Peter Sprung

Lunar tungsten isotopic evidence for the late veneer

According to the most widely accepted theory of lunar origin, a giant impact on the Earth led to the formation of the Moon, and also initiated the final stage of the formation of the Earth’s core. Core formation should have removed the highly siderophile elements (HSE) from Earth’s primitive mantle (that is, the bulk silicate Earth), yet HSE abundances are higher than expected. One explanation for this overabundance is that a ‘late veneer’ of primitive material was added to the bulk silicate Earth after the core formed. To test this hypothesis, tungsten isotopes are useful for two reasons: first, because the late veneer material had a different 182W/184W ratio to that of the bulk silicate Earth, and second, proportionally more material was added to the Earth than to the Moon. Thus, if a late veneer did occur, the bulk silicate Earth and the Moon must have different 182W/184W ratios. Moreover, the Moon-forming impact would also have created 182W differences because the mantle and core material of the impactor with distinct 182W/184W would have mixed with the proto-Earth during the giant impact. However the 182W/184W of the Moon has not been determined precisely enough to identify signatures of a late veneer or the giant impact. Here, using more-precise measurement techniques, we show that the Moon exhibits a 182W excess of 27xa0±xa04 parts per million over the present-day bulk silicate Earth. This excess is consistent with the expected 182W difference resulting from a late veneer with a total mass and composition inferred from HSE systematics. Thus, our data independently show that HSE abundances in the bulk silicate Earth were established after the giant impact and core formation, as predicted by the late veneer hypothesis. But, unexpectedly, we find that before the late veneer, no 182W anomaly existed between the bulk silicate Earth and the Moon, even though one should have arisen through the giant impact. The origin of the homogeneous 182W of the pre-late-veneer bulk silicate Earth and the Moon is enigmatic and constitutes a challenge to current models of lunar origin.

ZIRCONIUM—HAFNIUM ISOTOPE EVIDENCE FROM METEORITES FOR THE DECOUPLED SYNTHESIS OF LIGHT AND HEAVY NEUTRON-RICH NUCLEI

Recent work based on analyses of meteorite and terrestrial whole-rock samples showed that the r- and s- process isotopes of Hf were homogeneously distributed throughout the inner solar system. We report new Hf isotope data for Calcium-Aluminum-rich inclusions (CAIs) of the CV3 carbonaceous chondrite Allende, and novel high-precision Zr isotope data for these CAIs and three carbonaceous chondrites (CM, CO, CK). Our Zr data reveal enrichments in the neutron-rich isotope {sup 96}Zr (≤1e in {sup 96}Zr/{sup 90}Zr) for bulk chondrites and CAIs (∼2e). Potential isotope effects due to incomplete sample dissolution, galactic and cosmic ray spallation, and the nuclear field shift are assessed and excluded, leading to the conclusion that the {sup 96}Zr isotope variations are of nucleosynthetic origin. The {sup 96}Zr enrichments are coupled with {sup 50}Ti excesses suggesting that both nuclides were produced in the same astrophysical environment. The same CAIs also exhibit deficits in r-process Hf isotopes, which provides strong evidence for a decoupling between the nucleosynthetic processes that produce the light (A ≤ 130) and heavy (A > 130) neutron-rich isotopes. We propose that the light neutron-capture isotopes largely formed in Type II supernovae (SNeII) with higher mass progenitors than the supernovae that produced the heavymorexa0» r-process isotopes. In the context of our model, the light isotopes (e.g. {sup 96}Zr) are predominantly synthesized via charged-particle reactions in a high entropy wind environment, in which Hf isotopes are not produced. Collectively, our data indicates that CAIs sampled an excess of materials produced in a normal mass (12-25 M{sub ☉}) SNII.«xa0less

A rapid and efficient ion-exchange chromatography for Lu–Hf, Sm–Nd, and Rb–Sr geochronology and the routine isotope analysis of sub-ng amounts of Hf by MC-ICP-MS

The development and improvement of MC-ICP-MS instruments have fueled the growth of Lu–Hf geochronology over the last two decades, but some limitations remain. Here, we present improvements in chemical separation and mass spectrometry that allow accurate and precise measurements of 176Hf/177Hf and 176Lu/177Hf in high-Lu/Hf samples (e.g., garnet and apatite), as well as for samples containing sub-nanogram quantities of Hf. When such samples are spiked, correcting for the isobaric interference of 176Lu on 176Hf is not always possible if the separation of Lu and Hf is insufficient. To improve the purification of Hf, the high field strength elements (HFSE, including Hf) are first separated from the rare earth elements (REE, including Lu) on a first-stage cation column modified after Patchett and Tatsumoto (Contrib. Mineral. Petrol., 1980, 75, 263–267). Hafnium is further purified on an Ln-Spec column adapted from the procedures of Munker et al. (Geochem., Geophys., Geosyst., 2001, DOI: 10.1029/2001gc000183) and Wimpenny et al. (Anal. Chem., 2013, 85, 11258–11264) typically resulting in Lu/Hf < 0.0001, Zr/Hf < 1, and Ti/Hf < 0.1. In addition, Sm–Nd and Rb–Sr separations can easily be added to the described two-stage ion-exchange procedure for Lu–Hf. The isotopic compositions are measured on a Thermo Scientific Neptune Plus MC-ICP-MS equipped with three 1012 Ω resistors. Multiple 176Hf/177Hf measurements of international reference rocks yield a precision of 5–20 ppm for solutions containing 40 ppb of Hf, and 50–180 ppm for 1 ppb solutions (=0.5 ng sample Hf 0.5 in ml). The routine analysis of sub-ng amounts of Hf will facilitate Lu–Hf dating of low-concentration samples.

EVOLUTION OF THE ACASTA GNEISS COMPLEX THROUGH SR ISOTOPE ANALYSIS OF APATITE INCLUSIONS IN ZIRCON

(1) Department of Earth, Ocean and Atmospheric Sciences, University of British Columbia, Vancouver, Canada, (2) Department of Geosciences, Swedish Museum of Natural History, Stockholm, Sweden, (3) Institut für Mineralogie, Westfälische Wilhelms-Universität, Münster, Germany, (4) Institut für Geologie und Mineralogie, Universität zu Köln, Cologne, Germany, (5) Geological Survey of Canada, Ottawa, Ontario, Canada, (6) Institut für Geologie, Universität Bern, Bern, Switzerland.