Gas/solid carbon branching ratios in surface-mediated reactions and the incorporation of carbonaceous material into planetesimals

1Joseph A. Nuth,2Natasha M. Johnson,2,3Frank T. Ferguson,2Alicia Carayon
Meteoritics & Planetary Science (in Press)   Link to Article [DOI: 10.1111/maps.12666]
1Solar System Exploration Division, Code 690, NASA Goddard Space Flight Center, Greenbelt, Maryland 20771, USA
2Astrochemistry Laboratory, Code 691, NASA Goddard Space Flight Center, Greenbelt, Maryland 20771, USA
3Chemistry Department, The Catholic University of America, Washington, D.C. 20064, USA
4International Space University, Strasbourg Central Campus, France
Published by arrangement with John Wiley & Sons

We report the ratio of the initial carbon available as CO that forms gas-phase compounds compared to the fraction that deposits as a carbonaceous solid (the gas/solid branching ratio) as a function of time and temperature for iron, magnetite, and amorphous iron silicate smoke catalysts during surface-mediated reactions in an excess of hydrogen and in the presence of N2. This fraction varies from more than 99% for an amorphous iron silicate smoke at 673 K to less than 40% for a magnetite catalyst at 873 K. The CO not converted into solids primarily forms methane, ethane, water, and CO2, as well as a very wide range of organic molecules at very low concentration. Carbon deposits do not form continuous coatings on the catalytic surfaces, but instead form extremely high surface area per unit volume “filamentous” structures. While these structures will likely form more slowly but over much longer times in protostellar nebulae than in our experiments due to the much lower partial pressure of CO, such fluffy coatings on the surfaces of chondrules or calcium aluminum inclusions could promote grain–grain sticking during low-velocity collisions.

 

High-pressure phases in shock-induced melt of the unique highly shocked LL6 chondrite Northwest Africa 757

1Hu, J., 1Sharp, T. G
1School of Earth and Space Exploration, Arizona State University, Tempe, Arizona, USA

Northwest Africa 757 is unique in the LL chondrite group because of its abundant shock-induced melt and high-pressure minerals. Olivine fragments entrained in the melt transform partially and completely into ringwoodite. Plagioclase and Ca-phosphate transform to maskelynite, lingunite, and tuite. Two distinct shock-melt crystallization assemblages were studied by FIB-TEM analysis. The first melt assemblage, which includes majoritic garnet, ringwoodite plus magnetite-magnesiowüstite, crystallized at pressures of 20–25 GPa. The other melt assemblage, which consists of clinopyroxene and wadsleyite, solidified at ~15 GPa, suggesting a second veining event under lower pressure conditions. These shock features are similar to those in S6 L chondrites and indicate that NWA 757 experienced an intense impact event, comparable to the impact event that disrupted the L chondrite parent body at 470 Ma.

Reference
Hu J, Sharp TG (2016) High-pressure phases in shock-induced melt of the unique highly shocked LL6 chondrite Northwest Africa 757.
Meteoritics & Planetary Science (in Press)
Link to Article [DOI: 10.1111/maps.12672]
Published by arrangement with John Wiley & Sons

Mercury’s Low-Reflectance Material: Constraints from Hollows

1Rebecca J. Thomas, 1,2Brian M. Hynek, 3David A. Rothery, 4Susan J. Conway
1Laboratory for Atmospheric and Space Physics, University of Colorado, 3665 Discovery Drive, Boulder, CO 80303, USA
2Department of Geological Sciences, University of Colorado, 399 UCB, Boulder, CO 80309, USA
3Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes, MK7 6AA, UK
4Laboratoire de Planétologie et Géodynamique – UMR CNRS 6112, 2 rue de la Houssinière – BP 92208, 44322 Nantes Cedex 3, France

Unusually low reflectance material, within which depressions known as hollows appear to be actively forming by sublimation, is a major component of Mercury’s surface geology. The observation that this material is exhumed from depth by large impacts has the intriguing implication that the planet’s lower crust or upper mantle contains a significant volatile–rich, low–reflectance layer, the composition of which will be key for developing our understanding of Mercury’s geochemical evolution and bulk composition. Hollows provide a means by which the composition of both the volatile and non–volatile components of the low–reflectance material (LRM) can be constrained, as they result from the loss of the volatile component, and any remaining lag can be expected to be formed of the non–volatile component. However, previous work has approached this by investigating the spectral character of hollows as a whole, including that of bright deposits surrounding the hollows, a unit of uncertain character. Here we use high–resolution multispectral images, obtained as the MESSENGER spacecraft approached Mercury at lower altitudes in the latter part of its mission, to investigate reflectance spectra of inactive hollow floors where sublimation appears to have ceased, and compare this to those of the bright surrounding products and the parent material. This analysis reveals that the final lag after hollow–formation has a flatter spectral slope than that of any other unit on the planet and reflectance approaching that of more space–weathered parent material. This indicates firstly that the volatile material lost has a steeper spectral slope and higher reflectance than the parent material, consistent with (Ca,Mg) sulfides, and secondly, that the low–reflectance component of LRM is non–volatile and may be graphite.

Reference
Thomas RJ, Hynek BM, Rothery DA, Conway SJ (2016) Mercury’s Low-Reflectance Material: Constraints from Hollows. Icarus (in Press)
Link to Article [doi:10.1016/j.icarus.2016.05.036]
Copyright Elsevier

Reflectance spectroscopy of oxalate minerals and relevance to solar system carbon inventories

1Daniel M. Applin, 1,2,3Matthew R.M. Izawa,1Edward A. Cloutis
1Hyperspectral Optical Sensing for Extraterrestrial Reconnaissance Laboratory, Dept. Geography, University of Winnipeg, 515 Portage Avenue, Winnipeg, Manitoba, Canada R3B 2E9
2Dept. Earth Sciences, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, Ontario, Canada L2S 3A1
3Planetary Science Institute, 1700 East Fort Lowell, Suite 106, Tucson, AZ 85719-2395

The diversity of oxalate formation mechanisms suggests that significant concentrations of oxalic acid and oxalate minerals could be widely distributed in the solar system. We have carried out a systematic study of the reflectance spectra of oxalate minerals and oxalic acid, covering the 0.2-16 µm wavelength region.. Our analyses show that oxalates exhibit unique spectral features that enable discrimination between oxalate phases and from other commonly occurring compounds, including carbonates, in all regions of the spectrum except for the visible. Using these spectral data, we consider the possible contribution of oxalate minerals to previously observed reflectance spectra of many objects throughout the solar system, including satellites, comets, and asteroids. We find that polycarboxylic acid dimers and their salts may explain the reflectance spectra of many carbonaceous asteroids in the 3 µm spectral region.. We suggest surface concentration of these compounds may be a type of space weathering from the photochemical and oxidative decomposition of the organic polymer found in carbonaceous chondrites. The stability and ubiquity of these minerals on Earth, in extraterrestrial materials, and in association with biological processes make them useful for many applications in Earth and planetary sciences.

Reference
Applin DM, Izawa MRM, Cloutis EA (2016) Reflectance spectroscopy of oxalate minerals and relevance to solar system carbon inventories. Icarus (in Press)
Link to Article [doi:10.1016/j.icarus.2016.05.005]
Copyright Elsevier

On the iron isotope composition of Mars and volatile depletion in the terrestrial planets

1Paolo A. Sossi, 1,2Oliver Nebel, 3,4Mahesh Anand, 5Franck Poitrasson
1Research School of Earth Sciences, Australian National University, Canberra 2601, ACT, Australia
2School of Earth, Atmosphere and Environment, Monash University, Melbourne 3800, VIC, Australia
3Department of Physical Sciences, Open University, Milton Keynes, MK76AA, UK
4Department of Earth Sciences, The Natural History Museum, London, SW7 5BD, UK
5Laboratoire Géosciences Environnement Toulouse, CNRS UMR 5563 – UPS – IRD, 14-16, Avenue Edouard Belin, 31400, Toulouse, France

Iron is the most abundant multivalent element in planetary reservoirs, meaning its isotope composition (expressed as δ57Fe) may record signatures of processes that occurred during the formation and subsequent differentiation of the terrestrial planets. Chondritic meteorites, putative constituents of the planets and remnants of undifferentiated inner solar system bodies, have View the MathML sourceδFe57≈0‰; an isotopic signature shared with the Martian Shergottite–Nakhlite–Chassignite (SNC) suite of meteorites. The silicate Earth and Moon, as represented by basaltic rocks, are distinctly heavier, View the MathML sourceδFe57≈+0.1‰. However, some authors have recently argued, on the basis of iron isotope measurements of abyssal peridotites, that the composition of the Earth’s mantle is View the MathML sourceδFe57=+0.04±0.04‰, indistinguishable from the mean Martian value. To provide a more robust estimate for Mars, we present new high-precision iron isotope data on 17 SNC meteorites and 5 mineral separates. We find that the iron isotope compositions of Martian meteorites reflect igneous processes, with nakhlites and evolved shergottites displaying heavier View the MathML sourceδFe57(+0.05±0.03‰), whereas MgO-rich rocks are lighter (View the MathML sourceδFe57≈−0.01±0.02‰). These systematics are controlled by the fractionation of olivine and pyroxene, attested to by the lighter isotope composition of pyroxene compared to whole rock nakhlites. Extrapolation of the View the MathML sourceδFe57 SNC liquid line of descent to a putative Martian mantle yields a δ57Fe value lighter than its terrestrial counterpart, but indistinguishable from chondrites. Iron isotopes in planetary basalts of the inner solar system correlate positively with Fe/Mn and silicon isotopes. While Mars and IV-Vesta are undepleted in iron and accordingly have chondritic δ57Fe, the Earth experienced volatile depletion at low (1300 K) temperatures, likely at an early stage in the solar nebula, whereas additional post-nebular Fe loss is possible for the Moon and angrites.

Reference
Sossi PA, Nebel O, Anand A, Poitrasson F (2016) On the iron isotope composition of Mars and volatile depletion in the terrestrial planets. Earth and Planetary Science Letters (in Press)
Link to Article [doi:10.1016/j.epsl.2016.05.030]
Copyright Elsevier

Massive impact-induced release of carbon and sulfur gases in the early Earth’s atmosphere

1S. Marchi, 2B.A. Black, 3L.T. Elkins-Tanton, 1W.F. Bottke
1Southwest Research Institute, Boulder, CO, United States
2City College, City University of New York, New York, NY, United States
3Arizona State University, Tempe, AZ, United States

Recent revisions to our understanding of the collisional history of the Hadean and early-Archean Earth indicate that large collisions may have been an important geophysical process. In this work we show that the early bombardment flux of large impactors (>100 km) facilitated the atmospheric release of greenhouse gases (particularly CO2) from Earth’s mantle. Depending on the timescale for the drawdown of atmospheric CO2, the Earth’s surface could have been subject to prolonged clement surface conditions or multiple freeze-thaw cycles. The bombardment also delivered and redistributed to the surface large quantities of sulfur, one of the most important elements for life. The stochastic occurrence of large collisions could provide insights on why the Earth and Venus, considered Earth’s twin planet, exhibit radically different atmospheres.

Reference
Marchi S, Black BA, Elkins-Tanton LT, Bottke WF (2016) Massive impact-induced release of carbon and sulfur gases in the early Earth’s atmosphere. Earth and Planetary Science Letters 449, 96–104.
Link to Article [doi:10.1016/j.epsl.2016.05.032]
Copyright Elsevier

Synthesis of akaganeite in the presence of sulfate:Implications for akaganeite formation in Yellowknife Bay, Gale Crater, Mars

1T.S. Peretyazhko, 2A. Fox, 1B. Sutter, 3P.B. Niles, 4M. Adams, 3R.V. Morris, 3D.W. Ming
1Jacobs, NASA Johnson Space Center, Houston, TX 77058
2/sup>Indiana University, Bloomington, IN 47406
3NASA Johnson Space Center, Houston, TX 77058
4University of Hawaii at Hilo, Hilo, HI 96720

Akaganeite, a Cl-bearing Fe(III) (hydr)oxide, has been recently discovered in Yellowknife Bay in Gale crater on Mars by the Mars Science Laboratory (MSL) Curiosity Rover. Akaganeite was associated with sulfate and sulfide minerals at Yellowknife Bay indicating that sulfate ions could be present in solution during akaganeite formation. The mechanism and conditions of akaganeite formation in the Yellowknife Bay mudstone are unknown. We investigated formation of akaganeite through hydrolysis of ferric chloride solution in the presence of 0, 0.01, 0.05, 0.1 and 0.2 M sulfate and at initial pH of 1.5, 2 and 4 at 90 °C. Mineralogy of the precipitated Fe(III) phases was characterized by X-ray diffraction and infrared spectroscopy. The precipitates were also acid digested to determine total sulfate and chloride contents. Akaganeite and natrojarosite formed at initial solution pH of 1.5; akaganeite, goethite and natrojarosite precipitated in initial pH 2 solutions and goethite, hematite and 2-line ferrihydrite precipitated at initial solution pH of 4. Sulfate addition did not inhibit akaganeite formation. Increasing initial solution sulfate concentrations resulted in increasing sulfate to chloride ratio in the precipitated akaganeite. Infrared spectroscopy revealed akaganeite bands at ∼2 μm (H2O combination band) and at ∼2.46 μm (OH combination band). The H2O combination band position linearly correlated with total chloride content in akaganeite. Overall, laboratory studies demonstrated formation of akaganeite at initial sulfate concentration ⩽ 0.2 M (sulfate to chloride molar ratio ⩽0.3) and pH ⩽ 2, implying that those conditions might prevail (perhaps as micro-environments) during akaganeite formation in Yellowknife Bay mudstone. The occurrence of Fe(II) sulfides (pyrite and pyrrhotite) in Yellowknife Bay mudstone is a potential acidity source. Dissolution of sulfide minerals might occur under localized oxidizing water-limiting Cl-rich conditions creating favorable environments for akaganeite formation.

Reference
Peretyazhko TS, Fox A, Sutter B, Niles PB, Adams M, Morris RV, Ming DW (2016)
Synthesis of akaganeite in the presence of sulfate:Implications for akaganeite formation in Yellowknife Bay, Gale Crater, Mars. Geochmica et Cosmochmica Acta (in Press)
Link to Article [doi:10.1016/j.gca.2016.06.002]
Copyright Elsevier

Target rocks, impact glasses, and melt rocks from the Lonar crater, India: Highly siderophile element systematics and Sr-Nd-Os isotopic signatures

1Toni Schulz, 2Ambre Luguet, 1Wencke Wegner, 2David van Acken,1,3Christian Koeberl
1Department of Lithospheric Research, University Vienna, Vienna, Austria
2Steinmann Institut of Geology, Mineralogy and Palaeontology, University of Bonn, Bonn, Germany
3Natural History Museum, Vienna, Austria

The Lonar crater is a ~0.57-Myr-old impact structure located in the Deccan Traps of the Indian peninsula. It probably represents the best-preserved impact structure hosted in continental flood basalts, providing unique opportunities to study processes of impact cratering in basaltic targets. Here we present highly siderophile element (HSE) abundances and Sr-Nd and Os isotope data for target basalts and impactites (impact glasses and impact melt rocks) from the Lonar area. These tools may enable us to better constrain the interplay of a variety of impact-related processes such as mixing, volatilization, and contamination. Strontium and Nd isotopic compositions of impactites confirm and extend earlier suggestions about the incorporation of ancient basement rocks in Lonar impactites. In the Re-Os isochron plot, target basalts exhibit considerable scatter around a 65.6 Myr Re-Os reference isochron, most likely reflecting weathering and/or magma replenishment processes. Most impactites plot at distinctly lower 187Re/188Os and 187Os/188Os ratios compared to the target rocks and exhibit up to two orders of magnitude higher abundances of Ir, Os, and Ru. Moreover, the impactites show near-chondritic interelement ratios of HSE. We interpret our results in terms of an addition of up to 0.03% of a chondritc component to most impact glasses and impact melt rocks. The magnitude of the admixture is significantly lower than the earlier reported 12–20 wt% of extraterrestrial component for Lonar impact spherules, reflecting the typical difference in the distribution of projectile component between impact glass spherules and bulk impactites.

Reference
Schulz T, Luguet A, Wegner W, van Acken D, Koeberl C (2016) Target rocks, impact glasses, and melt rocks from the Lonar crater, India: Highly siderophile element systematics and Sr-Nd-Os isotopic signatures. Meteoritics & Planetary Science (in Press)
Link to Article [DOI: 10.1111/maps.12665]
Published by arrangement with John Wiley & Sons

Searching for calcium-aluminum-rich inclusions in cometary particles with Rosetta/COSIMA

1Paquette, J. A. et al. (>10)*
1Max-Planck-Institut für Sonnensystemforschung, Göttingen, Germany
*Find the extensive, full author and affiliation list on the publishers website

The calcium-aluminum-rich inclusions (CAIs) found in chondritic meteorites are probably the oldest solar system solids, dating back to 4567.30 ± 0.16 million years ago. They are thought to have formed in the protosolar nebula within a few astronomical units of the Sun, and at a temperature of around 1300 K. The Stardust mission found evidence of CAI-like material in samples recovered from comet Wild 2. The appearance of CAIs in comets, which are thought to be formed at lower temperatures and larger distances from the Sun, is only explicable if some mechanism allows the efficient transfer of such objects from the inner solar nebula to the outer solar nebula. Such mechanisms have been proposed such as an X-wind or turbulence. In this work, particles collected from within the coma of comet 67P/Churyumov–Gerasimenko are examined for compositional evidence of the presence of CAIs. COSIMA (the Cometary Secondary Ion Mass Analyzer) uses secondary ion mass spectrometry to analyze the composition of cometary dust captured on metal targets. While CAIs can have a radius of centimeters, they are more typically a few hundred microns in size, and can be smaller than 1 μm, so it is conceivable that particles visible on COSIMA targets (ranging in size from about 10 μm to hundreds of microns) could contain CAIs. Using a peak fitting technique, the composition of a set of 13 particles was studied, looking for material rich in both calcium and aluminum. One such particle was found.

Reference
Paquette JA et al. (2016) Searching for calcium-aluminum-rich inclusions in cometary particles with Rosetta/COSIMA. Meteoritics & Planetary Science (in Press)
Link to Article [DOI: 10.1111/maps.12669]
Published by arrangement with John Wiley & Sons

CV and CM Chondrite Impact Melts

1,2Nicole G. Lunning, 1Catherine M. corrigan, 2Harry Y. McSween, 3,4Travis J. Tenner, 3Noriko T. Kita, 5Robert. J. Bodnar
1Department of Earth and Planetary Sciences and Planetary Geosciences Institute, University of Tennessee, Knoxville, TN 37996, USA
2Department of Mineral Sciences, Smithsonian Institution, National Museum of Natural History, Washington, DC 20560, USA
3Department of Geosciences, University of Wisconsin, Madison, WI 53706, USA
4Chemistry Division, Nuclear and Radiochemistry, Los Alamos National Laboratory, MSJ514, Los Alamos, NM 87545, USA
5Department of Geosciences, Virginia Tech, Blacksburg, VA 24061, USA

Volatile-rich and typically oxidized carbonaceous chondrites, such as CV and CM chondrites, potentially respond to impacts differently than do other chondritic materials. Understanding impact melting of carbonaceous chondrites has been hampered by the dearth of recognized impact melt samples. In this study we identify five carbonaceous chondrite impact melt clasts in three host meteorites: a CV3red chondrite, a CV3oxA chondrite, and a regolithic howardite. The impact melt clasts in these meteorites respectively formed from CV3red chondrite, CV3oxA chondrite, and CM chondrite protoliths. We identified these impact melt clasts and interpreted their precursors based on their texture, mineral chemistry, silicate bulk elemental composition, and in the case of the CM chondrite impact melt clast, in situ measurement of oxygen three-isotope signatures in olivine. These impact melts typically contain euhedral-subhedral olivine microphenocrysts, sometimes with relict cores, in glassy groundmasses. Based on petrography and Raman spectroscopy, four of the impact melt clasts exhibit evidence for volatile loss: these melt clasts either contain vesicles or are depleted in H2O relative to their precursors. Volatile loss (i.e., H2O) may have reduced the redox state of the CM chondrite impact melt clast. The clasts that formed from the more oxidized precursors (CV3oxA and CM chondrites) exhibit phase and bulk silicate elemental compositions consistent with higher intrinsic oxygen fugacities relative to the clast that formed from a more reduced precursor (CV3red chondrite). The mineral chemistries and assemblages of the CV and CM chondrite impact melt clasts identified here provide a template for recognizing carbonaceous chondrite impact melts on the surfaces of asteroids.

Reference
Lunning NG, Corrigan CM, McSween HY, Tenner TJ,Kita NT, Bodnar RJ (2016) CV and CM Chondrite Impact Melts. Geochmica et Cosmochimica Acta (in Press)
Link to Article [doi:10.1016/j.gca.2016.05.038]
Copyright Elsevier