Neutron capture records of mesosiderites and an iron meteorite

The Sm and Gd isotopic compositions of silicates from six mesosiderites (Dalgaranga, Estherville, Morristown, Northwest Africa (NWA) 1242, NWA 2932, and Vaca Muerta) and one iron meteorite (Udei Station) were determined to elucidate the cosmic-ray exposure records. All seven samples showed significant ¹⁵⁰Sm/¹⁴⁹Sm and ¹⁵⁸Gd/¹⁵⁷Gd isotopic shifts from neutron capture reactions corresponding to neutron fluences of (1.3-21.8) × 10¹⁵ n cm⁻². In particular, Vaca Muerta showed a significantly higher neutron fluences than the other six samples. The parameter for the degree of neutron thermalization (ε_Sm/ε_Gd) also showed a significant difference between Vaca Muerta (0.76) and the other samples (0.93-1.20). These results suggest a two-stage irradiation of the Vaca Muerta silicates in the parent body (>50 Ma) before formation of the mesosiderite and during its transit to Earth (138 Ma). This is consistent with the ⁸¹Kr-Kr cosmic-ray exposure age data of a Vaca Muerta pebble from a previous noble gas isotopic study.     

A high field strength element perspective on early lunar differentiation

Lunar rocks are inferred to tap the different fossil cumulate layers formed during crystallisation of a lunar magma ocean (LMO). A coherent dataset, including Zr isotope data and high precision HFSE (W, Nb, Ta, Zr, Hf) and REE (Nd, Sm, Lu) data, all obtained by isotope dilution, can now provide new insights into the processes active during LMO crystallisation and during the petrogenesis of lunar magmas. Measured ⁹²Zr and ⁹¹Zr abundances agree with the terrestrial value within 0.2 ε-units. Incompatible-trace-element enriched rocks from the Procellarum KREEP Terrane (PKT) display Nb/Ta and Zr/Hf above the bulk lunar value (ca. 17), and mare basalts display lower ratios, generally confirming the presence of complementary enriched and depleted mantle reservoirs on the Moon. The full compositional spectrum of lunar basalts, however, also requires interaction with ilmenite-rich layers in the lunar mantle. Notably, the high-Ti mare basalts analysed display the lowest Nb/Ta and Zr/Hf of all lunar rocks, and also higher Sm/Nd at similar Lu/Hf than low-Ti basalts. The high-Ti basalts also exhibit higher and strongly correlated Ta/W (up to 25) and Hf/W (up to 140), at similar W contents, which is difficult to reconcile with ortho- and clinopyroxene-controlled melting. Altogether, these patterns can be explained via assimilation of up to ca. 20% of ilmenite- and clinopyroxene-rich LMO cumulates by more depleted melts from the lower lunar mantle. Direct melting of ilmenite-rich cumulates or the possible presence of residual metals in the lunar mantle both cannot easily account for the observed Ta/W and Hf/W patterns. Cumulate assimilation is also a viable mechanism that can partially buffer the Lu/Hf of mare basalts at relatively low values while generating variable Sm/Nd. Thus, the dichotomy between low Lu/Hf of lunar basalts and high time integrated source Lu/Hf as inferred from Hf isotope compositions can potentially be explained. The proposed assimilation model also has important implications for the short-lived nuclide chronology of the Earth-Moon system. The new Hf/W and Ta/W data, together with a compilation of existing W-Th-U data for lunar rocks, indicate that the terrestrial and lunar mantles are indistinguishable in their Hf/W. Virtually identical εW and Hf/W in the terrestrial and lunar mantle suggest a strong link between final core-mantle equilibration on Earth and the Moon forming giant impact. Previously, linear arrays of lunar samples in ¹⁸²W vs. Hf/W and ¹⁴²Nd vs. Sm/Nd spaces have been interpreted as isochrons, arguing for LMO crystallisation as late as 250 Myrs after solar system formation. Based on the proposed assimilation model, the ¹⁸²W and ¹⁴²Nd in many lunar magmas can be shown to be decoupled from their ambient Hf/W and Sm/Nd source compositions. As a consequence, the ¹⁸²W vs. Hf/W and ¹⁴²Nd vs. Sm/Nd arrays would constitute mixing lines rather than isochrons. Hence, the lunar ¹⁸²Hf-¹⁸²W and ¹⁴⁶Sm-¹⁴²Nd data would be fully consistent with an “early” crystallisation age of the LMO, even as early as 50 Myrs after solar system formation when the Moon was probably formed.     

Regolith history of the aubritic meteorite parent body revealed by neutron capture effects on Sm and Gd isotopes

Enstatite achondrites (aubrites) when compared to other stone meteorites have unusually long cosmic-ray exposure (CRE) ages. We report here the ¹⁵⁰Sm/¹⁴⁹Sm and ¹⁵⁸Gd/¹⁵⁷Gd ratios in six different structural phases, i.e., light and dark (shocked) grains and in matrix materials of Pesyanoe, in three different fragments from Pena Blanca Spring, and in one from Norton County, Shallowater, and Khor Temiki, to investigate the regolith history on the aubrite parent body. The results from phases components of Pesyanoe confirm earlier reported evidence for regolith irradiation of several aubrites. The inferred neutron fluences for six Pesyanoe separates vary between (2.13 and 2.82) × 10¹⁶ n cm⁻². The fluences also significantly exceed those expected from cosmic-ray irradiation during transit to Earth and approach those observed in the lunar regolith. These observations confirm that the brecciated Pesyanoe meteorite, which contains solar wind (SW) gases only in dark phases, was processed in a regolith and that structural phases were differentially irradiated before compaction. On the other hand, in some aubrites (Mt. Egerton, Shallowater, Pena Blanca Spring, Norton County) neutron capture effects may entirely be due to space irradiation.     

Sm and Gd isotopic shifts of Apollo 16 and 17 drill stem samples and their implications for regolith history

The isotopic compositions of Sm and Gd in lunar regolith samples from the Apollo 16 and 17 deep drill stems showed clear isotopic shifts in ¹⁵⁰Sm /¹⁴⁹Sm (ε = +124 to +191 for A-16, and +37 to +111 for A-17) and ¹⁵⁸Gd/¹⁵⁷Gd (ε = +107 to +169 for A-16, and +31 to +84 for A-17) corresponding to neutron fluences of (5.68-9.03) × 10¹⁶ n cm⁻² for A-16 and (1.85-5.04) × 10¹⁶ n cm⁻² for A-17. The depth profiles of neutron fluences suggest that the regoliths at both sites were due to incomplete mixing of three different slabs which experienced individual two-stage irradiation before and after deposition of the upper slabs. The variations in REE compositions provide chemical evidence for incompletely vertical mixing of regoliths especially at upper layers of the two sites. The thermal neutron energy index estimated from the combination of Sm and Gd isotopic shifts, defined as ε_Sm/ε_Gd, shows a small variation (0.61-0.64) in the A-16 core except for the surface layer. On the other hand, a large variation in ε_Sm/ε_Gd = 0.67 to 0.83 in the A-17 core may result from complicated history such as two-stage irradiation and incomplete mixing during the gardening processes. Isotopic enrichments of ¹⁵²Gd and ¹⁵⁴Gd correlated with Eu/Gd elemental abundances and neutron fluences were also observed in almost all of 15 samples, showing evidence of neutron-capture from ¹⁵¹Eu and ¹⁵³Eu, respectively.     

Cosmogenic effects on Li/Li, B/B, and W/W in CAIs from carbonaceous chondrites

This study focuses on cosmogenic effects on lithium, boron, and tungsten isotopes in CAIs from carbonaceous chondrites. The results for lithium isotopes have been used to properly correct experimental data obtained by Chaussidon et al. (2006a) for Allende CAI 3529-41 for cosmogenic contributions. After proper correction, the new inferred ratios slightly but systematically differ from the original ones, indicating that the original study slightly overestimated the cosmogenic corrections. A statistical interpretation of the data indicates that there is a non-linear correlation between ⁷Li/⁶Li and ⁹Be/⁶Li that might be interpreted as a disturbed isochron. For boron isotopes, the data obtained here confirm that cosmogenic corrections on the ¹⁰Be-¹⁰B dating system are indeed very minor and can in most cases be neglected. However, a statistical interpretation of the data demonstrates that the type of the fitting procedure used can significantly change the results. It is demonstrated that a fitting procedure using the uncertainties as weights gives a slope about 50% shallower compared to the slope obtained using a non-weighted fitting procedure (for the same data). Such a difference can be wrongly interpreted as an age difference of about one half-life. The modeled results for tungsten isotopes clearly demonstrate that cosmic-ray effects might be of importance for samples having high Ta/W ratios due to thermal neutron capture on ¹⁸¹Ta to form ¹⁸²W. This effect does not increase the scatter of the data around the isochron but increases the slope of the isochron and therefore gives too old formation ages for the studied CAIs. Consequently, a proper handling of cosmic-ray induced shifts is necessary for high precision ¹⁸²Hf-¹⁸²W dating studies.     

Nb/Zr fractionation on the Moon and the search for extinct Nb

A comprehensive Zr isotopic study was conducted on eleven lunar basalts and highland rocks to search for evidence of the extinct nuclide ⁹²Nb, which decays to ⁹²Zr with a half-life of 36 Ma. Internal isochrons were determined for two early highland rocks, 77215 and 60025. No resolvable Zr isotopic variations were detected in this wide range of lunar samples and thus there is no evidence for the former existence of live ⁹²Nb on the Moon. The Nb/Zr ratios of lunar ilmenites and bulk rock samples vary by only a factor of two to three relative to the chondritic Nb/Zr ratio. No evidence for larger Nb/Zr fractionation was found. This limited fractionation and late isotopic closure of the source region prevents the formation of measurable ⁹²Zr anomalies in high-Ti mare basalts. As a consequence, it is not possible to draw conclusions from the ⁹²Nb-⁹²Zr chronometer about the timing of early lunar differentiation and to constrain the role of ilmenite in the source region of high-Ti mare basalts. However, the fractionation is still sufficient to deduce an upper limit for the initial ⁹²Nb/⁹³Nb ratio of the solar system of <5 × 10⁻⁴.     

Experimental partitioning of Tc, Mo, Ru, and Re between solid and liquid during crystallization in Fe-Ni-S

Technetium isotopes ⁹⁷Tc, ⁹⁸Tc and ⁹⁹Tc decay to ⁹⁷Mo, ⁹⁸Ru and ⁹⁹Ru, with half-lives of 2.6 My, 4.1 My, and 0.21 My respectively. If there were early solar system processes that resulted in significant fractionation of Tc from the daughter elements, decay of extant Tc could have led to the creation of Mo and Ru isotopic heterogeneities. To assess the potential of metallic core crystallization to fractionate these elements, we examine the partitioning behavior of Tc relative to Re, Mo and Ru in the Fe-Ni-S system between solid metal and liquid metal alloy. The experimental evidence shows that Tc behaves more like the modestly compatible siderophile element Ru than the more highly compatible siderophile element Re, and that Tc is substantially more compatible than Mo. We also demonstrate a pressure effect in the partitioning of Mo during the crystallization of Fe-Ni-S melts. For a sulfur concentration in the liquid fraction of the core of 10 wt% (16.3 at%), the Jones and Malvin (1990) parameter is −ln(1-2 × 1.09 × 0.163) ≅ 0.44, which yields: D(Re) ≅ 4.1; D(Ru) ≅ 2.3; D(Tc) ≅ 1.7; D(Mo)_Lo-P ≅ 1.0;.and D(Mo)_Hi-P ≅ 0.5. Our results suggest that detectable Tc-induced isotopic anomalies (≥0.1 ε unit) in Ru and Mo could only be produced by unrealistically extreme degrees of crystallization of metal during asteroidal core fractionation, regardless of the time scales and initial Tc abundances involved.     

Formation and geochemical significance of micrometallic aggregates including fissiogenic platinum group elements in the Oklo natural reactor, Gabon

Metallic aggregates with a size of a few tens μm and consisting mainly of Ru, Rh, Pd, Te, Pb, As, Sb, S and Bi were found in the acid residue of SD37-S2/CD uraninite taken from Oklo natural reactor zone (RZ) 13. Quantitative analyses of major elements using an electron probe microanalyzer and in situ isotopic analyses of Zr, Mo, Ru, Pb and U using a sensitive high-resolution ion microprobe were performed on the metallic aggregates to determine the geochemical behaviors of fission products and actinides and to ascertain the processes of formation of the aggregates in the RZs. The chemical compositions of the aggregates investigated in this study are significantly different from those reported previously, showing lower Pb content and no correlation between the contents of Pb and S in the individual grains. The ²³⁵U/²³⁸U ratios in metallic aggregates vary significantly from 0.00478 to 0.01466, indicating chemical fractionation between U and Pu during the formation of the aggregates. The Pb isotopic data indicate that most of the Pb in the aggregates decayed from 2.05 Ga-old uraninite that existed in the RZ originally and that there was chemical fractionation between U and Pb in some aggregates. The Zr and Mo isotopic ratios, ⁹⁰Zr/⁹¹Zr and ⁹⁵Mo/⁹⁷Mo, for most of the aggregates had small variations, which can be simply explained by constant separate mixing of fissiogenic and nonfissiogenic components. On the other hand, a large variation in the ⁹⁹Ru/¹⁰¹Ru ratio (0.324-1.73) cannot be explained only by a two component mixing theory; thus, chemical fractionation between Tc and Ru during the reactor criticality is suggested. The large variations in the ²³⁵U/²³⁸U and ⁹⁹Ru/¹⁰¹Ru isotopic ratios suggest that the aggregates formed under various redox conditions owing to the radiolysis of water.     

Chemical characterization of earth’s most ancient clastic metasediments from the Isua Greenstone Belt, southern West Greenland

New and published major and trace element abundances of clastic metasediments (mainly garnet-biotite-plagioclase schists) from the ∼3.8 Ga Isua Greenstone Belt (IGB), southern West Greenland, are used in an attempt to identify the compositional characteristics of the protoliths of these sediments. Compositionally, the metasediments are heterogeneous with enrichment of LREE (La/Sm_chond = 1.1-3.9) and variable enrichment and depletion of HREE (Gd/Yb_chond = 0.8-4.3). Chondrite-normalized Eu is also variable, spanning a range from relative Eu depletion to enrichment (Eu/Eu* = 0.6-1.3). A series of geochemical and geological criteria provides conclusive evidence for a sedimentary origin, in disagreement with some previous studies that questioned the presence of genuine clastic metasediments. In particular, trace element systematics of IGB metasediments show strong resemblance to other well-documented Archaean clastic sediments, and are consistent with a provenance consisting of ultramafic, mafic and felsic igneous rocks. Two schists, identified as metasomatized mafic igneous rocks from petrographic and field evidence, show distinct compositional differences to the metasediments.Major element systematics document incipient-to-moderate source weathering in the majority of metasediments, while signs of secondary K-addition are rare. Detailed inspection of Eu/Eu*, Fe₂O₃ and CIW (chemical index of weathering) relationships reveals that elevated iron contents (when compared to averages for continental crust) and strong relative enrichment in Eu may be due to precipitation of marine Fe-oxyhydroxides during deposition or diagenesis on the seafloor.Some of the IGB metasediments have yielded anomalous ¹⁴²Nd and ¹⁸²W isotopic compositions that were respectively interpreted in terms of early mantle differentiation processes and the presence of a meteorite component. Alternatively, W and possibly Nd isotopes could have been affected by thermal neutron capture on the Hadean surface. The latter process was tested in this study by analysis of Sm isotope compositions, which serve as an effective monitor for neutron capture effects. As no anomalous variation from terrestrial values was detected, we infer that isotope systematics (including ¹⁸²W and ¹⁴²Nd) of IGB metasediments were not affected by neutron capture, but reflect decay of radioactive parent isotopes.     

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.     

Magmatic fractionation of Hf and W: constraints on the timing of core formation and differentiation in the Moon and Mars

Excesses of ¹⁸²W have previously been measured in samples from the Moon and Mars, and can be derived from high Hf/W regions in their interiors during their early histories. Although planetary mantles will have superchondritic Hf/W after core formation, the extent to which high Hf/W regions could be generated by magmatic fractionation has not been evaluated. In order to address the latter possibility, we have carried out experiments from 100 MPa to 10.0 GPa, 1150 to 1850°C, at oxygen fugacities near the IW (iron-wüstite) buffer, and measured partition coefficients for W and Hf for plagioclase-liquid, olivine-liquid, orthopyroxene-liquid, clinopyroxene-liquid, garnet-liquid, and metal-liquid pairs. Clinopyroxene and garnet are both capable of fractionating Hf from W during magmatic crystallization or mantle melting, and minor variations in the measured D’s can be attributed to crystal chemical effects. Excesses of ¹⁸²W and ¹⁴²Nd in lunar samples can be explained by fractionation of Hf from W, and Sm from Nd (by ilmenite and clinopyroxene) during crystallization of the latest stages of a lunar magma ocean. Correlations of ε_W with ε_Nd in martian samples could be a result of early silicate fractionation in the martian mantle (clinopyroxene and/or garnet).     

Re-evaluating Nd/Nd in lunar mare basalts with implications for the early evolution and bulk Sm/Nd of the Moon

The Moon likely accreted from melt and vapor ejected during a cataclysmic collision between Proto-Earth and a Mars-sized impactor very early in solar system history. The identical W, O, K, and Cr isotope compositions between materials from the Earth and Moon require that the material from the two bodies were well-homogenized during the collision process. As such, the ancient isotopic signatures preserved in lunar samples provide constraints on the bulk composition of the Earth. Two recent studies to obtain high-precision ¹⁴²Nd/¹⁴⁴Nd ratios of lunar mare basalts yielded contrasting results. In one study, after correction of neutron fluence effects imparted to the Nd isotope compositions of the samples, the coupled ¹⁴²Nd-¹⁴³Nd systematics were interpreted to be consistent with a bulk Moon having a chondritic Sm/Nd ratio [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372]. The other study found that their data on the same and similar lunar mare basalts were consistent with a bulk Moon having a superchondritic Sm/Nd ratio [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516]. Delineating between these two potential scenarios has key ramifications for a comprehensive understanding of the formation and early evolution of the Moon and for constraining the types of materials available for accretion into large terrestrial planets such as Earth.To further examine this issue, the same six lunar mare basalt samples measured in Rankenburg et al. [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372] were re-measured for high-precision Nd isotopes using a multidynamic routine with reproducible internal and external precisions to better than ±3 ppm (2σ) for ¹⁴²Nd/¹⁴⁴Nd ratios. The measurements were repeated in a distinct second analytical campaign to further test their reproducibility. Evaluation of accuracy and neutron fluence corrections indicates that the multidynamic Nd isotope measurements in this study and the 3 in Boyet and Carlson [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516] are reproducible, while static measurements in the previous two studies show analytical artifacts and cannot be used at the resolution of 10 ppm to determine a bulk Moon with either chondritic or superchondritic Sm/Nd ratios. The multidynamic data are best explained by a bulk Moon with a superchondritic Sm/Nd ratio that is similar to the present-day average for depleted MORB. Hafnium isotope data were collected on the same aliquots measured for their ¹⁴²Nd/¹⁴⁴Nd isotope ratios in order to assess if the correlation line for ¹⁴²Nd-¹⁴³Nd systematics reflect mixing processes or times at which lunar mantle sources formed. Based on the combined ¹⁴²Nd-¹⁴³Nd-¹⁷⁶Hf obtained we conclude that the ¹⁴²Nd-¹⁴³Nd correlation line measured in this study is best interpreted as an isochron with an age of 229⁺²⁴₋₂₀Ma after the onset of nebular condensation. The uncertainties in the data permit the sources of these samples to have formed over a 44 Ma time interval. These new results for lunar mare basalts are thus consistent with a later Sm-Nd isotope closure time of their source regions than some recent studies have postulated, and a superchondritic bulk Sm/Nd ratio of the Moon and Earth. The superchondritic Sm/Nd signature was inherited from the materials that accreted to make up the Earth-Moon system. Although collisional erosion of crust from planetesimals is favored here to remove subchondritic Sm/Nd portions and drive the bulk of these bodies to superchondritic in composition, removal of explosive basalt material via gravitational escape from such bodies, or chondrule sorting in the inner solar system, may also explain the compositional features that deviate from average chondrites that make up the Earth-Moon system. This inferred superchondritic nature for the Earth similar to the modern convecting mantle means that there is no reason to invoke a missing, subchondritic reservoir to mass balance the Earth back to chondritic for Sm/Nd ratios. However, to account for the subchondritic Sm/Nd ratios of continental crust, a second superchondritic Sm/Nd mantle reservoir is required.     

地球早期演化的Hf-W同位素制约

~(182)Hf-~(182)W作为短周期放射性衰变体系,可有效约束地球早期演化吸积增生和内部分异过程。本文通过系统总结、归纳太阳系形成初期地球核幔分异过程中Hf-W同位素变化规律、月球与地球硅酸盐的W同位素组成,提出利用~(182)Hf-~(182)W体系测定地球核幔分异时间不确定性的主要原因是地球核幔分异的持续性及开放性,大碰撞时间的~(182)Hf-~(182)W同位素限定主要受控于硅酸盐地球和硅酸盐月球的Hf/W比值,讨论了地幔W同位素不均一性的形成机制,与现代地幔不同的~(182)W/~(184)W组成可能代表了后增生作用之前整体硅酸盐地球的W同位素组成,也可能是~(182)Hf未完全灭绝时形成的区域性Hf/W比值差异经~(182)Hf衰变形成的结果。这些结论为探索类地行星形成与演化提供了重要制约。     

Noble gases in the unique Kaidun meteorite

Two examined fragments of the Kaidun meteorite principally differ in the concentrations of isotopes of noble gases and are very heterogeneous in terms of the isotopic composition of the gases. Because these fragments belong to two basically different types of meteoritic material (EL and CR chondrites), these characteristics of noble gases could be caused by differences in the cosmochemical histories of the fragments before their incorporation into the parent asteroid. As follows from the escape kinetics of all gases, atoms of trapped and cosmogenic noble gases are contained mostly in the structures of two carrier minerals in the samples. The concentrations and proportions of the concentrations of various primary noble gases in the examined fragments of Kaidun are obviously unusual compared to data on most currently known EL and CR meteorites. In contrast to EL and CR meteorites, which contain the primary component of mostly solar provenance, the elemental ratios and isotopic composition of Ne and He in the fragments of Kaidun correspond to those typical of the primary components of A and Q planetary gases. This testifies to the unique conditions under which the bulk of the noble gases were trapped from the early protoplanetary nebula. The apparent cosmic-ray age of both of the Kaidun fragments calculated based on cosmogenic isotopes from ³He to ¹²⁶Xe varies from 0.027 to 246 Ma as a result of the escape of much cosmogenic isotopes at relatively low temperatures. The extrapolated cosmic-ray age of the Kaidun meteorite, calculated from the concentrations of cosmogenic isotopes of noble gases, is as old as a few billion years, which suggests that the material of the Kaidun meteorite could be irradiated for billions of years when residing in an unusual parent body.     

Tungsten and hafnium distribution in calcium-aluminum inclusions (CAIs) from Allende and Efremovka

Recent ¹⁸²Hf-¹⁸²W age determinations on Allende Ca-, Al-rich refractory inclusions (CAIs) and on iron meteorites indicate that CAIs have initial ε¹⁸²W (−3.47 ± 0.20, 2σ) identical to that of magmatic iron meteorites after correction of cosmogenic ¹⁸²W burn-out (−3.47 ± 0.35, 2σ). Either the Allende CAIs were isotopically disturbed or the differentiation of magmatic irons (groups IIAB, IID, IIIAB, and IVB) all occurred <1 m.y. after CAI formation. To assess the extent of isotopic disturbance, we have analyzed the elemental distribution of Hf and W in two CAIs, Ef2 from Efremovka (CV3 reduced), and Golfball from Allende (CV3 oxidized). Fassaite is the sole host of Hf (10-25 ppm) and, therefore, of radiogenic W in CAIs, with ¹⁸⁰Hf/¹⁸⁴W > 10³, which is lowered by the ubiquitous presence of metal inclusions to ¹⁸⁰Hf/¹⁸⁴W > 10 in bulk fassaite. Metal alloy (Ni ∼ 50%) is the sole host of W (∼500 ppm) in Ef2, while opaque assemblages (OAs) and secondary veins are the hosts of W in Golfball. A large metal alloy grain from Ef2, EM2, has ¹⁸⁰Hf/¹⁸⁴W < 0.006. Melilite has both Hf and W below detection limits (<0.01 ppm), but the presence of numerous metallic inclusions or OAs makes melilite a carrier for W, with ¹⁸⁰Hf/¹⁸⁴W < 1 in bulk melilite. Secondary processes had little impact on the ¹⁸²Hf-¹⁸²W systematics of Ef2, but a vein cross-cutting fassaite in Golfball has >100 ppm W with no detectable Pt or S. This vein provides evidence for transport of oxidized W in the CAI. Because of the ubiquitous distribution of OAs, interpretations of the ¹⁸²Hf-¹⁸²W isochron reported for Allende CAIs include: (i) all W in the OAs was derived by alteration of CAI metal, or (ii) at least some of the W in OAs may have been equilibrated with radiogenic W during metamorphism of Allende. Since (ii) cannot be ruled out, new ¹⁸²Hf-¹⁸²W determinations on CAIs from reduced CV3 chondrites are needed to firmly establish the initial W isotopic composition of the solar system.     

Neon and argon in the Allende meteorite

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

Stony-iron meteorites: History of the metal phase according to tungsten isotopes

The global composition of the early solar system is thought to be roughly chondritic in terms of refractory components, and this means that metal and silicate should be present together in early planetesimals. To fully understand the metal-silicate differentiation process within the eucrite parent body (EPB), it is important to try and identify the metal reservoir that is complementary to the silicate part. The isotope 182 of tungsten (W), a siderophile element, is partly formed from the decay of ¹⁸²Hf, and W isotopes are useful for examining metal-silicate segregation. The W isotopic composition expected for the metal that is complementary to eucrites falls in the range of iron meteorites. However, mesosiderites seem to be genetically linked to eucrites based on petrologic and oxygen isotopic similarities. Therefore, we undertook the analysis of the metal phase of these stony-irons. Here we present tungsten isotopic data for mesosiderite and pallasite metal to characterize their parent body (bodies) and to assess possible relationships with eucrites.All stony-iron metals are depleted in radiogenic tungsten by −1.3 to −4.2 ε units, relative to the terrestrial standard, while chondrites, for comparison, are depleted by −1.9 ε units. In addition to W isotopic heterogeneity from one stony-iron to another, there is also W isotopic heterogeneity within individual meteorites. A formation model is tentatively proposed, where we show that mesosiderites, pallasites, and eucrites could possibly come from the same parent body. Several hypotheses are discussed to explain the isotopic heterogeneity: the production of cosmogenic tungsten, the in situ decay of hafnium present in inclusions, and tungsten diffusion processes after metal-silicate mixing during the cooling of the meteorites. The two latter hypotheses provide the best explanation of our data.     

Weathering process at the natural fission reactor of Bangombé

 The uranium deposits in the basin of Franceville (Gabon) host the only natural fission reactors known in the world. Unique geological conditions favoured a natural fission reaction 2 Ga ago. This was detected by anomalous isotopic compositions of uranium and rare earth elements (REE), which are produced by the fission reaction. In total, 16 reactor zones were found. Most of them are mined out. The reactor zone of Bangombé, is only 10–11 m below the surface. This site has been influenced by surface weathering processes. Six drill cores have been sampled at the site of the reactor zone of Bangombé during the course of the study and only one drill core (BAX 08) hit the core of the reactor. From these data and previous drilling campaigns, the reactor size is estimated to be 10 cm thick, 2–3 m wide and 4–6 m long. The migration of fission products can be traced by the anomalous isotope ratios of REE because of the fission process. The ¹⁴⁹Sm/¹⁴⁷Sm ratio close to the reactor zone is only 0.28 (normal: 0.92) because of the intense neutron capture of ¹⁴⁹Sm and subsequent transmutation, whereas ¹⁴⁷Sm is enriched by the fission reaction. Similar changes in isotopic patterns are detectable on other REE. The isotope ratios of Sm and Nd of whole rock and fracture samples surrounding the reactor indicate that fission-genic REE migrated only a few decimetres above and mainly below the reactor zone. Organic matter (bitumen) seems to act as a trap for fission-genic REE. Additional REE-patterns show less intense weathering with increasing depth in the log profile and support a simple weathering model. Received: 26 November 1999 · Accepted: 2 May 2000     

Solar and cosmogenic argon in dated lunar impact spherules

We have studied lunar impact spherules from the Apollo 12 and Apollo 14 landing sites, examining the isotopic composition of argon released by stepwise heating. Elsewhere, we reported the formation ages of these spherules, determined by the ⁴⁰Ar/³⁹Ar isochron method. Here, we discuss solar and cosmogenic argon from the same spherules, separating these two components by correlating their partial releases with the releases of calcium-derived ³⁷Ar on a “cosmochron” diagram. We use the abundances of cosmogenic argon to derive a cosmic ray exposure age for each spherule, and demonstrate that single scoops of lunar soil contain spherules which have experienced very different histories of exposure and burial. The solar argon is seen to be separated into isotopically lighter and heavier fractions, which presumably were implanted to different depths in the spherules. The abundance of the isotopically heavy solar argon is too great to explain as a minor constituent of the solar particle flux, such as the suprathermal tail of the solar wind. The fact that the spherules have been individually dated allows us to look for possible variations in the solar wind as a function of time, over the history of the Solar System. However, the isotopic composition and fluence of solar argon preserved in the lunar spherules appear to be independent of formation age. We believe that most of the spherules are saturated with solar argon, having reached a condition in which implantation by the solar wind is offset by losses from solar-wind sputtering and diffusion.     

Isotopic evidence for trapped fissiogenic REE and nucleogenic Pu in apatite and Pb evolution at the Oklo natural reactor

A part of the boundary layer of reactor zone 10 at the Oklo natural reactor shows a unique petrologic texture, which contains high-grade uraninite and massive apatite concretions. In order to study distribution behavior of fission products around the boundary between the reactor zone and the wall rock and to clarify the relation of migration mechanisms of fission products with geochemical factors, in-situ isotopic analyses of Nd, Sm, Gd, Pb and U in uraninite and apatite from the sample were performed by Sensitive High Resolution Ion Microprobe (SHRIMP). Sm and Gd isotopic ratios of uraninite and apatite show evidence of neutron irradiation with fluence between 4.4-6.8×10¹⁹ n/cm². Judging from the isotopic anomalies of Nd and U, the apatite coexisting with the uraninite plays an important role in trapping fissiogenic LREE and nucleogenic ²³⁹Pu into the structure. Systematic Pb isotopic data from apatite, uraninite, galena and minium suggest the following chronological interpretations.

1.

The apatite formed 1.92±0.01 Ga ago and trapped fissiogenic light REE and nucleogenic ²³⁹Pu that migrated from the reactor during the criticality.

2.

The uraninite around the boundary between reactor and sandstone dissolved once 1.1∼1.2 Ga ago.

3.

Galena grains were formed by U-Pb mobilization in association with the intrusion of dolerite dyke 0.45∼0.83 Ga ago.

4.

Minium was derived from recent dissolution of galena under locally oxidizing conditions.