Extreme deuterium enrichment of organic radicals in the Orgueil meteorite: Revisiting the interstellar interpretation?

The insoluble organic matter of the carbonaceous meteorites contains radicals having a polyaromatic structure and a heterogeneous distribution. By using Hyperfine Sublevel Correlation spectroscopy (HYSCORE) in pulsed Electron Paramagnetic Resonance (pulsed-EPR), whereby nuclear frequencies of magnetic nuclei and their hyperfine interaction with electron spin of radicals are detected with high resolution, the radicals are shown to be considerably enriched in deuterium in the Orgueil meteorite, with a D/H ratio of 1.5 ± 0.5 × 10⁻². These radicals hold 3.6 ± 1.2 × 10⁻³ H relative to total organic H.Analysis of hydrogen and deuterium hyperfine interactions indicates that the deuterium atoms are localized in the benzylic position, on aliphatic carbons bonded to aromatic radical moieties. This type of C-H bond exhibits one of the smallest bond energy, reinforcing the recent finding that the lower the C-H bond energy the higher the deuterium-enrichment (Remusat L., Palhol F., Robert F., Derenne S. and France-Lanord C. (2006) Enrichment of deuterium in insoluble organic matter from primitive meteorites: a solar system origin? Earth Planet. Sci. Lett.243, 15-25). Such a behavior is difficult to reconcile with the usual interpretation according to which high D/H ratios represent survivals of interstellar grains. More likely, the deuterium-enrichment process took place after the formation of organic grains whose initial isotopic compositions was close to the protosolar D/H ratio. These grains were possibly loaded at the surface of the protosolar disk where they exposed to the intense solar UV irradiation, triggering an isotopic exchange with deuterium-rich highly reactive ions.     

Diverse nucleosynthetic components in barium isotopes of carbonaceous chondrites: Incomplete mixing of s- and r-process isotopes and extinct Cs in the early solar system

Barium isotopic compositions of chemical leachates from six carbonaceous chondrites, Orgueil (CI), Mighei (CM2), Murray (CM2), Efremovka (CV3), Kainsaz (CO3), and Karoonda (CK4), were determined using thermal ionization mass spectrometry in order to assess the chemical evolution in the early solar system.The Ba isotopic data from most of the leachates show variable ¹³⁵Ba excesses correlated with ¹³⁷Ba excesses, suggesting the presence and heterogeneity of additional nucleosynthetic components for s- and r-processes in the solar system. The isotopic deviations observed in this study were generally small (−1 < ε < +1) except in the case of the acid residues of CI and CM meteorites. Large deviations of ¹³⁵Ba (ε = −13.5 to −5.0) and ¹³⁷Ba (ε = −6.2∼−1.2) observed in the acid residues from one CI and two CM meteorites show significant evidence for the enrichment of s-process isotopes derived from presolar grains. Two models were proposed to estimate the ¹³⁵Cs isotopic abundances by subtraction of the s- and r-isotopic components from the total Ba isotopic abundances in the three CM meteorites, Mighei, Murchison (measured in a previous study), and Murray. The data points show individual linear trends between ¹³⁵Cs/¹³⁶Ba ratios and ¹³⁵Ba isotopic deviations for the three samples. Considering the different trends observed in the three CM meteorites, the Ba isotopic composition of the CM meteorite parent body was heterogeneous at its formation. Chronological information is unclear in the data for Murchison and Murray because of large analytical uncertainties imposed by error propagation. Only the Mighei meteorite data indicate the possible existence of presently extinct ¹³⁵Cs (¹³⁵Cs/¹³³Cs = (2.7 ± 1.6) × 10⁻⁴) in the early solar system. Another explanation of the data for the three CM meteorite is mixing of at least three components with different Ba isotopic compositions, although this is model-dependent.     

Evidence for aqueous activity on comet 81P/Wild 2 from sulfide mineral assemblages in Stardust samples and CI chondrites

The discovery of nickel-, copper-, and zinc-bearing iron sulfides from comet 81P/Wild 2 (Wild 2) represents the strongest evidence, in the Stardust collection, of grains that formed in an aqueous environment. We investigated three microtomed TEM sections which contain crystalline sulfide assemblages from Wild 2 and twelve thin sections of the hydrothermally altered CI chondrite Orgueil. Detailed structural and compositional characterizations of the sulfide grains from both collections reveal striking similarities. The Stardust samples include a cubanite (CuFe₂S₃) grain, a pyrrhotite [(Fe,Ni)_1−xS]/pentlandite [(Fe,Ni)₉S₈] assemblage, and a pyrrhotite/sphalerite [(Fe,Zn)S] assemblage. Similarly, the CI-chondrite sulfides include individual cubanite and pyrrhotite grains, cubanite/pyrrhotite assemblages, pyrrhotite/pentlandite assemblages, as well as possible sphalerite inclusions within pyrrhotite grains. The cubanite is the low temperature orthorhombic form, which constrains temperature to a maximum of 210 °C. The Stardust and Orgueil pyrrhotites are the 4C monoclinic polytype, which is not stable above ∼250 °C. The combinations of cubanite and pyrrhotite, as well as pyrrhotite and pentlandite signify even lower temperatures. The crystal structures, compositions, and petrographic relationships of these sulfides constrain formation and alteration conditions. Taken together, these constraints attest to low-temperature hydrothermal processing.Our analyses of these minerals provide constraints on large scale issues such as: heat sources in the comet-forming region; aqueous activity on cometary bodies; and the extent and mechanisms of radial mixing of material in the early nebula. The sulfides in the Wild 2 collection are most likely the products of low-temperature aqueous alteration. They provide evidence of radial mixing of material (e.g. cubanite, troilite) from the inner solar system to the comet-forming region and possible secondary aqueous processing on the cometary body.     

γ-ray irradiation in the early Solar System and the conundrum of the Lu decay constant

When recent geological calibrations of the ¹⁷⁶Lu decay constant are used, the ¹⁷⁶Lu-¹⁷⁶Hf ages of chondrites are consistently 4% too old (∼4.75 Ga). Here, we suggest that this discrepancy reflects the photoexcitation of the long-lived ¹⁷⁶Lu ground state to the short-lived isomeric state (T_1/2 = 3.7 h) by γ-rays irradiating early condensates. Irradiation may have been of solar origin and taking place at the inner edge of the nebular disk. Alternatively, the source of γ-rays could have been one or more supernova(e) exploding in the vicinity of the solar nebula. Such photoexcitation has been experimentally observed, but requires γ-ray photons that have energies in excess of 838 keV. At this stage, we cannot assess whether the Hf isotope composition of the Bulk Silicate Earth differs from that of chondrites, eucrites, and the 4.56 Ga old Martian meteorite ALH84001, and therefore, whether the precursor material for these different planetary bodies received comparable fluences of γ-rays.     

Timescales for the evolution of oxygen isotope compositions in the solar nebula

We review two models for the origin of the calcium-, aluminum-rich inclusion (CAI) oxygen isotope mixing line in the solar nebula: (1) CO self-shielding, and (2) chemical mass-independent fractionation (MIF). We consider the timescales associated with formation of an isotopically anomalous water reservoir derived from CO self-shielding, and also the vertical and radial transport timescales of gas and solids in the nebula. The timescales for chemical MIF are very rapid. CO self-shielding models predict that the Sun has Δ¹⁷O_SMOW ∼ −20‰ (Clayton, 2002), and chemical mass-independent fractionation models predict Δ¹⁷O_SMOW ∼0‰. Preliminary Genesis results have been reported by McKeegan et al. (McKeegan K. D., Coath C. D., Heber, V., Jarzebinski G., Kallio A. P., Kunihiro T., Mao P. H. and Burnett D. S. (2008b) The oxygen isotopic composition of captured solar wind: first results from the Genesis. EOS Trans. AGU 89(53), Fall Meet. Suppl., P42A-07 (abstr)) and yield a Δ¹⁷O_SMOW of ∼ −25‰, consistent with a CO self-shielding scenario. Assuming that subsequent Genesis analyses support the preliminary results, it then remains to determine the relative contributions of CO self-shielding from the X-point, the surface of the solar nebula and the parent molecular cloud.The relative formation ages of chondritic components can be related to several timescales in the self-shielding theories. Most importantly the age difference of ∼1-3 My between CAIs and chondrules is consistent with radial transport from the outer solar nebula (>10 AU) to the meteorite-forming region, which supports both the nebular surface and parent cloud self-shielding scenarios. An elevated radiation field intensity is predicted by the surface shielding model, and yields substantial CO photolysis (∼50%) on timescales of 0.1-1 My. An elevated radiation field is also consistent with the parent cloud model. The elevated radiation intensities may indicate solar nebula birth in a medium to large cluster, and may be consistent with the injection of ⁶⁰Fe from a nearby supernova and with the photoevaporative truncation of the solar nebula at KBO orbital distances (∼47 AU). CO self-shielding is operative at the X-point even when H₂ absorption is included, but it is not yet clear whether the self-shielding signature can be imparted to silicates. A simple analysis of diffusion times shows that oxygen isotope exchange between ¹⁶O-depleted nebular H₂O and chondrules during chondrule formation events is rapid (∼minutes), but is also expected to be rapid for most components of CAIs, with the exception of spinel. This is consistent with the observation that spinel grains are often the most ¹⁶O-rich component of CAIs, but is only broadly consistent with the greater degree of exchange in other CAI components. Preliminary disk model calculations of self-shielding by N₂ demonstrate that large δ¹⁵N enrichments (∼ +800‰) are possible in HCN formed by reaction of N atoms with organic radicals (e.g., CH₂), which may account for ¹⁵N-rich hotspots observed in lithic clasts in some carbonaceous chondrites and which lends support to the CO self-shielding model for oxygen isotopes.     

Confined pyrolysis of Tertiary lacustrine source rocks in the Western Qaidam Basin,Northwest China: Implications for generative potential and oil maturity evaluation

The parameter S₁ + S₂ (genetic potential) of Rock-Eval analysis is widely used as an evaluation of the genetic potential for the source rocks. Oligocene–Miocene saline lacustrine source rocks in the western Qaidam basin have low total organic C contents (TOC), most around 0.5% with a few exceptions >1.0%. Mineral matrix effects are substantial for source rocks with low TOC, resulting in relatively low S₁ and S₂ peaks. Based on the results of confined pyrolyses (sealed Au capsules) on 6 Oligocene–Miocene source rocks from the western Qaidam basin, with TOC ranging between 0.48% and 2.22%, the relationship between the S₁ + S₂ parameter and the maximum amount of extracted bitumen or saturated and aromatic hydrocarbons (SA) after the confined pyrolysis has been established as follows: bitumen (mg/g rock) = 1.4924 × (S₁ + S₂) + 0.3201 (r = 0.987), or SA (saturates + aromatics) (mg/g rock) = 0.7083 × (S₁ + S₂) + 0.4045 (r = 0.992). Based on these formulas, the amounts of hydrocarbons generated from source rocks can be reasonably estimated. The typical crude oils with low biomarker maturities in this region appear substantially different to the pyrolysates of these six rocks at 180–300 °C but comparable to the pyrolysates at 320 °C and higher temperatures based on molecular parameters. This result, in combination with the physical and gross compositions of the crude oils, suggests that the majority of these crude oils were generated from the source rocks during the main oil-generative stage, possibly at a maturity higher than R_o 0.74%.     

Molecular and compound-specific hydrogen isotope analyses of insoluble organic matter from different carbonaceous chondrite groups

We have conducted the first systematic analyses of molecular distribution and δD values of individual compounds in pyrolysates of insoluble organic matter (IOM) from different carbonaceous chondrite groups, using flash pyrolysis coupled to gas chromatography-mass spectrometry and compound-specific D/H analysis. IOM samples from six meteorites of different classifications, Elephant Moraine (EET) 92042 (CR2), Orgueil (CI1), Allan Hills (ALH) 83100 (CM1/2), Murchison (CM2), ALH 85013 (CM2), and Tagish Lake (C2) were isolated and studied. Except for the pyrolysate of Tagish Lake IOM, pyrolysates of all five meteorite IOM samples were dominated by an extensive series of aromatic (C₁ to C₇ alkyl-substituted benzenes, C₀ to C₂ alkyl-substituted naphthalenes), with aliphatic (straight chain and branched C₁₀ to C₁₅ alkanes) hydrocarbons and several S- and O- containing compounds (C₁ to C₂ alkylthiophenes, benzothiophene, benzaldehyde) being also present. The strong similarity in the pyrolysates of different carbonaceous chondrites suggests certain common characteristics in the formation mechanisms of IOM from different meteorites. The Tagish Lake IOM sample is unique in that its pyrolysate lacks most of the alkyl-substituted aromatic hydrocarbons detected in other meteorite IOM samples, suggesting distinctively different formation processes. Both bulk δD values of meteorite IOMs and weighted-average δD values of individual compounds in pyrolysates show a decreasing trend: CR2 > CI1 > CM2 > C2 (Tagish Lake), with the EET 92042 (CR2) IOM having the highest δD values (∼2000‰ higher than other samples). We attribute the high D contents in the IOM to primitive interstellar organic sources.     

The distribution of short-lived radioisotopes in the early solar system and the chronology of asteroid accretion, differentiation, and secondary mineralization

We evaluate initial (²⁶Al/²⁷Al)_I, (⁵³Mn/⁵⁵Mn)_I, and (¹⁸²Hf/¹⁸⁰Hf)_I ratios, together with ²⁰⁷Pb/²⁰⁶Pb ages for igneous differentiated meteorites and chondrules from ordinary chondrites for consistency with radioactive decay of the parent nuclides within a common, closed isotopic system, i.e., the early solar nebula. The relative initial isotopic abundances of ²⁶Al, ⁵³Mn, and ¹⁸²Hf in differentiated meteorites and chondrules are consistent with decay from common solar system initial values, here denoted by I(Al)_SS, I(Mn)_SS, and I(Hf)_SS, respectively. I(Mn)_SS and I(Hf)_SS = 9.1 ± 1.7 × 10⁻⁶ and 1.07 ± 0.08 × 10⁻⁴, respectively, correspond to “canonical” I(Al)_SS = 5.1 × 10⁻⁵. I(Hf)_SS so determined is consistent with I(Hf)_SS = 9.72 ± 0.44 × 10⁻⁵ directly determined from an internal Hf-W isochron for CAI minerals. I(Mn)_SS is within error of the lowest value directly measured for CAIs. We suggest that erratically higher values measured for CAIs in carbonaceous chondrites may reflect proton irradiation of unaccreted CAIs by the early Sun after other asteroids destined for melting by ²⁶Al decay had already accreted. The ⁵³Mn incorporated within such asteroids would have been shielded from further “local” spallogenic contributions from within the solar system. The relative initial isotopic abundances of the short-lived nuclides are less consistent with the ²⁰⁷Pb/²⁰⁶Pb ages of the corresponding materials than with one another. The best consistency of short- and long-lived chronometers is obtained for (¹⁸²Hf/¹⁸⁰Hf)_I and the ²⁰⁷Pb/²⁰⁶Pb ages of angrites. (¹⁸²Hf/¹⁸⁰Hf)_I decreases with decreasing ²⁰⁷Pb/²⁰⁶Pb ages at the rate expected from the 8.90 ± 0.09 Ma half-life of ¹⁸²Hf. The model solar system age thus determined is T_SS,Hf-W = 4568.3 ± 0.7 Ma. (²⁶Al/²⁷Al)_I and (⁵³Mn/⁵⁵Mn)_I are less consistent with ²⁰⁷Pb/²⁰⁶Pb ages of the corresponding meteorites, but yield T_SS,Mn-Cr = 4568.2 ± 0.5 Ma relative to I(Al)_SS = 5.1 × 10⁻⁵ and a ²⁰⁷Pb/²⁰⁶Pb age of 4558.55 ± 0.15 Ma for the LEW86010 angrite. The Mn-Cr method with I(Mn)_SS = 9.1 ± 1.7 × 10⁻⁶ is useful for dating accretion (if identified with chondrule formation), primary igneous events, and secondary mineralization on asteroid parent bodies. All of these events appear to have occurred approximately contemporaneously on different asteroid parent bodies. For I(Mn)_SS = 9.1 ± 1.7 × 10⁻⁶, parent body differentiation is found to extend at least to ∼5 Ma post-T_SS, i.e., until differentiation of the angrite parent body ∼4563.5 Ma ago, or ∼4564.5 Ma ago using the directly measured ²⁰⁷Pb/²⁰⁶Pb ages of the D’Orbigny-clan angrites. The ∼1 Ma difference is characteristic of a remaining inconsistency for the D’Orbigny-clan between the Al-Mg and Mn-Cr chronometers on one hand, and the ²⁰⁷Pb/²⁰⁶Pb chronometer on the other. Differentiation of the IIIAB iron meteorite and ureilite parent bodies probably occurred slightly later than for the angrite parent body, and at nearly the same time as one another as shown by the Mn-Cr ages of IIIAB irons and ureilites, respectively. The latest recorded episodes of secondary mineralization are for carbonates on the CI carbonaceous chondrite parent body and fayalites on the CV carbonaceous chondrite parent body, both extending to ∼10 Ma post-T_SS.     

Mn-Cr systematics of the early Solar System revisited

We have reinvestigated the Mn-Cr systematics in a number of primitive meteorites, differentiated planetesimals and terrestrial planets in order to address the chronology of the early stages of protoplanetary disk evolution and planetary formation. Our analytical procedure is based on the assumption of terrestrial abundances for ⁵⁰Cr and ⁵²Cr only; recognizing that a data reduction scheme based on Earth-like ⁵⁴Cr/⁵²Cr abundances in all meteorites is not tenable. Here we show that initial ε_⁵³Cr compositions of ⁵⁴Cr-rich and ⁵⁴Cr-poor acid leach fractions in the primitive carbonaceous chondrite Orgueil differ by 0.9ε, reflecting primordial mineral-scale heterogeneity. However, asteroidal processing effectively homogenized any ε_⁵³Cr variations on the planetesimal scale, providing a uniform present-day solar ε_⁵³Cr=0.20±0.10. Thus, our ⁵³Mn-⁵³Cr data argue against the previously suggested ⁵³Mn heliocentric gradient. Instead, we suggest that inner Solar System objects possessed an initially homogeneous ⁵³Mn/⁵⁵Mn composition, which determined by two independent means is estimated at (6.28 ± 0.66) × 10⁻⁶. Our revised Mn-Cr age for Ste. Marguerite (SM) metamorphism of 4562.9 ± 1.0 Ma is identical to the Pb-Pb age of SM phosphates. Using this age, we confirm that mantle differentiation of the eucrite parent body occurred 4564.9 ± 1.1 Ma ago, and revise the time interval between this event and CAI formation to 2.2 ± 1.1 Ma. We also constrain metamorphism in carbonaceous chondrites of type 2 and 3 to have occurred between 1 and 6 Ma after CAI formation. The ⁵³Mn-⁵³Cr correlation among chondrites, planetesimals and terrestrial planets (the eucrite parent body, Mars and Earth) provides evidence for Mn/Cr fractionation within the protoplanetary disk recorded by all precursor materials of the terrestrial planets and primitive asteroids. This fractionation appears to have occurred within 2 Ma of CAI formation.     

Diffusion induced Li isotopic fractionation during the cooling of magmatic rocks: The case of pyroxene phenocrysts from nakhlite meteorites

Ion-microprobe was used to measure Li abundances and isotopic compositions in pyroxenes from three Martian meteorites belonging to the nakhlite family. The profiles performed across augite crystals from Northwest Africa 817 show a large isotopic zoning from crystal cores (δ⁷Li ∼ 0‰) to rims (δ⁷Li ∼ +20‰) while Li abundances are almost constant (∼9.2 μg/g). Unlike NWA 817, the pyroxene studied in the Miller Range 03346 nakhlite shows a zoning in Li abundance, with concentrations increasing from ∼2.5 μg/g in the core to ∼9 μg/g in the rim. The augite rim (δ⁷Li = +7‰) is slightly enriched in ⁷Li with regard to the core (δ⁷Li = +4‰), but most of the isotopic variations observed occur at an intermediate position along the profile, where δ⁷Li falls down to ∼−11‰. In the case of Nakhla, Li concentrations in augite increase from cores (∼3.5 μg/g) to rims (∼6.5 μg/g), while the δ⁷Li variation is restricted (i.e., between δ⁷Li = +6.0 and +12.6‰). For the three meteorites the Li abundances were also measured in the groundmass, which was found to be enriched in lithium (∼10 μg/g). Conventional magmatic and post-magmatic processes such as alteration and fractional crystallization, fail to explain the dataset obtained on nakhlites. Degassing processes, which were previously proposed to explain the Li distribution in shergottite crystals, cannot result in the strong decoupling between Li abundances and isotopic composition observed in nakhlites. We suggest that the original magmatic Li distributions (concentrations and isotopic compositions) in nakhlites have been modified by diffusion of Li from the Li-rich groundmass towards the pyroxene crystals during sub-solidus cooling. Diffusion appears to have been efficient for NWA 817 and MIL 03346 but, apparently, did not produce a significant migration of Li in Nakhla, possibly because of the lower abundance of groundmass in the latter. Diffusion induced Li redistributions may also affect terrestrial porphyric rocks but very specific cooling rates are required to quench the diffusion profiles as observed in two of the present nakhlites.     

Hf-W mineral isochron for Ca,Al-rich inclusions: Age of the solar system and the timing of core formation in planetesimals

Application of ¹⁸²Hf-¹⁸²W chronometry to constrain the duration of early solar system processes requires the precise knowledge of the initial Hf and W isotope compositions of the solar system. To determine these values, we investigated the Hf-W isotopic systematics of bulk samples and mineral separates from several Ca,Al-rich inclusions (CAIs) from the CV3 chondrites Allende and NWA 2364. Most of the investigated CAIs have relative proportions of ¹⁸³W, ¹⁸⁴W, and ¹⁸⁶W that are indistinguishable from those of bulk chondrites and the terrestrial standard. In contrast, one of the investigated Allende CAIs has a lower ¹⁸⁴W/¹⁸³W ratio, most likely reflecting an overabundance of r-process relative to s-process isotopes of W. All other bulk CAIs have similar ¹⁸⁰Hf/¹⁸⁴W and ¹⁸²W/¹⁸⁴W ratios that are elevated relative to average carbonaceous chondrites, probably reflecting Hf-W fractionation in the solar nebula within the first ∼3 Myr. The limited spread in ¹⁸⁰Hf/¹⁸⁴W ratios among the bulk CAIs precludes determination of a CAI whole-rock isochron but the fassaites have high ¹⁸⁰Hf/¹⁸⁴W and radiogenic ¹⁸²W/¹⁸⁴W ratios up to ∼14 ε units higher than the bulk rock. This makes it possible to obtain precise internal Hf-W isochrons for CAIs. There is evidence of disturbed Hf-W systematics in one of the CAIs but all other investigated CAIs show no detectable effects of parent body processes such as alteration and thermal metamorphism. Except for two fractions from one Allende CAI, all fractions from the investigated CAIs plot on a single well-defined isochron, which defines the initial ε¹⁸²W = −3.28 ± 0.12 and ¹⁸²Hf/¹⁸⁰Hf = (9.72 ± 0.44) × 10⁻⁵ at the time of CAI formation. The initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios of the angrites D’Orbigny and Sahara 99555 are consistent with the decay from initial abundances of ¹⁸²Hf and ²⁶Al as measured in CAIs, suggesting that these two nuclides were homogeneously distributed throughout the solar system. However, the uncertainties on the initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios are too large to exclude that some ²⁶Al in CAIs was produced locally by particle irradiation close to an early active Sun. The initial ¹⁸²Hf/¹⁸⁰Hf of CAIs corresponds to an absolute age of 4568.3 ± 0.7 Ma, which may be defined as the age of the solar system. This age is 0.5-2 Myr older than the most precise ²⁰⁷Pb-²⁰⁶Pb age of Efremovka CAI 60, which does not seem to date CAI formation. Tungsten model ages for magmatic iron meteorites, calculated relative to the newly and more precisely defined initial ε¹⁸²W of CAIs, indicate that core formation in their parent bodies occurred in less than ∼1 Myr after CAI formation. This confirms earlier conclusions that the accretion of the parent bodies of magmatic iron meteorites predated chondrule formation and that their differentiation was triggered by heating from decay of abundant ²⁶Al. A more precise dating of core formation in iron meteorite parent bodies requires precise quantification of cosmic-ray effects on W isotopes but this has not been established yet.     

Beryllium-10 concentrations of tektites from the Ivory Coast and from Central Europe: Evidence for near-surface residence of precursor materials

By using accelerator mass spectrometry, we measured ¹⁰Be (T_1/2 = 1.5 Ma) concentrations in nine Ivory Coast (IVC) tektites, in six soil samples collected near the Bosumtwi impact crater, the likely source region, and in a depth profile taken through a 23 g moldavite. In the core of the moldavite sample we also measured an upper limit on the ³⁶Cl (T_1/2 = 0.3 My) concentration. The average ¹⁰Be concentration in IVC tektites of (22 ± 11) × 10⁶ atom/g exceeds reasonable limits for a meteoritic component or cosmic-ray production in situ after tektite formation. The ¹⁰Be must be meteoric, which implies that IVC tektites formed from soils or sediments. Corrected to the time of formation (ToF) 1.07 Ma ago and for a small in situ component, the average ¹⁰Be concentration of (35 ± 7) × 10⁶ atom/g (1 − σ mean) is considerably lower than those of contemporary Bosumtwi soils, ∼250 × 10⁶ atom/g, or of Australasian tektites at their ToF, 0.8 Ma B.P. near Lake Bosumtwi today the soil column is only ∼1 m thick. If the landscape was similar 1.07 Ma ago, then the total thickness of the tektite formation zone probably did not exceed 10 m. With increasing depth below the surface of the moldavite, the ¹⁰Be concentrations decrease rapidly owing to the presence of a surface component, probably of recent origin. The main interior mass of the sample contains ∼0.8 × 10⁶ atom ¹⁰Be/g and fewer than 0.1 × 10⁶ atom ³⁶Cl/g, little of which can be meteoritic. Although not definitive, consideration of several possible cosmic-ray exposure histories suggests that about half the interior ¹⁰Be has a meteoric origin, which if corrected to the time of formation yields a concentration compatible with those measured in typical contemporary soils. The observations are consistent with the formation of three of the four main tektite groups from surface soils or sediments.     

Spatial interpolation of the deuterium and oxygen-18 composition of global precipitation using temperature as ancillary variable

To aid our research in geographical forensic provenancing and food authentication we have developed high resolution prediction maps of the annual mean deuterium and oxygen-18 composition of modern precipitation. The maps have a spatial resolution of 10′ (∼ 20 × 20 km at the equator) and cover the global land surface excluding the Antarctic. To achieve this, the relation between various temperature related variables and the isotopic composition of modern precipitation was explored using a combination of high resolution climate maps and global isotope records from the GNIP database. This revealed that the isotopic composition of precipitation is somewhat better correlated to the temperature during the coldest – often driest – period of year than the temperatures during the warmest – often wettest – period of year (especially below 0 °C). Although the reason for this effect is not directly clear, the temperature during the coldest quarter is used as ancillary variable in simple kriging with varying local means (SKlm). In SKlm, only the residual isotope values from the regression with T_cq are kriging interpolated, which are then added to the predicted isotope map based on T_cq. Because the ancillary variable explains the bulk of the isotopic variation (R² = 0.79–0.85), the deuterium and oxygen-18 maps mainly reflect the large scale global temperature pattern. More local isotope effects are accounted for by the interpolation of the residual values. This study furthermore shows that surface temperature better explains the global isotopic variation compared to a combination of latitude and altitude (R² = 0.68–0.69). Yet, at very low temperatures (< − 40 °C) our maps might underestimate the true isotope signal. The new isotope maps and the maps of the 95% confidence intervals can be downloaded from www.waterisotopes.org.     

Determination of fluid/melt partition coefficients by LA-ICPMS analysis of co-existing fluid and silicate melt inclusions: Controls on element partitioning

Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log fO₂ = NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1-14 mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (D_Pb ∼ 6 ∗ m_Cl, D_Zn ∼ 8 ∗ m_Cl, D_Ag ∼ 4 ∗ m_Cl, D_Fe ∼ 1.4 ∗ m_Cl, where m_Cl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1-2 mol/kg Cl) fluids with maximum values of D_Mo ∼ 20, D_B ∼ 15, D_As ∼ 13, D_Sb ∼ 8, D_Bi ∼ 15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (D_Cu ? 2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (D_Sn = 0.3-42, D_W = 0.8-60), and decrease with decreasing oxygen fugacity or melt peraluminosity.     

Compressibility of molten Apollo 17 orange glass and implications for density crossovers in the lunar mantle

We performed density measurements on a synthetic equivalent of lunar Apollo 17 74,220 “orange glass”, containing 9.1 wt% TiO₂, at superliquidus conditions in the pressure range 0.5-8.5 GPa and temperature range 1723-2223 K using the sink/float technique. In the lunar pressure range, two experiments containing pure forsterite (Fo₁₀₀) spheres at 1.0 GPa and 1727 K, and at 1.3 GPa-1739 K, showed neutral buoyancies, indicating that the density of molten orange glass was equal to the density of Fo₁₀₀ at these conditions (3.09 ± 0.02 g cm⁻³). A third tight sink/float bracket using Fo₉₀ spheres corresponds to a melt density of 3.25 ± 0.02 g cm⁻³ at ∼2.8 GPa and ∼1838 K.Our data predict a density crossover for the molten orange glass composition with equilibrium orthopyroxene at ∼2.8 GPa, equivalent to a depth of ∼600 km in the lunar mantle, and a density of ∼3.25 g cm⁻³. This crossover depth is close to the orange glass multiple saturation point, representing its minimum formation depth, at the appropriate oxygen fugacity (2.8-2.9 GPa). A density crossover with equilibrium olivine is predicted to fall outside the lunar pressure range (>4.7 GPa), indicating that molten orange glass is always less dense than its equilibrium olivines in the Moon. Our data therefore suggest that that lunar liquids with orange glass composition are buoyant with respect to their source region at P < ∼2.8 GPa, enabling their initial rise to the surface without the need for additional external driving forces.Fitting the density data to a Birch-Murnaghan equation of state at 2173 K leads to an array of acceptable solutions ranging between 16.1 and 20.3 GPa for the isothermal bulk modulus K₂₁₇₃ and 3.6-8 for its pressure derivative K′, with best-fit values K₂₁₇₃ = 18.8 GPa and K′ = 4.4 when assuming a model 1 bar density value of 2.86 g cm⁻³. When assuming a slightly lower 1 bar density value of 2.84 g cm⁻³ we find a range for K₂₁₇₃ of 14.4-18.0 and K′ 3.7-8.7, with best-fit values of 17.2 GPa and 4.5, respectively.     

Mapping lithospheric boundaries using Os isotopes of mantle xenoliths: An example from the North China Craton

The petrology, mineral compositions, whole rock major/trace element concentrations, including highly siderophile elements, and Re-Os isotopes of 99 peridotite xenoliths from the central North China Craton were determined in order to constrain the structure and evolution of the deep lithosphere. Samples from seven Early Cretaceous-Tertiary volcanic centers display distinct geochemical characteristics from north to south. Peridotites from the northern section are generally more fertile (e.g., Al₂O₃ = 0.9-4.0%) than those from the south (e.g., Al₂O₃ = 0.2-2.2%), and have maximum whole-rock Re-depletion Os model ages (T_RD) of ∼1.8 Ga suggesting their coeval formation in the latest Paleoproterozoic. By contrast, peridotites from the south have maximum T_RD model ages that span the Archean-Proterozoic boundary (2.1-2.5 Ga). Peridotites with model ages from both groups are found at Fansi, the southernmost locality in the northern group, which likely marks a lithospheric boundary. The Neoarchean age of the lithospheric mantle in the southern section matches that of the overlying crust and likely reflects the time of amalgamation of the North China Craton via collision between the Eastern and Western blocks. The Late Paleoproterozoic (∼1.8 Ga) lithospheric mantle beneath the northern section is significantly younger than the overlying Archean crust, indicating that the original lithospheric mantle was replaced in this region, either during a major north-south continent-continent collision that occurred during assembly of the Columbia supercontinent at ∼1.8-1.9 Ga, or from extrusion of ∼1.9 Ga lithosphere from the Khondalite Belt beneath the northern Trans-North China Orogen, during the ∼1.85 Ga continental collision between Eastern and Western blocks. Post-Cretaceous heating of the southern section is indicated by high temperatures (>1000 °C) recorded in peridotites from the 4 Ma Hebi suite, which are significantly higher than the temperatures recorded in peridotites from the nearby Early Cretaceous Fushan suite (<720 °C), and likely reflects significant lithospheric thinning after the Early Cretaceous. Combining previous Os isotope results on mantle xenoliths from the eastern North China Craton with our new data, it appears that lithospheric thinning and replacement may have evolved from east to west with time, commencing before the Triassic on the eastern edge of the craton, occurring during the Jurassic-Cretaceous within the interior, and post-dating 125 Ma on the westernmost boundary.     

Analysis of raw soils and their re-suspended PM10 fractions: Characterisation of source profiles and enrichment factors

In this work, the inorganic chemical profiles of soil samples collected at different sites in the Salentum peninsula (Italy, Apulia region) are discussed. The samples were re-suspended in the laboratory, for PM10 sampling, using a ventilated wooden chamber and were then chemically analysed measuring the abundances of 17 elements. Different land use categories of soils (olive grove, arable land, vineyards, sand, and urban dust) were included in the 50 samples analysed: 45 collected in background areas and five collected in the urban area of Lecce. The objectives were to compare the chemical profiles of raw soil and re-suspended PM10 for different crustal sources and to estimate the potential improvements in the calculation of the enrichment factors of atmospheric PM10. The variability of elemental abundances in samples of the same category of soil collected in different zones was of the same order of magnitude as the differences observed between the various categories of soil. This allows the calculation of a weighted average composition of soil and urban dust and the corresponding weighted average composition of re-suspended PM10. In re-suspended PM10 from average background soil, all of the elements except Ca, Na, K and V have larger abundances with respect to raw soil. In urban dust, this is limited to Ca, V and Mg. The crustal enrichment factors (EFs) of atmospheric PM10 were evaluated by considering different reference elements and different reference tables. Results indicated that it is possible to apply a two-threshold (S₁ and S₂) scheme for the interpretation of EF, with thresholds derived from uncertainty in soil categories and from the choice of the reference element. A specific element is likely of crustal origin if EF < S₁ and likely of anthropogenic origin if EF > S₂. Between the two thresholds, the element can be considered of mixed origin. The thresholds vary according to the geological composition used in the evaluation of EF. If the average composition of local re-suspended soils is used, the thresholds are S₁ = 2 and S₂ = 4. If raw soil is used, the thresholds become S₁ = 5 and S₂ = 10. If the average upper-crust composition from literature data is used, the thresholds further increase to S₁ = 10 and S₂ = 20.     

Silver isotope variations in chondrites: Volatile depletion and the initial Pd abundance of the solar system

The extinct radionuclide ¹⁰⁷Pd decays to ¹⁰⁷Ag (half-life of 6.5 Ma) and is an early solar system chronometer with outstanding potential to study volatile depletion in the early solar system. Here, a comprehensive Ag isotope study of carbonaceous and ordinary chondrites is presented. Carbonaceous chondrites show limited variations (ε¹⁰⁷Ag = −2.1 to +0.8) in Ag isotopic composition that correlate with the Pd/Ag ratios. Assuming a strictly radiogenic origin of these variations, a new initial ¹⁰⁷Pd/¹⁰⁸Pd of 5.9 (±2.2) × 10⁻⁵ for the solar system can be deduced. Comparing the Pd-Ag and Mn-Cr data for carbonaceous chondrites suggests that Mn-Cr and Pd-Ag fractionation took place close to the time of calcium-aluminium-rich inclusion (CAI) and chondrule formation ∼4568 Ma ago. Using the new value for the initial ¹⁰⁷Pd abundance, the revised ages for the iron-rich meteorites Gibeon (IVA, 8.5 +3.2/−4.6 Ma), Grant (IIIAB, 13.0 +3.5/−4.9 Ma) and Canyon Diablo (IA, 19.5 +24.1/−10.4 Ma) are consistent with cooling rates and the closure temperature of the Pd-Ag system. In contrast to carbonaceous chondrites, ordinary chondrites show large stable isotope fractionation of order of 1 permil for ¹⁰⁷Ag/¹⁰⁹Ag. This indicates that different mechanisms of volatile depletion were active in carbonaceous and ordinary chondrites. Nebular processes and accretion, as experienced by carbonaceous chondrites, did not led to significant Ag isotope fractionation, while the significant Ag isotope variations in ordinary chondrites are most likely inflicted by open system parent body metamorphism.     

Thermodynamic properties of H4SiO4 in the ideal gas state as evaluated from experimental data

Solid phases of silicon dioxide react with water vapor with the formation of hydroxides and oxyhydroxides of silica. Recent transpiration and mass-spectrometric studies convincingly demonstrate that H₄SiO₄ is the predominant form of silica in vapor phase at water pressure in excess of 10⁻² MPa. Available literature transpiration and solubility data for the reactions of solid SiO₂ phases and low-density water, extending from 424 to 1661 K, are employed for the determination of Δ_fG⁰, Δ_fH⁰ and S⁰ of H₄SiO₄ in the ideal gas state at 298.15 K, 0.1 MPa. In total, there are 102 data points from seven literature sources. The resulting values of the thermodynamic functions of H₄SiO₄(g) are: Δ_fG⁰ = −1238.51 ± 3.0 kJ mol⁻¹, Δ_fH⁰ = −1340.68 ± 3.5 kJ mol⁻¹ and S⁰ = 347.78 ± 6.2 J K⁻¹ mol⁻¹. These values agree quantitatively with one set of ab initio calculations. The relatively large uncertainties are mainly due to conflicting data for H₄SiO₄(g) from various sources, and new determinations of would be helpful. The thermodynamic properties of this species, H₄SiO₄(g), are necessary for realistic modeling of silica transport in a low-density water phase. Applications of this analysis may include the processes of silicates condensation in the primordial solar nebula, the precipitation of silica in steam-rich geothermal systems and the corrosion of SiO₂-containing alloys and ceramics in moist environments.