Aubrites and diogenites: Trace element clues to their origin

We have analyzed by RNAA 25 aubrite and 9 diogenite samples for 13 to 29 siderophile, volatile, and lithophile trace elements. Both meteorite classes show a typically igneous siderophile element pattern, with Ir, Os, Re, Ge more depleted than Au, Ni, Pd, Sb. But aubrites tend to have about 10 × higher abundances (10^?3 ? 10 ^{? 4} × Cl for the first 4 and 10^?2?10^?3 × Cl for the last 4 siderophiles), apparently reflecting smaller metal/silicate distribution coefficients at lowerf(O₂), or less complete segregation of metal. Se is surprisingly abundant in aubrites (up to 0.4 × Cl), but Te is less so ($\text{Se}\text{Te}\text{? 5 × Cl}$), apparently due to its stronger siderophile character. Other volatiles (Ag, Zn, In, Cd, Bi, T1) show depletions intermediate between lunar dunite and the Earth's mantle.Of 7 aubrites analyzed for REE (Ce, Nd, Eu, Tb, Yb, Lu), 6 are depleted in REE (0.08?0.5 × Cl) and 5 show negative Eu anomalies (the exceptions are Bishopville and Mt. Egerton silicate). This supports an igneous origin, as already noted by Boynton and Schmitt (1972). No samples of the complementary, basaltic and feldspathic rocks have been found thus far, but one of our samples of Khor Temiki dark is a candidate for the basalt. It is 5?7 × enriched in REE and only slightly less so in Rb, Cs, and U. Though shocked and enriched in siderophiles to ~0.05 × Cl, it apparently represents a new meteorite class.Three diogenites analyzed for REE show very diverse patterns, from strongly depleted in light REE for Tatahouine (Ce = 0.01 × Cl) to flat for Garland (~2.5 × Cl). The data confirm the trends found by Fukuokaet al. (1977) as well as their interpretations.Factor analysis shows several parallel groupings for aubrites and diogenites: siderophiles (Re, Ir, Os, Pd, Ge), chalcophiles (Se, Te), volatiles (Ag, In, Tl) and incompatibles (U, REE, and Cs or Rb). But there are some differences for elements such as Ni, Sb, Cd, Bi, Au, and Zn, most of which behave more sensibly in aubrites than in diogenites.Several element pairs that differ greatly in volatility (Cs-U, Ge-Ir) correlate closely in aubrites, in approximately Cl-chondrite proportions. These correlations, and other lines of evidence, suggest strongly that aubrites originated by igneous processes in their parent body, not by direct nebular condensation. The source material may have resembled EL chondrites in oxidation state and depletion of refractories, metal, and volatiles.     

Distribution of gold and rhenium between nickel-iron and silicate melts: implications for the abundance of siderophile elements on the Earth and Moon

The distribution equilibrium of Au and Re between nickel-iron and basaltic melts was studied at 1400–1600°C, using radioactive tracers. Metal/silicate distribution coefficients were 1–3 orders of magnitude higher than earlier estimates, as follows. Mauna Loa basalt—Fe₁₀Ni₉₀: D_Au = 3.3 × 10⁴, D_Re = (2.4?89) × 10⁴. Gorda Ridge basalt—Fe₁₀Ni₉₀: D_Au = (18?75) × 10⁴. Synthetic lunar basalt—Fe₇₀ Ni₃₀: D_Au≥ 2 × 10⁴, D_Re ≥ 2 × 10³. The experimental ΔG₁₈₀₀^° for the distribution of Au between nickel-iron and Mauna Loa basalt is ?40 kcal/mole, compared to a calculated value of about ?110 kcal/mole for a reaction involving simple Au³⁺ ions. Presumably the difference represents stabilization of Au(III) by complex formation with ligands such as Cl^?, H₂O, etc.Gold abundances in lunar basalts are roughly consistent with the measured D_Au, but those in terrestrial basalts are two orders of magnitude too high. This discrepancy may reflect complexing by volatiles in the Earth's upper lithosphere, as well as oxidative destruction of metal in the final stages of accretion. In the absence of a metal phase, siderophile trace elements would remain trapped in the upper mantle and crust.     

Geochemical constraints on the origin of the Moon

Hypotheses for the origin of the Moon involve variants on capture, double-planet, and fission processes. Double-planet and fission hypotheses are examined in the light of siderophile trace elements. The siderophile trace elements chosen (W, Re, Mo, P, Ga, Ge) have well understood geochemical behavior such that appropriate metal/silicate partition coefficients are available and their abundances in the lunar and terrestrial mantles 4.4–4.5 × 10⁹ years ago may be reasonably inferred. The fission hypothesis of Ringwood (1979) is not consistent with the behavior of Re, Mo, and P. The hybrid fission hypothesis of Wankeet al. (1983) overcomes many of the deficiencies of ringwood's hypothesis, but is not readily reconcilable with the behavior of Re and Ir. The double-planet hypothesis as most recently advanced by Newsom and Drake (1982, 1983) appears to be consistent with siderophile element behavior in the Moon.     

Volatile and siderophile trace elements in anorthositic rocks from Fiskenaesset. West Greenland: comparison with lunar and meteoritic analogues

Seventeen trace elements (Ag, Au, Bi, Br, Cd, Cs, Ge, Ir, Ni, Rb, Re, Sb, Se, Te, Tl, U, Zn) were analyzed by radiochemical neutron activation and 13 other elements (Ce, Co, Cr, Eu, Fe, Hf, La, Lu, Na, Sc, Sm, Tb, Yb) by instrumental neutron activation in a total of 12 rocks from the layered anorthositic complex at Fiskenaesset, West Greenland and in the plagioclase-rich unbrecciated eucrite, Serra de Magé.Garnet anorthosite 84428, which has an unusually sodic plagioclase, is spectacularly enriched in Cs, K, Rb. Tl and, to a lesser degree, Te. This appears to be the result of later metasomatism and not a reflection of fractionation trends within the anorthositic complex. For the remaining Fiskenaesset rocks, a factor analysis yields 5 principal factors for linear data for 22 elements and 6 factors for data transformed (log, ³√, √) to give approximately normal distributions. Linear correlations are controlled by high values, whereas the logarithmic transform increases the influence of the lowest values. Enrichment of several elements in chromitite 132022 underlies linear Factor 1. Six of these elements Co, Cr, Fe, Ir, Ni, Zn and possibly Re are probably hosted by chromite. In other zones of the intrusion, different fractionation trends may be more important, since in the transformed analysis these elements divide between Factor 1 (Co, Zn, Ni, Fe) and Factor 4 (Ir, Cr and also Au). Linear Factor 2 reflects the strong mutual correlation between Tl, Rb and An, the anorthite content of plagioclase. Transformed Factor 3 emphasizes the anticorrelation of Na and Sm with An. The positive correlations of Cs, U and Ge (linear Factor 3; transformed Factor 2) are largely due to their concentration in later crystallizates, but enrichment in lower zone gabbros of high An content perhaps indicates concentration in minor or accessory cumulate minerals. Flat chondrite-normalized rare earth element patterns in several anorthosites (except for a small positive Eu anomaly) suggests that the Fiskenaesset magma was relatively unfractionated.Factor 4 (linear) and Factor 5 (transformed) reflects the geochemical coherence of Se and Te. The sympathetic enrichment of Sb and Cd in 3 rocks, resulting in Factor 5 (linear) and Factor 6 (transformed) may be due to the lack of a suitable Zn sulfide host for Cd.In 3 rocks of true anorthosite composition, 8 volatile elements show rather constant abundance when normalized to Cl chondrites (mean 4.2 ± 0.4% Cl), possibly suggesting that volatile-rich material was accreted late in the Earth's formation, perhaps after core segregation. These anorthosites are higher than lunar anorthosite 15415 by a factor of 58 ± 9 in volatile elements. Siderophile and chalcophile elements are much more variable in Cl-normalized abundances in both lunar and terrestrial anorthosites, but surprisingly give somewhat similar Earth/Moon abundance ratios.Volatile elements in terrestrial oceanic basalts and lunar mare basalts are not as uniformly abundant as in anorthosites. but nevertheless yield a similar Earth/Moon ratio of 44 ± 8.Volatile elements in Serra de Magé are more abundant than in lunar anorthosites, but lower than in terrestrial equivalents, averaging (3.6 ± 0.8) × 10^?3C1.     

Light element geochemistry and spallogenesis in lunar rocks

The abundances and isotopic compositions of carbon, nitrogen and sulfur were measured in eleven lunar rocks. Samples were combusted sequentially at three temperatures to resolve terrestrial contamination from indigenous volatiles.Sulfur abundances in Apollo 16 highland rocks range from 73 to 1165 μg/g-whereas sulfur contents in Apollo 15 and 17 basalts range from 719 to 1455 μg/g and correlate with TiO₂ content. Lunar rocks as a group have a remarkably uniform sulfur isotopic composition, which may reflect the low oxygen fugacity of the basaltic magmas. Much of the range of reported δ³⁴S_cd values (?2 to + 2.5 permil) is caused by systematic analytical discrepancies between laboratories.Lunar rocks very likely contain less than 0.1 μg/g of nitrogen. The measured spallogenic production rate, 4.1 × 10^?6 μg ¹⁵N/g sample/m.y., agrees remarkably closely with previous estimates. An estimate which includes all available data is 3.7 × 10^?6 μg¹⁵N/g sample/m.y.Lunar basalts may contain no indigenous lunar carbon in excess of procedural blank levels (~0.7 μg/g). Highlands rocks consistently release about 1 to 5 μg/g of carbon in excess of blank levels, but this carbon might either derive from ancient meteoritic debris or be a mineralogie product of terrestrial weathering. The average measured spallogenic ¹³C production rate is 4.1 × 10^?6 μg¹³C/g sample/m.y. The ¹³C spallation exposure ages of rocks 15058 and 15499 are 184 and 135 m.y., respectively.     

汉诺坝玄武岩Re-Os同位素地球化学——Re的挥发性丢失和壳-幔相互作用的证据

本文报道了采自汉诺坝玄武岩区周坝和白龙硐剖面以及白布洛张20井等地29个玄武岩样品的Re、Os含量和~(187)Os/~(188)Os比值。Os含量为11×10~(-12)～314×10~(-12),Re含量为40×10~(-12)～238×10~(-12),Re和Os含量有正相关趋势。碱性玄武岩(AK)的Re、Os含量高于拉斑玄武岩(TH)和过渡玄武岩(TR),玄武岩Os含量变化与分离结晶作用有关,玄武岩的低Re含量与地面喷发的火山岩浆脱气过程中Re的挥发性丢失作用有关。玄武岩的~(187)Os/~(188)Os比值为0.14735～0.61136,AK的~(187)Os/~(188)Os比值比TH和TR低且变化小。玄武岩的~(187)Os/~(188)Os比值与Os含量有负相关性。随着Os含量降低到小于75×10~(-12),~(187)Os/~(188)Os比值迅速升高,反映了地壳混染在TH和TR成因中的贡献。在以往的研究中没有观察到类似的地壳混染作用,说明了Re-Os同位素体系在示踪壳源物质上的优势。一些Os含量较高的TH的~(187)Os/~(188)Os比值表明其地幔源区既非亏损的又非经交代富集的SCLM,可能是混入了地壳俯冲物质的"Marble cake"型地幔。总之,汉诺坝玄武岩的Re-Os同位素地球化学研究支持了以往研究的主要成果,两类玄武岩地球化学差异性和异源成因论;分离结晶和部分熔融过程在玄武岩成因中的重要作用;碱性玄武岩的成因与地幔柱的关系等。同时揭示了一些新的现象:汉诺坝玄武岩形成中存在少量的地壳混染作用;地面喷发的火山熔岩在脱气过程中Re的挥发性丢失;拉斑玄武岩的源区更有可能为"Marble cake"型地幔。     

Origin of highly siderophile and chalcogen element fractionations in the components of unequilibrated H and LL chondrites

Osmium isotopic compositions, abundances of highly siderophile elements (HSE: platinum group elements, Re and Au), the chalcogen elements S, Se and Te and major and minor elements were analysed in physically separated size fractions and components of the ordinary chondrites WSG 95300 (H3.3, meteorite find) and Parnallee (LL3.6, meteorite fall). Fine grained magnetic fractions are 268-65 times enriched in HSE compared to the non-magnetic fractions. A significant deviation of some fractions of WSG 95300 from the 4.568 Ga ¹⁸⁷Re-¹⁸⁷Os isochron was caused by redistribution of Re due to weathering of metal. HSE abundance patterns show that at least four different types of HSE carriers are present in WSG 95300 and Parnallee. The HSE carriers display (i) CI chondritic HSE ratios, (ii) variable Re/Os ratios, (iii) lower than CI chondritic Pd/Ir and Au/Ir and (iv) higher Pt/Ir and Pt/Ru than in CI chondrites. These differences between components clearly indicate the loss of refractory HSE carrier phases before accretion of the components. Tellurium abundances correlate with Pd and are decoupled from S, suggesting that most Te partitioned into metal during the last high-temperature event. Tellurium is depleted in all fractions compared to CI chondrite normalized Se abundances. The depletion of Te is likely associated with the high temperature history of the metal precursors of H and LL chondrites and occurred independent of the metal loss event that depleted LL chondrites in siderophile elements. Most non-magnetic and slightly magnetic fractions have S/Se close to CI chondrites. In contrast, the decoupling of Te and Se from S in magnetic fractions suggests the influence of volatility and metal-silicate partitioning on the abundances of the chalcogen elements. The influence of terrestrial weathering on chalcogen element systematics of these meteorites appears to be negligible.     

Re-Os isotopic systematics and platinum group element composition of the Tagish Lake carbonaceous chondrite

The Tagish Lake meteorite is a primitive C2 chondrite that has undergone aqueous alteration shortly after formation of its parent body. Previous work indicates that if this type of material was part of a late veneer during terrestrial planetary accretion, it could provide a link between atmophile elements such as H, C, N and noble gases, and highly siderophile element replenishment in the bulk silicate portions of terrestrial planets following core formation. The systematic Re-Os isotope and highly siderophile element measurements performed here on five separate fractions indicate that while Tagish Lake has amongst the highest Ru/Ir (1.63 ± 0.08), Pd/Ir (1.19 ± 0.06) and ¹⁸⁷Os/¹⁸⁸Os (0.12564-0.12802) of all carbonaceous chondrites, these characteristics still fall short of those necessary to explain the observed siderophile element systematics of the primitive upper mantles of Earth and Mars. Hence, a direct link between atmophile and highly siderophile elements remains elusive, and other sources for replenishment are required, unless an as yet poorly constrained process fractionated Re/Os, Ru/Ir, and Pd/Ir following late accretion on both the Earth and Mars mantles.The unique elevated Ru/Ir combined with elevated ¹⁸⁷Os/¹⁸⁸Os of Tagish Lake may be attributed to Ru and Re mobility during aqueous alteration very early in its parent body history. The Os, Ir, Pt, and Pd abundances of Tagish Lake are similar to CI chondrites. The elevated Ru/Ir and the higher Re/Os and consequent ¹⁸⁷Os/¹⁸⁸Os in Tagish Lake, are balanced by a lower Ru/Ir and lower Re/Os and ¹⁸⁷Os/¹⁸⁸Os in CM-chondrites, relative to CI chondrites. A model that links Tagish Lake with CI and CM chondrites in the same parent body may explain the observed systematics. In this scenario, CM chondrite material comprises the exterior, grading downward to Tagish Lake material, which grades to CI material in the interior of the parent body. Aqueous alteration intensifies towards the interior with increasing temperature. Ruthenium and Re are mobilized from the CM layer into the Tagish Lake layer. This model may thus provide a potential direct parent body relationship between three separate groups of carbonaceous chondrites.     

Contribution of recycled sediments to the mantle reservoir beneath Hainan Island: Evidence from Sr,Nd, Pb,Hf, and Mg isotopic analyses of Late Cenozoic basalts

Magnesium isotopes are a useful tool for constraining the origin of basalts with EM-like isotopic signatures in relation to ancient subducted slabs and recycled materials incorporated in mantle plumes. In this study, we present new SrNdPbHf and Mg isotopic data that were used to determine the origin of the basalt on Hainan Island and investigate the EM mantle reservoir beneath the island. Cenozoic basalts from northern Hainan Island are mainly tholeiitic, with a small amount of alkaline basalts. The Hainan basalts exhibited depleted SrNd isotopic compositions and EM2-like Pb isotopic signatures. The δ²⁶Mg values of the Hainan basalts ranged from ?0.40‰ to ?0.28‰. The origin of the low δ²⁶Mg signature can be attributed to carbonate sediments from recycled oceanic slab. Hainan basalts show a negative concave curve relationship between ⁸⁷Sr/⁸⁶Sr and ε_Nd values, a positive relationship between ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb values and exhibit an evolution trend from depleted mantle towards marine sediments. This indicates that Hainan Island basalts can be explained by the mixing between depleted mantle and marine sediments. Most Hainan basalts have higher K/U × 10^?3 and Ba/Th ratios than primitive mantle (K/U × 10^?3 ≈ 11.8, Ba/Th ≈ 83), moreover, display highly correlated K/U × 10^?3 and Ba/Th compositions with low-pressure (6–8 GPa) carbonated melt released from initial sediments. Therefore, we speculate that the primitive mantle peridotite, coupled with the low-pressure carbonated melt, ultimately became the mantle source of Hainan Island basalts.     

Volatile elements in chondrites: metamorphism or nebular fractionation?

Three of the most highly metamorphosed meteorites of their respective classes, Shaw (LL7), Karoonda (C5), and Coolidge (C4), were analyzed by radiochemical neutron activation analysis for Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Ni, Os, Pd, Rb, Re, Sb, Se, Te, Tl, U, and Zn. Comparison with data by Lipschutz and coworkers on artificially heated primitive meteorites shows that the natural metamorphism of meteorites cannot have taken place in a system open to volatiles. Shaw, metamorphosed at 1300°C for >10⁶ yr, is less depleted in In, Bi, Ag, Te, Zn, and Tl than Krymka heated at 1000°C for 1 week. Karoonda, metamorphosed at 600°C for many millennia, is less depleted in Bi and Tl than Allende heated at 600°C for 1 week.Data on primordial noble gases also show that the volatile-element patterns of ordinary and carbonaceous chondrites were established by nebular condensation, and changed little if at all during metamorphism. For enstatite chondrites, the evidence is still incomplete, but seems to favor a nebular origin of the volatile pattern.The general constancy of Tl/Rb, Tl/Cs and Tl/U ratios in terrestrial and lunar rocks suggests that loss of volatile metals such as Tl is rare during normal magmatism or metamorphism. Only impact melts show such loss with any frequency.     

Ti K-edge XANES study on the coordination number and oxidation state of Titanium in pyroxene,olivine, armalcolite,ilmenite, and silicate glass during mare basalt petrogenesis

Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO₂) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (>?100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti³⁺ under fO₂ conditions relevant to lunar magmatism (IW ??1.5 to ??1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% ^[IV]Ti⁴⁺ in the pyroxene. In addition, our results can help to better constrain the Ti³⁺/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.     

Chemical fractionations in meteorites—VI. Accretion temperatures of H-, LL- and E-chondrites,from abundance of volatile trace elements

Extending our earlier work on 11 L-chondrites, we have measured 9 volatile elements (Ag, Bi, Cs, In, Rb, Tl, Se, Cd, Zn) by neutron activation analysis in 11 LL- and 10 E-chondrites; the first 6 elements also in 22 H-chondrites. The observed fractionation patterns are consistent with theoretical condensation curves and hence were apparently established during condensation from the solar nebula. Ordinary chondrites seem to have accreted between 420 and 500°K at $\text{P ≈ 10}{}^{\mathrm{?5}}$ atm; enstatite chondrites, at 460 to 520°K and P ≈ 5 x? 10^?4 atm. The values for ordinary chondrites agree with O¹⁸-based temperatures by Onuma. et al. (1972) and with other characteristics such as Fe²⁺ content, presence of FeS and absence of Fe₃O₄.A few detailed trends were noted. Seven of the 54 meteorites seem to contain small amounts of a material enriched in Ag, Bi and especially T1; possibly a late condensate from a region depleted in metal. Silver shows considerable scatter, which suggests inhomogeneous distribution in the meteorites. Xenon correlates with In approximately as expected for equilibrium solubility, with some differences (petrologic type 3; E-chondrites) attributable to mineralogical factors. Meteorites of higher petrologic types are slightly deficient in Xe, probably due to gas losses during metamorphism. Cesium also appears to have been redistributed during metamorphism.Various features of the two-component model are critically examined in the light of the latest evidence. Apparently this model still is an adequate approximation of reality.     

Apatite as a probe of halogen and water fugacities in the terrestrial planets

Apatite preserves a record of the halogen and water fugacities that existed during the waning stages of crystallization of planetary magmas, when they became saturated in phosphates. We develop a thermodynamic formalism based on apatite-merrillite equilibria that makes it possible to compare the relative values of halogen and water fugacities in Martian, lunar and terrestrial basalts, accounting for possible differences in pressure, temperature and oxygen fugacities among the planets. We show that each of these planetary bodies has distinctive ratios among volatile fugacities at apatite saturation and that these fugacities are in some cases related in a consistent way to volatile fugacities in the mantle magma sources. Our analysis shows that the Martian mantle parental to basaltic SNC meteorites was dry and poor in both fluorine and chlorine compared to the terrestrial mantle. The limited data available from Mars show no secular variation in mantle halogen and water fugacities from ∼4 Ga to ∼180 Ma. The water and halogens found in present-day Martian surface rocks have thus resided in the planet’s surficial systems since at least 4 Ga, and may have been degassed from the planet’s interior during a primordial crust-forming event. In comparison to the Earth and Mars, the Moon, and possibly the eucrite parent body too, appear to be strongly depleted not only in H₂O but also in Cl₂ relative to H₂O. Chlorine depletion is strongest in mare basalts, perhaps reflecting an eruptive process characteristic of large-scale lunar magmatism.     

Origin of planetary cores: evidence from highly siderophile elements in martian meteorites

We present new bulk compositional data for 6 martian meteorites, including highly siderophile elements Ni, Re, Os, Ir and Au. These and literature data are utilized for comparison versus the siderophile systematics of igneous rocks from Earth, the Moon, and the HED asteroid. The siderophile composition of ALH84001 is clearly anomalous. Whether this reflects a more reducing environment on primordial Mars when this ancient rock first crystallized, or secondary alteration, is unclear. QUE94201 shows remarkable similarity with EET79001-B for siderophile as well as lithophile elements; both are extraordinarily depleted in the “noblest” siderophiles (Os and Ir), to roughly 0.00001 × CI chondrites. As in terrestrial igneous rocks, among martian rocks Ni, Os and Ir show strong correlations vs. MgO. In the case of MgO vs. Ni, the martian trend is displaced toward lower Ni by a large factor (5), but the Os and Ir trends are not significantly displaced from their terrestrial counterparts. For Mars, Re shows a rough correlation with MgO, indicating compatible behavior, in contrast to its mildly incompatible behavior on Earth. Among martian MgO-rich rocks, Au shows a weak anticorrelation vs. MgO, resembling the terrestrial distribution except for a displacement toward 2–3 times lower Au. The same elements (Ni, Re, Os, Ir and Au) show similar correlations with Cr substituted for MgO. Data for lunar and HED rocks generally show less clear-cut trends (relatively few MgO-rich samples are available). These trends are exploited to infer the compositions of the primitive Earth, Mars, Moon and HED mantles, by assuming that the trend intercepts the bulk MgO or Cr content of the primitive mantle at the approximate primitive mantle concentration of the siderophile element. Results for Earth show good agreement with earlier estimates. For Mars, the implied primitive mantle composition is remarkably similar to the Earth’s, except for 5 times lower Ni. The best constrained of the extremely siderophile elements, Os and Ir, are present in the martian mantle at 0.005 times CI, in comparison to 0.007 times CI in Earth’s mantle. This similarity constitutes a key constraint on the style of core-mantle differentiation in both Mars and Earth. Successful models should predict similarly high concentrations of noble siderophile elements in both the martian and terrestrial mantles (“high” compared to the lunar and HED mantles, and to models of simple partitioning at typical low-pressure magmatic temperatures), but only predict high Ni for the Earth’s mantle. Models that engender the noble siderophile excess in Earth’s mantle through a uniquely terrestrial process, such as a Moon-forming giant impact, have difficulty explaining the similarity of outcome (except for Ni) on Mars. The high Ni content of the terrestrial mantle is probably an effect traceable to Earth’s size. For the more highly siderophile elements like Os and Ir, the simplest model consistent with available constraints is the veneer hypothesis. Core-mantle differentiation was notably inefficient on the largest terrestrial planets, because during the final ∼ 1% of accretion these bodies acquired sufficient H₂O to oxidize most of the later-accreting Fe-metal, thus eliminating the carrier phase for segregation of siderophile elements into the core.     

Refractory trace elements in Ca-Al-rich inclusions in the Allende meteorite

The condensation temperatures are calculated for a number of refractory trace metals from a gas of solar composition at 10^?3 and 10^?4 atm. total pressure. Instrumental neutron activation analysis of Ca-Al-rich inclusions in the Allende carbonaceous chondrite reveals enrichments of 22.8 ± 2.2 in the concentrations of Ir, Sc and the rare earths relative to Cl chondrites. Such enrichments cannot be due to magmatic differentiation processes because of the marked differences in chemical behavior between Ir and Sc, exhibited by their distributions in terrestrial igneous rocks and meteorites. All of these elements should have condensed from a cooling gas of solar composition above or within the range of condensation temperatures of the major mineral phases of the inclusions, which suggests that these inclusions are high-temperature condensates from the primitive solar nebula. Gas-dust fractionation of these materials may have been responsible for the depletion of refractory elements in the ordinary and enstatite chondrites relative to the carbonaceous chondrites.     

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.     

Abundance of 17 trace elements in carbonaceous chondrites

Seventeen trace elements (Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Rb, Re, Sb, Se, Te, Tl, U and Zn) were measured by neutron activation analysis in 8 C1 samples (1 Alais, 3 Ivuna, 4 Orgueil) and in 3 C2 samples (one each of Mighei, Murchison, Murray). The results show far less scatter than earlier literature data. The standard deviation of a single measurement from the mean of 8 C1 samples lies between 2 and 14 per cent, except for the following 4 elements: Au ±18 per cent, Ag ±22 per cent, Rb ±19 per cent and Br ±33 per cent. The first two probably reflect contamination and sample heterogeneity, the last two, analytical error. Apparently C1 chondrites have a far more uniform composition than some authors have claimed.The new data suggest significant revisions in cosmic abundance for the following elements (old values in parentheses): Zn 1250 (1500), Cd 1.51 (2.12), Ir 0.72 (0.43) atoms/10⁶ Si atoms. The Br value is also lower, 6.8 vs 20.6, but may be affected by analytical error.Relative to C1 chondrites, the C2 chondrites Mighei, Murchison and Murray are depleted in volatile elements by a factor of 0.508 ± 0.038, much more constant than indicated by oldor data. Ordinary chondrites also show a more uniform depletion relative to the new C1 data. The mean depletion factor of Sb, F, Cu, Ga, Ge, Sn, S, Se, Te and Ag is 0.227 ± 0.027 in H-chondrites. This constancy further strengthens the case for the two-component model of chondrite formation.     

New W-isotope evidence for rapid terrestrial accretion and very early core formation

The short-lived ¹⁸²Hf-¹⁸²W-isotope system is an ideal clock to trace core formation and accretion processes of planets. Planetary accretion and metal/silicate fractionation chronologies are calculated relative to the chondritic ¹⁸²Hf-¹⁸²W-isotope evolution. Here, we report new high-precision W-isotope data for the carbonaceous chondrite Allende that are much less radiogenic than previously reported and are in good agreement with published internal Hf-W chronometry of enstatite chondrites. If the W-isotope composition of terrestrial rocks, representing the bulk silicate Earth, is homogeneous and 2.24 ε_182W units more radiogenic than that of the bulk Earth, metal/silicate differentiation of the Earth occurred very early. The new W-isotope data constrain the mean time of terrestrial core formation to 34 million years after the start of solar system accretion. Early terrestrial core formation implies rapid terrestrial accretion, thus permitting formation of the Moon by giant impact while ¹⁸²Hf was still alive. This could explain why lunar W-isotopes are more radiogenic than the terrestrial value.     

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.     

Records of ancient cosmic radiation in extraterrestrial rocks

Recent results on cosmic ray interactions in lunar samples and meteorites resulting in production of stable and radionuclides, particle tracks and thermoluminescence are reviewed. A critical examination of²⁶A1 depth profiles in lunar rocks and soil cores, together with particle track data, enables us to determine the long term average fluxes of energetic solar protons (>10 MeV) which can be represented by (J _s,R _o)=(125, 125). The lunar rock data indicate that this flux has remained constant for 5×10⁵ to 2×10⁶ years. Production rates of stable and radionuclides produced by galactic cosmic rays is given as a function of size and depth of the meteoroid. Radionuclide (⁵³Mn,²⁸Al) depth profiles in meteorite cores, whose preatmospheric depths are deduced from track density profiles are used to develop a general procedure for calculating isotope production rates as a function of meteoroid size. Based on the track density and²²Ne/²¹Ne production rates, a criterion is developed to identify meteorites with multiple exposure history.²²Ne/²¹Ne ratio <1·06 is usually indicative of deep shielded exposure. An examination of the available data suggests that the frequency of meteorites with multiple exposure history is high, at least 15% for LL, 27% for L and 31% for H chondrites. The epi-thermal and the thermal neutron density profiles in different meteorites are deduced from⁶⁰Co and track density data in Dhajala, Kirin and Allende chondrites. The data show that the production profile depends sensitively on the size and the chemical composition of the meteoroid. Cosmic ray-induced thermoluminescence in meteorites of known preatmospheric sizes has been measured which indicates that its production profile is nearly flat and insensitive to the size of the meteoroid. Some new possibilities in studying cosmic ray implanted radionuclides in meteorites and lunar samples using resonance ionisation spectroscopy are discussed.