Tracing metal–silicate segregation and late veneer in the Earth and the ureilite parent body with palladium stable isotopes

International audienceStable isotope studies of highly siderophile elements (HSE) have the potential to yield valuable insights into a range of geological processes. In particular, the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal-silicate segregation, making them sensitive tracers of planetary differentiation processes. We present the first techniques for the precise determination of palladium stable isotopes by MC-ICPMS using a 106Pd-110Pd double-spike to correct for instrumental mass fractionation. Results are expressed as the per mil (‰) difference in the 106Pd/105Pd ratio (δ106Pd) relative to an in-house solution standard (Pd_IPGP) in the absence of a certified Pd isotopic standard. Repeated analyses of the Pd isotopic composition of the chondrite Allende demonstrate the external reproducibility of the technique of ±0.032‰ on δ106Pd. Using these techniques, we have analysed Pd stable isotopes from a range of terrestrial and extraterrestrial samples. We find that chondrites define a mean δ106Pdchondrite = -0.19 ± 0.05‰. Ureilites reveal a weak trend towards heavier δ106Pd with decreasing Pd content, similar to recent findings based on Pt stable isotopes (Creech et al., 2017), although fractionation of Pd isotopes is significantly less than for Pt, possibly related to its weaker metal-silicate partitioning behaviour and the limited field shift effect. Terrestrial mantle samples have a mean δ106Pdmantle = -0.182 ± 0.130‰, which is consistent with a late-veneer of chondritic material after core formation

Isotopic fractionation of Cu in tektites

Tektites are terrestrial natural glasses of up to a few centimeters in size that were produced during hypervelocity impacts on the Earth’s surface. It is well established that the chemical and isotopic composition of tektites is generally identical to that of the upper terrestrial continental crust. Tektites typically have very low water content, which has generally been explained by volatilization at high temperature; however, the exact mechanism is still debated. Because volatilization can fractionate isotopes, comparing the isotopic composition of volatile elements in tektites with those of their source rocks may help to understand the physical conditions during tektite formation.Interestingly, volatile chalcophile elements (e.g., Cd and Zn) seem to be the only elements for which isotopic fractionation is known so far in tektites. Here, we extend this study to Cu, another volatile chalcophile element. We have measured the Cu isotopic composition for 20 tektite samples from the four known different strewn fields. All of the tektites (except the Muong Nong-types) are enriched in the heavy isotopes of Cu (1.98 < δ65Cu < 6.99) in comparison to the terrestrial crust (δ65Cu ≈ 0) with no clear distinction between the different groups. The Muong Nong-type tektites and a Libyan Desert Glass sample are not fractionated (δ65Cu ≈ 0) in comparison to the terrestrial crust. To refine the Cu isotopic composition of the terrestrial crust, we also present data for three geological reference materials (δ65Cu ≈ 0).An increase of δ65Cu with decreasing Cu abundance probably reflects that the isotopic fractionation occurred by evaporation during heating. A simple Rayleigh distillation cannot explain the Cu isotopic data and we suggest that the isotopic fractionation is governed by a diffusion-limited regime. Copper is isotopically more fractionated than the more volatile element Zn (δ66/64Zn up to 2.49‰). This difference of behavior between Cu and Zn is predicted in a diffusion-limited regime, where the magnitude of the isotopic fractionation is regulated by the competition between the evaporative flux and the diffusive flux at the diffusion boundary layer. Due to the difference of ionic charge in silicates (Zn2+ vs. Cu+), Cu has a diffusion coefficient that is larger than that of Zn by at least two orders of magnitude. Therefore, the larger isotopic fractionation in Cu than in Zn in tektites is due to the significant difference in their respective chemical diffusivity

Towards consistent chronology in the early Solar System: high resolution 53Mn-53Cr chronometry for chondrules.

New high-precision {sup 53}Mn-{sup 53}Cr data obtained for chondrules extracted from a primitive ordinary chondrite, Chainpur (LL3.4), define an initial {sup 53}Mn/{sup 55}Mn ratio of (5.1 {+-} 1.6) x 10{sup -6}. As a result of this downward revision from an earlier higher value of (9.4 {+-} 1.7) x 10{sup -6} for the same meteorite (Nyquist et al. 2001), together with an assessment of recent literature, we show that a consistent chronology with other chronometers such as the {sup 26}Al-{sup 26}Mg and {sup 207}Pb-{sup 206}Pb systems emerges in the early Solar System

Investigating magmatic processes in the early Solar System using the Cl isotopic systematics of eucrites

Generally, terrestrial rocks, martian and chondritic meteorites exhibit a relatively narrow range in bulk and apatite Cl isotope compositions, with δ37Cl (per mil deviation from standard mean ocean chloride) values between − 5.6 and + 3.8 ‰. Lunar rocks, however, have more variable bulk and apatite δ37Cl values, ranging from ∼ − 4 to + 40 ‰. As the Howardite-Eucrite-Diogenite (HED) meteorites represent the largest suite of crustal and sub-crustal rocks available from a differentiated basaltic asteroid (4 Vesta), studying them for their volatiles may provide insights into planetary differentiation processes during the earliest Solar System history. Here the abundance and isotopic composition of Cl in apatite were determined for seven eucrites representing a broad range of textural and petrological characteristics. Apatite Cl abundances range from ∼ 25 to 4900 ppm and the δ37Cl values range from − 3.98 to + 39.2 ‰. Samples with lower apatite H2O contents were typically also enriched in 37Cl but no systematic correlation between δ37Cl and δD values was observed across samples. Modelled Rayleigh fractionation and a strong positive correlation between bulk δ66Zn and apatite δ37Cl support the hypothesis that Cl degassed as metal chlorides from eucritic magmas, in a hydrogen-poor environment. In the case of lunar samples, it has been noted that δ37Cl values of apatite positively correlate with bulk La/Yb ratio. Interestingly, most eucrites show a negative correlation with bulk La/Yb ratio. Recently, isotopically light Cl values have been suggested to record the primary solar nebular signature. If this is the case then 4 Vesta, which accreted rapidly and early in Solar System history, could also record this primary nebular signature corresponding to the lightest Cl values measured here. The significant variation in Cl isotope composition observed within the eucrites are likely related to degassing of metal chlorides

Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment

The History, Relevance, and Applications of the Periodic System in Geochemistry

Geochemistry is a discipline in the earth sciences concerned with understanding the chemistry of the Earth and what that chemistry tells us about the processes that control the formation and evolution of Earth materials and the planet itself. The periodic table and the periodic system, as developed by Mendeleev and others in the nineteenth century, are as important in geochemistry as in other areas of chemistry. In fact, systemisation of the myriad of observations that geochemists make is perhaps even more important in this branch of chemistry, given the huge variability in the nature of Earth materials – from the Fe-rich core, through the silicate-dominated mantle and crust, to the volatile-rich ocean and atmosphere. This systemisation started in the eighteenth century, when geochemistry did not yet exist as a separate pursuit in itself. Mineralogy, one of the disciplines that eventually became geochemistry, was central to the discovery of the elements, and nineteenth-century mineralogists played a key role in this endeavour. Early “geochemists” continued this systemisation effort into the twentieth century, particularly highlighted in the career of V.M. Goldschmidt. The focus of the modern discipline of geochemistry has moved well beyond classification, in order to invert the information held in the properties of elements across the periodic table and their distribution across Earth and planetary materials, to learn about the physicochemical processes that shaped the Earth and other planets, on all scales. We illustrate this approach with key examples, those rooted in the patterns inherent in the periodic law as well as those that exploit concepts that only became familiar after Mendeleev, such as stable and radiogenic isotopes

Seeking Signs of Life on Mars: the Importance of Sedimentary Suites as Part of a Mars Sample Return Campaign

Seeking the signs of life on Mars is often considered the "first among equal" objectives for any potential Mars Sample Return (MSR) campaign. Among the geological settings considered to have the greatest potential for recording evidence of ancient life or its pre-biotic chemistry on Mars are lacustrine (and marine, if ever present) sedimentary depositional environments. This potential, and the possibility of returning samples that could meaningfully address this objective, have been greatly enhanced by investigations of an ancient redox stratified lake system in Gale crater by the Curiosity rover

Seeking Signs of Life on Mars: A Strategy for Selecting and Analyzing Returned Samples from Hydrothermal Deposits

Highly promising locales for biosignature prospecting on Mars are ancient hydrothermal deposits, formed by the interaction of surface water with heat from volcanism or impacts. On Earth, they occur throughout the geological record (to at least approx. 3.5 Ga), preserving robust mineralogical, textural and compositional evidence of thermophilic microbial activity. Hydrothermal systems were likely present early in Mars' history, including at two of the three finalist candidate landing sites for M2020, Columbia Hills and NE Syrtis Major. Hydrothermal environments on Earth's surface are varied, constituting subaerial hot spring aprons, mounds and fumaroles; shallow to deep-sea hydrothermal vents (black and white smokers); and vent mounds and hot-spring discharges in lacustrine and fluvial settings. Biological information can be preserved by rapid, spring-sourced mineral precipitation, but also could be altered or destroyed by postdepositional events. Thus, field observations need to be followed by detailed laboratory analysis to verify potential biosignatures. See Attachmen

Silicon isotopic variation in enstatite meteorites:Clues to their origin and Earth-forming material

Of the primitive meteorite groups, the enstatite chondrites are among the most chemically dissimilar to terrestrial, which should preclude them as major components of the proto-Earth. However, for many isotope systems (most notably oxygen), enstatite chondrites show very little variation away from terrestrial, hinting at a common origin. One isotope system which appears to differ from this trend is silicon, but no satisfactory explanation has been proposed as to why these meteorites should be significantly lighter than both the silicate Earth and other primitive meteorite groups. This study presents a comprehensive investigation into the Si isotope composition of enstatite chondrites and their differentiated counterparts, the aubrites, and confirms that these meteorites are, with respect to Si isotopes, the lightest macroscale solar system objects so far analysed. Crucially, the results show that EH chondrites are significantly lighter (δSi=-0.77±0.08‰) than EL chondrites (δSi=-0.59±0.09‰) and aubrites (δSi=-0.60±0.11‰). Silicon isotope analyses of the metal-free components of EH and EL reveal that these are identical, within error, to each other and with carbonaceous/ordinary chondrite bulk measurements (viz., δSi ~-0.47), which is taken as evidence that Si isotope variation in the nebular gas is not the cause of the light Si isotope enrichment in enstatite chondrites. From this, one can infer that silicates condensing from the solar nebula over a wide range of compositions and, presumably, heliocentric distances have very similar Si isotope compositions. A statistically significant negative correlation between bulk δSi and Si content in enstatite chondrite kamacite indicates that the presence of isotopically light Si in the metal phase (as the result of formation under reducing conditions) is the principal cause of the bulk enrichment in lighter Si isotopes. Based on the Si isotope offset between enstatite meteorites and the silicate Earth, the extant enstatite meteorites cannot represent a significant proportion of the material that accreted to form the proto-Earth, as unfeasibly large amounts of Si would have to enter the core to satisfy mass balance equations. However, we posit that material enriched in refractory lithophile elements which condensed in the same region as E-chondrites, could still be an important component