (EH4) meteorite was studied by scanning electron microscopy (SEM), by ion probe analysis for C and Si isotopic compositions, and by static source mass spectrometry for noble gas and C isotopic compositions. The data obtained are compared to SiC data from other meteorites, especially from Murchison (CM2), for which there is the most information available. The isotopic compositions of the major elements in SiC from Indarch and Murchison are similar. Stepped combustion data suggest a mean δ¹³C for SiC from both meteorites of ～+1430%o. Silicon isotopes in Indarch and Murchison SiC also compare well. In some other important respects, however, SiC in the two meteorites are different. Morphologically, SiC from Indarch appears finer grained than SiC from Murchison and is entirely composed of submicron grains. The finer-grained nature of Indarch SiC is confirmed by its noble gas characteristics. The mean Ne-E/Xe-S ratio for bulk Indarch SiC is significantly lower than the same ratio in Murchison (625 ± 47 vs. ～3500) but is similar to that of the finest grain-size fractions (<1 μm) in Murchison. A comparison of noble gas data from SiC from several different meteorites suggests that it might be Murchison SiC, rather than Indarch SiC, that is unusual. The grain-size disparities in SiC between meteorites are difficult to explain by residue processing differences or differing parent body processing. Instead, we speculate that a grain-size sorting mechanism for SiC may have operated in the solar nebula.     

Nitrogen components in IAB/IIICD iron meteorites

Abstract— Isotopic variations have been reported for many elements in iron meteorites, with distinct N signatures found in the metal and graphite of IAB irons. In this study, a dozen IAB/IIICD iron meteorites (see Table 1 for new classifications) were analyzed by stepwise pyrolysis to resolve nitrogen components. Although isotopic heterogeneity has been presumed to be lost in thermally processed parent objects, the high‐resolution nitrogen isotopic data indicate otherwise. At least one reservoir has a light nitrogen signature, δ¹⁵N = ?(74 ± 2)‰, at 900 °C to 1000 °C, with a possible second, even lighter, reservoir in Copiapo (δ¹⁵N ≤ ?82‰). These releases are consistent with metal nitride decomposition or low‐temperature metal phase changes. Heavier nitrogen reservoirs are observed in steps ≤700 °C and at 1200 °C to 1400 °C. The latter release has a δ¹⁵N signature with a limit of ≥?16‰. Xenon isotopic signatures are sensitive indicators for the presence of inclusions because of the very low abundances of Xe in metal. The combined high‐temperature release shows ¹³¹Xe and ¹²⁹Xe excesses to be consistent with shifts expected for Te(n,γ) reaction in troilite by epithermal neutrons, but there are also possible alterations in the isotopic ratios likely due to extinct ¹²⁹I and cosmic‐ray spallation. The IAB/IIICD iron data imply that at least one light N component survived the formation processes of iron parent objects which only partially exchanged nitrogen between phases. Preservation of separate N reservoirs conflicts with neither the model of impact‐heating effects for these meteorites nor reported age differences between metal and silicates.     

Stable isotope analysis of carbon and nitrogen in angrites

Angrites are a small group of ancient basaltic achondrites, notable for their unusual chemistry and extreme volatile depletion. No comprehensive study of indigenous light elements currently exists for the group. Measurement of the abundances and isotopic composition of carbon and nitrogen could provide information pertaining to the evolution of the angrite parent body. Bulk‐sample stepped combustion analyses of five angrites and a glass separate from D'Orbigny were combined with earlier data and acid dissolution experiments of carbonates found in D'Orbigny to compile an inventory of indigenous carbon and nitrogen. Indigenous carbon combusted between 700 °C and 1200 °C, with abundances of 10–140 ppm and a mass‐weighted δ¹³C of ?25 to ?20‰ with the exception of D'Orbigny (δ¹³C approximately ?5‰). Nitrogen was released at 850–1200 ºC, 1–20 ppm with a δ¹⁵N ?3‰ to +4‰; again, D'Orbigny (δ¹⁵N approximately +20 to +25‰) was an exception. We interpret these components as largely indigenous and decoupled; the carbon in graphitic or amorphous form, while the nitrogen is present as a dissolved component in the silicates. No relationship with the textural sub‐classification of angrites is apparent. We suggest that the angrite parent body contains a reservoir of reduced carbon and thus may have undergone a change in redox conditions, although the timing and mechanism for this remain unclear.     

A nitrogen and argon stable isotope study of Allan Hills 84001: Implications for the evolution of the Martian atmosphere

Abstract— The abundances and isotopic compositions of N and Ar have been measured by stepped combustion of the Allan Hills 84001 (ALH 84001) Martian orthopyroxenite. Material described as shocked is N-poor ([N] ～ 0.34 ppm; δ¹⁵N ～ +23%); although during stepped combustion, ¹⁵N-enriched N (δ¹⁵N ～ +143%) is released in a narrow temperature interval between 700 °C and 800 °C (along with ¹³C-enriched C (δ¹³C ～ +19%) and ⁴⁰Ar). Cosmogenic species are found to be negligible at this temperature; thus, the iso-topically heavy component is identified, in part, as Martian atmospheric gas trapped relatively recently in the history of ALH 84001. The N and Ar data show that ALH 84001 contains species from the Martian lithosphere, a component interpreted as ancient trapped atmosphere (in addition to the modern atmospheric species), and excess ⁴⁰Ar from K decay. Deconvolution of radiogenic ⁴⁰Ar from other Ar components, on the basis of end-member ³⁶Ar/¹⁴N and ⁴⁰Ar/³⁶Ar ratios, has enabled calculation of a K-Ar age for ALH 84001 as 3.5–4.6 Ga, depending on assumed K abundance. If the component believed to be Martian palaeoatmos-phere was introduced to ALH 84001 at the time the K-Ar age was set, then the composition of the atmosphere at this time is constrained to: δ¹⁵N ≥ +200%, ⁴⁰Ar/³⁶Ar ≤ 300 and ³⁶Ar/¹⁴N ≥ 17 × 10^?5. In terms of the petrogenetic history of the meteorite, ALH 84001 crystallised soon after differentiation of the planet, may have been shocked and thermally metamorphosed in an early period of bombardment, and then subjected to a second event. This later process did not reset the K-Ar system but perhaps was responsible for introducing (recent) atmospheric gases into ALH 84001; and it might mark the time at which ALH 84001 suffered fluid alteration resulting in the formation of the plagioclase and carbonate mineral assemblages.