Influence of redox processes on the germanium isotopic composition of ordinary chondrites

1,2Guillaume Florin,1Béatrice Luais,2 Tracy Rushmer,2,3Olivier Alard
Geochimica et Cosmochimica Acta 269, 270-291 Link to Article [https://doi.org/10.1016/j.gca.2019.10.038]
1Centre de Recherches Pétrographiques et Géochimiques, CRPG-CNRS – UMR 7358, Université de Lorraine, 15 Rue Notre Dame des Pauvres, 54500 Vandœuvre-lès-Nancy, France
2Department of Earth and Planetary Sciences, Macquarie University, NSW 2109, Australia
3Géosciences Montpellier, UMR 5243, CNRS & Université Montpellier, 34095 Montpellier, France
Copyright Elsevier

Ordinary chondrites (OCs) are classified into three groups, according to their oxidation state, which increases from the H to L to LL groups. This is demonstrated by the decrease in metal content (H = ∼8 vol%, L = ∼4 vol%, and LL = ∼2 vol%), and by a positive correlation between Δ17O and %Fa through the OC sequence. Compared to other chondrites, OCs exhibit the largest variation in oxidation state, but there is an ongoing debate on the processes that control this variation. To constrain the causes of the variations in the oxidation state with respect to the associated nebular versus parent bodies processes, we investigated the elemental and isotopic variations of germanium (moderately siderophile and volatile) in the bulk sample, as well as in the metal, silicate and sulfide phases, over a range of petrographic types for the H, L, and LL ordinary chondrites.

We found that δ74/70Gemetal is a proxy for the δ74/70Gebulk composition and that each OC group is distinguishable by their δ74/70Gemetal, which increases from −0.51 ± 0.09‰ for H chondrites, −0.31 ± 0.06‰ for L chondrites, and, finally, to −0.26 ± 0.09‰ for LL chondrites (2σ SD). Additionally, the OC sequence exhibited a positive correlation, from H to L to LL, between δ74/70Gemetal and %Fa, as well as oxygen isotopes (δ17O, δ18O and Δ17O), that was not a consequence of a “size sorting effect” on chondrules (i.e., chondrule mixing) or metamorphic processes in the parent bodies but, rather, was the result of nebular processes. We propose that the correlation between the δ74/70Ge values and %Fa, Δ17O, δ18O can be explained by an increasing proportion of accreted hydrated phyllosilicates, from the H, L to LL groups, with high δ74/70Ge and Δ17O. We found that 10 to 15% of phyllosilicates, with a composition of [Ge] = 4–7 ppm and δ74/70Ge = 3–2.5‰, is needed to change the δ74/70Ge from H to LL, which corresponds to a Δ17O ≈ 8–7‰. This value agrees with the Δ17O ≈ 7‰ composition of the accreted nebular component reported by Choi et al. (1998). During thermal metamorphism, phyllosilicates destabilize, liberating germanium that will be incorporated in the metal, then leading to its high δ74/70Ge signature.

High-temperature metamorphism can explain the lack of δ74/70Gemetal variation with the petrologic type in the OC, even for the type 3 chondrites (T ≈ 675 °C), implying a complete reaction even at low petrologic types. In addition, metal-silicate re-equilibration in response to thermal metamorphism results in a decrease in Δ74/70Gemetal-silicate from 0.33‰ to 0.06‰, within the H chondrite group, which is interpreted as the result of δ74/70Gesilicate variation. The mean positive Δ74/70Gemetal-silicate fractionation factor of +0.22 ± 0.36‰ (error propagation on individual error) also displays a remarkable similarity to the direction of isotopic fractionation with other germanium isotopic metal-silicate datasets, such as the magmatic iron meteorites, the Earth silicate reservoirs. We propose that the Δ74/70Gemetal-silicate and the negative δ74/70Ge values of OCs are inherited from metal-silicate melting and partial exchange before planetesimal accretion in a light isotope-enriched gas. Finally, the δ74/70Gemetal-Δ17Osilicate correlation between the IIE iron meteorites and OCs, provides new evidence for the existence of a highly reduced HH group.

Mineralogy and geochemistry of sedimentary rocks and eolian sediments in Gale crater, Mars: A review after six Earth years of exploration with Curiosity

1,2E.B.Rampe et al. (>10)
Geochemistry (in Press) Link to Article [https://doi.org/10.1016/j.chemer.2020.125605]
1NASA Johnson Space Center, Houston, TX, USA
2Chesapeake Energy, Oklahoma City, OK, USA
Copyright Elsevier

The Mars Science Laboratory Curiosity rover arrived at Mars in August 2012 with a primary goal of characterizing the habitability of ancient and modern environments. Curiosity was sent to Gale crater to study a sequence of ∼3.5 Ga old sedimentary rocks that, based on orbital visible and near- to short-wave infrared reflectance spectra, contain secondary minerals that suggest deposition and/or alteration in liquid water. The sedimentary sequence in the lower slopes of Mount Sharp in Gale crater preserves a dramatic shift on early Mars from a relatively warm and wet climate to a cold and dry climate, based on a transition from smectite-bearing strata to sulfate-bearing strata. The rover is equipped with instruments to examine the sedimentology and identify compositional changes in the stratigraphy. The Chemistry and Mineralogy (CheMin) instrument is one of two internal laboratories on Curiosity and includes a transmission X-ray diffractometer (XRD) and X-ray fluorescence (XRF) spectrometer. CheMin measures loose sediment samples scooped from the surface and drilled rock powders, and the XRD provides quantitative mineralogy to a detection limit of ∼1 wt.% for crystalline phases. Curiosity has traversed >20 km since landing and has primarily been exploring an ancient lake environment fed by streams and groundwater. Of the 19 drilled rock samples analyzed by CheMin as of sol 2300 (January 2019), 15 are from fluvio-lacustrine deposits that comprise the Bradbury and Murray formations. Most of these samples were drilled from units that did not have a clear mineralogical signature from orbit. Results from CheMin demonstrate an astounding diversity in the mineralogy of these rocks that signifies geochemical variations in source rocks, transportation mechanisms, and depositional and diagenetic fluids. Most detrital igneous minerals are basaltic, but the discovery in a few samples of abundant silicate minerals that usually crystallize from evolved magmas on Earth remains enigmatic. Trioctahedral smectite and magnetite at the base of the section may have formed from low-salinity pore waters with a circumneutral pH in lake sediments. A transition to dioctahedral smectite, hematite, and Ca-sulfate going up section suggests a change to more saline and oxidative aqueous conditions in the lake waters themselves and/or in diagenetic fluids. Perhaps one of the biggest mysteries revealed by CheMin is the high abundance of X-ray amorphous materials (15 to 73 wt.%) in all samples drilled or scooped to date. CheMin has analyzed three modern eolian sands, which have helped constrain sediment transport and mineral segregation across the active Bagnold Dune Field. Ancient eolian sandstones drilled from the Stimson formation differ from modern eolian sands in that they contain abundant magnetite but no olivine, suggesting that diagenetic processes led to the alteration of olivine to release Fe(II) and precipitate magnetite. Fracture-associated halos in the Stimson and the Murray formations are evidence for complex aqueous processes long after the streams and lakes vanished from Gale crater. The sedimentology and composition of the rocks analyzed by Curiosity demonstrate that habitable environments persisted intermittently on the surface or in the subsurface of Gale crater for perhaps more than a billion years.

The composition of Mars

1Takashi Yoshizaki,1,2,3William F.McDonough
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2020.01.011]
1Department of Earth Science, Graduate School of Science, Tohoku University, Sendai, Miyagi 980-8578, Japan
2Department of Geology, University of Maryland, College Park, MD 20742, USA
3Research Center of Neutrino Sciences, Tohoku University, Sendai, Miyagi 980-8578, Japan
Copyright Elsevier

Comparing compositional models of the terrestrial planets provides insights into physicochemical processes that produced planet-scale similarities and differences. The widely accepted compositional model for Mars assumes Mn and more refractory elements are in CI chondrite proportions in the planet, including Fe, Mg, and Si, which along with O make up >90% of the mass of Mars. However, recent improvements in our understandings on the composition of the solar photosphere and meteorites challenge the use of CI chondrite as an analog of Mars. Here we present an alternative model composition for Mars that avoids such an assumption and is based on data from Martian meteorites and spacecraft observations. Our modeling method was previously applied to predict the Earth’s composition. The model establishes the absolute abundances of refractory lithophile elements in the bulk silicate Mars (BSM) at 2.26 times higher than that in CI carbonaceous chondrites. Relative to this chondritic composition, Mars has a systematic depletion in moderately volatile lithophile elements as a function of their condensation temperatures. Given this finding, we constrain the abundances of siderophile and chalcophile elements in the bulk Mars and its core. The Martian volatility trend is consistent with ⩽7 wt% S in its core, which is significantly lower than that assumed in most core models (i.e., >10 wt% S). Furthermore, the occurrence of ringwoodite at the Martian core-mantle boundary might have contributed to the partitioning of O and H into the Martian core.

40Ar/39Ar systematics of melt lithologies and target rocks from the Gow Lake impact structure, Canada

1,2A.E.Pickersgill,2,3D.F.Mark,1M.R.Lee,4,5G.R.Osinski
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2020.01.025]
1School of Geographical & Earth Sciences, University of Glasgow, Gregory Building, Lilybank Gardens, Glasgow G12 8QQ, UK
2NERC Argon Isotope Facility, Scottish Universities Environmental Research Centre (SUERC), Rankine Avenue, East Kilbride G75 0QF, UK
3Department of Earth & Environmental Science, University of St Andrews, St Andrews, KY16 9AJ, UK
4Institute for Earth and Space Exploration, University of Western Ontario, 1151 Richmond Street, London, ON, Canada
5Department of Earth Sciences, University of Western Ontario, 1151 Richmond Street, London, ON, Canada
Copyright Elsevier

The age of the Gow Lake impact structure (Saskatchewan, Canada) is poorly constrained, with previous estimates ranging from 100 to 250 Ma. Using a combination of step-heating and UV laser in situ 40Ar/39Ar analyses we have sought to understand the 40Ar/39Ar systematics of this small impact crater and obtain a more precise and accurate age. This structure is challenging for 40Ar/39Ar geochronology due to its small size (∼5 km diameter), the silicic composition of the target rock, and the large difference in age between the impact event and the target rock (∼1.2 Ga). These factors can serve to inhibit argon mobility in impact melts, leading to retention of ‘extraneous’ 40Ar and anomalously older measured ages. We mitigated the undesirable effects of extraneous 40Ar retention by analysing small volume aliquots of impact glass using step-heating and even smaller volumes via the UV laser in situ 40Ar/39Ar technique. Although primary hydration of impact-generated glasses enhanced the diffusivity of 40Ar inherited from silica-rich melts, data still had to be corrected for extraneous 40Ar by using isotope correlation plots to define the initial trapped 40Ar/36Ar components. Our inverse isochron age of 196.8 ± 9.6/9.9 Ma (2σ, analytical/external precision) demonstrates that the Gow Lake event occurred within uncertainty of the Triassic-Jurassic boundary, but there is no evidence that it was part of an impact cluster.

Multiple mineral horizons in layered outcrops at Mawrth Vallis, Mars, signify changing geochemical environments on early Mars

1,2Janice L.Bishop,2Christoph Gross,1,3 Jacob Danielsen,4Mario Parente,5Scott L.Murchie,6 Briony Horgan,7James J.Wray,6Christina Viviano,6Frank P.Seelos
Icarus (in Press) Link to Article [https://doi.org/10.1016/j.icarus.2020.113634]
1SETI Institute, Mountain View, CA, United States of America
2Freie Universität Berlin, Berlin, Germany
3San Jose State University, San Jose, CA, United States of America
4University of Massachusetts at Amherst, Amherst, MA, United States of America
5Johns Hopkins University Applied Physics Lab, Laurel, MD, United States of America
6Purdue University, West Lafayette, IN, United States of America
7Georgia Institute of Technology, Atlanta, GA, United States of America
Copyright Elsevier

Refined calibrations of CRISM images are enabling identification of smaller deposits of unique aqueous materials on Mars that reveal changing environmental conditions at the region surrounding Mawrth Vallis. Through characterization of these clay-sulfate assemblages and their association with the layered, phyllosilicate units of this region, more details of the aqueous geochemical history can be gleaned. A stratigraphy including five distinct mineral horizons is mapped using compositional data from CRISM over CTX and HRSC imagery across 100s of km and from CRISM over HiRISE imagery across 100s of meters. Transitions in mineralogic units were characterized using visible/near-infrared (VNIR) spectral properties and surface morphology. We identified and characterized complex “doublet” type spectral signatures with two bands between 2.2 and 2.3 μm at one stratigraphic horizon. Based on comparisons with terrestrial sites, the spectral “doublet” unit described here may reflect the remnants of a salty, evaporative period that existed on Mars during the transition from formation of Fe-rich phyllosilicates to Al-rich phyllosilicates. Layered outcrops observed at Mawrth Vallis are thicker than in other altered regions of Mars, but may represent processes that were more widespread in wet regions of the planet during its early history. The aqueous geochemical environments supporting the outcrops observed here include: (i) the formation of Fe3+-rich smectites in a warm and wet environment, (ii) overlain by a thin ferrous-bearing clay unit that could be associated with heating or reducing conditions, (iii) followed by a transition to salty and/or acidic alteration phases and sulfates (characterized by the spectral “doublet” shape) in an evaporative setting, (iv) formation of Al-rich phyllosilicates through pedogenesis or acid leaching, and (v) finally persistence of poorly crystalline aluminosilicates marking the end of the warm climate on early Mars. The “doublet” type units described here are likely composed of clay-sulfate assemblages formed in saline, acidic evaporative environments similar to those found in Western Australia and the Atacama desert. Despite the chemically extreme and variable waters present at these terrestrial, saline lake environments, active ecosystems are present; thus, these “doublet” type units may mark exciting areas for continued exploration important to astrobiology on Mars.

Determination of trace rare earth elements in rock samples including meteorites by ICP-MS coupled with isotope dilution and comparison methods

1Ebihara, M.,1Hayano,1K.,1Shirai, N.
Analytica Chimica Acta (in Press) Link to Article [DOI: 10.1016/j.aca.2019.12.031]
1Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo, 192-0397, Japan

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On impact and volcanism across the Cretaceous-Paleogene boundary

1Pincelli M. Hull et al. (>10)
Science 367, 266-272 Link to Article [DOI: 10.1126/science.aay5055]
1Department of Geology and Geophysics, Yale University, New Haven, CT 06511, USA.
Reprinted with Permission of AAAS

The cause of the end-Cretaceous mass extinction is vigorously debated, owing to the occurrence of a very large bolide impact and flood basalt volcanism near the boundary. Disentangling their relative importance is complicated by uncertainty regarding kill mechanisms and the relative timing of volcanogenic outgassing, impact, and extinction. We used carbon cycle modeling and paleotemperature records to constrain the timing of volcanogenic outgassing. We found support for major outgassing beginning and ending distinctly before the impact, with only the impact coinciding with mass extinction and biologically amplified carbon cycle change. Our models show that these extinction-related carbon cycle changes would have allowed the ocean to absorb massive amounts of carbon dioxide, thus limiting the global warming otherwise expected from postextinction volcanism.

Lifetimes of interstellar dust from cosmic ray exposure ages of presolar silicon carbide

1,2,3Philipp R. Heck,1,2,3Jennika Greer,1,2,3Levke Kööp,4Reto Trappitsch,5,6Frank Gyngard,7Henner Busemann,7Colin Madeg,8Janaína N. Ávila,1,2,3,9Andrew M. Davis,7Rainer Wieler
Proceedings of the National Academy of Sciences of the United States of America (in Press) Link to Article [https://doi.org/10.1073/pnas.1904573117]
1Robert A. Pritzker Center for Meteoritics and Polar Studies, The Field Museum of Natural History, Chicago, IL 60605;
2Chicago Center for Cosmochemistry, The University of Chicago, Chicago, IL 60637;
3Department of the Geophysical Sciences, The University of Chicago, Chicago, IL 60637;
4Nuclear and Chemical Sciences Division, Lawrence Livermore National Laboratory, Livermore, CA 94550;
5Physics Department, Washington University, St. Louis, MO 63130;
6Center for NanoImaging, Harvard Medical School, Cambridge, MA 02139;
7Institute of Geochemistry and Petrology, ETH Zürich, 8092 Zürich, Switzerland;
8Research School of Earth Sciences, The Australian National University, Canberra, ACT 2601, Australia;
9Enrico Fermi Institute, The University of Chicago, Chicago, IL 60637

We determined interstellar cosmic ray exposure ages of 40 large presolar silicon carbide grains extracted from the Murchison CM2 meteorite. Our ages, based on cosmogenic Ne-21, range from 3.9 ± 1.6 Ma to ∼3 ± 2 Ga before the start of the Solar System ∼4.6 Ga ago. A majority of the grains have interstellar lifetimes of <300 Ma, which is shorter than theoretical estimates for large grains. These grains condensed in outflows of asymptotic giant branch stars <4.9 Ga ago that possibly formed during an episode of enhanced star formation ∼7 Ga ago. A minority of the grains have ages >1 Ga. Longer lifetimes are expected for large grains. We determined that at least 12 of the analyzed grains were parts of aggregates in the interstellar medium: The large difference in nuclear recoil loss of cosmic ray spallation products 3He and 21Ne enabled us to estimate that the irradiated objects in the interstellar medium were up to 30 times larger than the analyzed grains. Furthermore, we estimate that the majority of the grains acquired the bulk of their cosmogenic nuclides in the interstellar medium and not by exposure to an enhanced particle flux of the early active sun.

Heterogeneous accretion of Earth inferred from Mo-Ru isotope systematics

1,2Timo Hopp,1,3Gerrit Budde,1Thorsten Kleine
Earth and Planetary Science Letters 534, 116065 Link to Article [https://doi.org/10.1016/j.epsl.2020.116065]
1Institut für Planetologie, University of Münster, Wilhelm-Klemm-Str. 10, 48149 Münster, Germany
2Origins Laboratory, Department of Geophysical Sciences and Enrico Fermi Institute, The University of Chicago, 5743 South Ellis Avenue, Chicago, IL 60637, USA.
3The Isotoparium, Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA.
Copyright Elsevier

The Mo and Ru isotopic compositions of meteorites and the bulk silicate Earth (BSE) hold important clues about the provenance of Earth’s building material. Prior studies have argued that non-carbonaceous (NC) and carbonaceous (CC) meteorite groups together define a Mo-Ru ‘cosmic’ correlation, and that the BSE plots on the extension of this correlation. These observations were taken as evidence that the final 10–15% of Earth’s accreted material derived from a homogeneous inner disk reservoir with an enstatite chondrite-like isotopic composition. Here, using new Mo and Ru isotopic data for previously uninvestigated meteorite groups, we show that the Mo-Ru correlation only exists for NC meteorites, and that both the BSE and CC meteorites fall off this Mo-Ru correlation. These observations indicate that the final stages of Earth’s accretion were heterogeneous and consisted of a mixture of NC and CC materials. The Mo-Ru isotope systematics are best accounted for by either an NC heritage of the late veneer combined with a CC heritage of the Moon-forming giant impactor, or by mixed NC-CC compositions for both components. The involvement of CC bodies in the late-stage accretionary assemblage of Earth is consistent with chemical models for core-mantle differentiation, which argue for the addition of more oxidized and volatile-rich material toward the end of Earth’s formation. As such, this study resolves the inconsistencies between homogeneous accretion models based on prior interpretations of the Mo-Ru systematics of meteorites and the chemical evidence for heterogeneous accretion of Earth.

The chemical case for Mercury mantle stripping

1Helffrich, G.,1Brasser, R.,2Shahar, A.
Progress in Earth and Planetary Science 6, 66 Link to Article [DOI: 10.1186/s40645-019-0312-z]
1Earth-Life Science Institute, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8550, Japan
2Geophysical Laboratory, Carnegie Institution for Science, 5251 Broad Branch Road NW, Washington, DC 20015, United States

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