¹Elizabeth B. Rampe, ²Richard V. Morris, ³P. Douglas Archer Jr, ⁴David G. Agresti, ²Douglas W. Ming
¹Aerodyne Industries, Jacobs JETS Contract at NASA Johnson Space Center, 2101 NASA Parkway, Mail Code XI3, Houston, Texas 77058, U.S.A.
²NASA Johnson Space Center, Houston, Texas 77058, U.S.A.
³Jacobs, NASA Johnson Space Center, Houston, Texas 77058, U.S.A.
⁴Department of Physics, University of Alabama at Birmingham, Birmingham, Alabama 35294, U.S.A.

Orbital and in-situ data from the surface of Mars indicate that nanophase weathering products are important constituents of martian rocks and soils. Nanophase minerals have the capacity to chemisorb anions like sulfate and phosphate onto their surfaces, but it is not known whether chemisorption is an important or even detectable process via orbital and in-situ observations. The detection of chemisorbed sulfate and phosphate anions on nanophase minerals would constrain the speciation of these anions and past aqueous environmental conditions. Here, we synthesized two nanophase weathering products that are common in terrestrial volcanic soils and have been identified on the martian surface: allophane and nanophase ferric oxide as represented by ferrihydrite. We specifically adsorbed sulfate and phosphate separately onto the nanophase mineral surfaces (4.5 and 1.6 wt% SO42−, and 6.7 and 8.9 wt% PO43− on allophane and ferrihydrite, respectively) and analyzed the untreated and chemisorbed materials using instruments similar to those on orbital and landed Mars missions (including X-ray diffraction, evolved gas analysis, Mössbauer spectroscopy, and VNIR and thermal-IR spectroscopy). Evolved gas analysis is the optimum method to detect chemisorbed sulfate, with SO2(g) being released at >900 °C for allophane and 400–800 °C for ferrihydrite. Chemisorbed sulfate and phosphate anions affect the thermal-IR spectra of allophane and ferrihydrite in the S-O and P-O stretching region when present in abundances of only a few weight percent; S-O and P-O stretching bands are apparent as short-wavelength shoulders on Si-O stretching bands. Sulfate and phosphate anions chemisorbed to allophane have small but measurable effects on the position of the OH-H2O bands at 1.4 and 1.9 μm in near-IR spectra. Chemisorbed sulfate and phosphate anions did not affect the X-ray diffraction patterns, Mössbauer spectra, and visible/near-IR spectra of ferrihydrite. These data suggest that sulfate chemisorbed onto the surfaces of nanophase minerals can be detected with the Sample Analysis at Mars (SAM) instrument on the Mars science laboratory Curiosity rover, and subtle signatures of chemisorbed sulfate and phosphate may be detectable by IR spectrometers on landed missions. The combined use of SAM, the Chemistry and Mineralogy (CheMin) instrument, and the Alpha Particle X-ray Spectrometer (APXS) on Curiosity allows for the most detailed characterization to date of nanophase minerals in martian rocks and soils and the potential presence of chemisorbed anionic complexes.

References
Rampe EB, Morris RV, Archer Jr PD, Agresti DG, Ming DW (2016) Recognizing sulfate and phosphate complexes chemisorbed onto nanophase weathering products on Mars using in-situ and remote observations. American Mineralogist 101, 627-643
Link to Article [doi:10.2138/am-2016-5305]
Copyright: The Mineralogical Society of America

¹Javier Cuadros, ¹Joe R. Michalski, ²Vesselin Dekov, ³Janice L. Bishop
¹Department of Earth Sciences, Natural History Museum, Cromwell Road, London SW7 5BD, U.K.
²Laboratoire de Géochimie et Métallogénie, Département Géosciences Marines, IFREMER, Z.I. Pointe du diable, BP 70, 29280 Plouzané, France
³SETI Institute, Mountain View, California 94043, U.S.A.

With the arrival of Curiosity on Mars, the MSL has started its ground validation of some of the phyllosilicate characterization carried out with remote sensing near-IR spectroscopy from orbital instruments. However, given the limited range of action of the rover, phyllosilicate identification and characterization will have to rely mainly on orbital near-IR data. Investigation of Earth analogs can greatly assist interpretation of martian spectra and enable more robust analyses. In this contribution, Mg/Fe-rich clays from submarine hydrothermal origin that had been thoroughly characterized previously were investigated with near-IR reflectance spectroscopy. The clays are mixed-layer glauconite-nontronite, talc-nontronite, talc-saponite, and nontronite samples. The hydroxyl bands in the range 2.1–2.35 μm were decomposed into their several individual components to investigate correlations between the octahedral chemistry of the samples and the normalized intensity of several bands. Good correlations were found for the samples of exclusive dioctahedral character (glauconite-nontronite and nontronite), whereas poor or no correlations emerged for the samples with one (talc-nontronite) or two (talc-saponite) trioctahedral layer components, indicating a more complex spectral response. Because these bands analyzed are a combination of the fundamental OH stretching and OH bending vibrations, the response of these fundamental bands to octahedral chemistry was considered. For 2:1 dioctahedral phyllosilicates, Fe and Mg substitution for Al displaces both fundamental bands to lower wavenumbers (longer wavelengths), so that their effect on the position of the combination band is coherent. In contrast, for trioctahedral clays, Al and Fe3+ substitution of octahedral Mg displaces the OH stretching band to lower wavenumber values, and the OH bending band to higher wavenumber values, resulting in partial or total mutual cancelation of their effects. As a result, clays with near-IR spectra indicating Mg-dominated octahedral compositions may in fact contain abundant Fe and some Al substitution. Thus, remote-sensing near-IR mineralogical and chemical identification of clays on Mars appears relatively straightforward for dioctahedral clay minerals but more problematic for trioctahedral clays, for which it may require a more detailed investigation of their near-IR spectra.

Reference
Cuadros J, Michalski JR, Dekov V, Bishop JL (2016) Octahedral chemistry of 2:1 clay minerals and hydroxyl band position in the near-infrared: Application to Mars. American Mineralogist 101, 554-563
Link to Article [doi:10.2138/am-2016-5366]
Copyright: The Mineralogical Society of America

¹Christopher D. K. Herd, ²Robert W. Hilts, ²Aaron W. Skelhorne,¹Danielle N. Simkus
¹Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, Alberta, Canada
²Department of Physical Sciences, MacEwan University, Edmonton, Alberta, Canada

The curation and handling of volatile-bearing astromaterials is of prime importance in current and future plans for sample return missions to targets containing organic compounds, ices, or other volatile components. We report on the specific curation constraints required for the preservation of the Tagish Lake meteorite, a C2 ungrouped chondrite that contains significant concentrations of organic matter, including compounds of prebiotic interest or volatile in character, and which was recovered from a frozen lake surface a few days after its fall. Here, we review the circumstances of the meteorite’s handling, its complement of intrinsic and contaminant organic compounds, and an unusual reaction between some of the specimens and the Al foil in which they were enclosed. From our results, we derive the requirements for curation of the meteorite, and describe a specialized facility that enables its curation and handling. The Subzero Facility for Curation of Astromaterials consists of a purified Ar glove box enclosed within a freezer chamber, and enables investigations relevant to curation of samples at or below −10 °C. We provide several recommendations based on insights obtained from the commissioning and initial use of the facility that are relevant to collection of freshly fallen meteorites, curation of volatile-bearing meteorites and other astromaterials, and planning and implementation of curation plans for future sample return missions to volatile-bearing targets.

Reference
Herd CDK, Hilts RW, Skelhorne AW, Simkus DN (2016) Cold curation of pristine astromaterials: Insights from the Tagish Lake meteorite. Meteoritics & Planetary Science (in Press)
Link to Article [DOI: 10.1111/maps.12603]
Published by arrangement with John Wiley & Sons

¹Marc M. Hirschmann
¹Department of Earth Sciences, University of Minnesota, Minneapolis, Minnesota 55455, U.S.A.

Earth’s inventory of principle volatiles C, H, N, and S is a legacy of its early stages of accretion and differentiation. Elemental ratios (C/H, C/N, C/S) are powerful tools for understanding early processing of Earth’s volatiles, as they monitor relative fractionations through important processes even when absolute concentrations are less well defined. The C/H ratio of the bulk silicate Earth (BSE), defined from surface reservoirs and minimally degassed oceanic basalts is 1.3 ± 0.3, which is 5–15 times lower than the C/H ratio of carbonaceous and enstatite chondrites and 2–5 times lower than ordinary chondrites. The BSE C/N ratio is superchondritic (40 ± 8; Bergin et al. 2015) while the C/S ratio (0.49 ± 0.14) is nearly chondritic. Successful models of volatile acquisition and processing must account for the effects of accretion, core formation, and atmospheric loss on all three of these ratios.
Simple models of equilibration between a magma ocean, the overlying atmosphere, and alloy destined for the core are used to explore the influence of core formation and atmospheric loss on major volatile concentrations and ratios. Among major volatile elements, C is most siderophile, and consequently core formation leaves behind a non-metallic Earth with low C/H, C/N, and C/S ratios compared to originally accreted materials and compared to the BSE. Compared to the predicted effect of early differentiation, the relatively high C/X ratios of the BSE argue in part that significant volatile replenishment occurred after core formation ceased, possibly in the form of a late veneer. However, a late veneer with chondritic composition is insufficient to explain the pattern of major volatile enrichments and depletions because BSE C/H and C/N ratios are non-chondritic. The C/H ratio is best explained if an appreciable fraction of H in the BSE predates delivery in the late veneer. Although atmospheric blow-off is an attractive explanation for the high C/N ratio, available data for C and N solubility and metal/silicate partitioning suggest that atmospheric blow-off cannot counter core formation to produce subchondritic C/N. Thus, unless virtually all core-forming metal segregated prior to volatile accretion (or relative C and N solubilities are appreciably different from those assumed here), the BSE C/N ratio suggests that accreting materials had elevated ratios compared to carbonaceous chondrites. One possibility is that a fraction of Earth’s volatiles accreted from differentiated C-rich planetesimals similar to the ureilite parent body. Reconciling C/H, C/N, and C/S ratios of the BSE simultaneously presents a major challenge that almost certainly involves a combination of parent body processing, core formation, catastrophic atmospheric loss, and partial replenishment by a late veneer. The chondritic C/S ratio of the BSE and relatively low S content of the BSE constrains the BSE C concentration, but a potential complicating factor in interpreting the BSE C/S ratio is the possible effect of segregation of an S-rich matte to the core during the later parts of core-mantle differentiation.

Reference
Hischmann MM (2016) Constraints on the early delivery and fractionation of Earth’s major volatiles from C/H, C/N, and C/S ratios. American Mineralogist 101, 540-553
Link to Article [doi: 10.2138/am-2016-5452]
Copyright: The Mineralogical Society of America

^1,2Anna Losiak, ³Izabela Golebiowska, ⁴Ludovic Ferrière, ⁵Jacek Wojciechowski, ^2,6Matthew S. Huber,^2,4Christian Koeberl
¹Institute of Geological Sciences, Polish Academy of Sciences, Wrocław, Poland
²Department of Lithospheric Research, University of Vienna, Vienna, Austria
³Cartography and Remote Sensing, Department of Geoinformatics, Faculty of Geography and Regional Studies, University of Warsaw, Warszawa, Poland
⁴Natural History Museum, Vienna, Austria
⁵Smart Information Systems GmbH, Vienna, Austria
⁶Department of Geology, University of the Free State, Bloemfontein, South Africa

Planar deformation features (PDFs) in quartz are the most important diagnostic features that allow the unambiguous identification of impact structures on Earth. In order to confirm that these features (that are characterized by planar character and form along specific crystallographic planes) are indeed PDFs, they need to be properly investigated and indexed. Following universal-stage measurements, the process of indexing is usually performed manually, using a Wulff stereonet and following a strict procedure, which is time consuming and error prone. In this article, we present WIP, a new Web-based program for indexing planar deformation features in quartz. The correctness of our program is shown by its application to measurements that had previously been indexed manually. The observed minor differences, especially in the absolute frequency percentage of PDFs, are negligible and not significant enough to influence the estimation of shock pressure that could be calculated from the indexed results. Usability of this program is shown using the spatial relationships between a statistically significant number of 278 quartz grains with 409 sets of PDFs analyzed within the area (~35 mm2) of a single thin section of a meta-greywacke from the Bosumtwi impact structure. Our program is not only more accurate and faster than the manual (graphical) method but also removes the human error from the plotting process and allows control of several parameters, such as the value of estimated measurement error used in the indexing calculation or method of aggregated error handling. The program also provides information about the angles between the planes of the measured PDF sets present in a grain, which allows determination of the angles between (for example) indexed {inline image} and {inline image} sets.

Reference
Losiak A, Golebiowska I, Ferrière L, Wojciechowski J, Huber MS, Koeberl C (2016)
WIP: A Web-based program for indexing planar features in quartz grains and its usage.
Meteoritics & Planetary Science (in Press)
Link to Article [DOI: 10.1111/maps.12614]
Published by arrangement with John Wiley & Sons

¹N.Mangold et al. (>10)*
¹Laboratoire de Planétologie et Géodynamique de Nantes, CNRS, UMR6112, Université de Nantes, Nantes, France
*Find the extensive, full author and affiliation list on the publishers website

The Curiosity rover has analyzed various detrital sedimentary rocks at Gale crater, among which fluvial and lacustrine rocks are predominant [Grotzinger et al., 2014, 2015]. Conglomerates correspond both to the coarsest sediments analyzed and the least modified by chemical alteration, enabling us to link their chemistry to that of source rocks on the Gale crater rims. In this study, we report the results of 6 conglomerate targets analyzed by APXS and 40 analyzed by ChemCam. The bulk chemistry derived by both instruments suggests two distinct end-members for the conglomerate compositions. The first group (Darwin type) is typical of conglomerates analyzed before sol 540; it has a felsic alkali-rich composition, with a Na2O/K2O > 5. The second group (Kimberley type) is typical of conglomerates analyzed between sol 540 and 670 in the vicinity of the Kimberley waypoint; it has an alkali-rich potassic composition with Na2O/K2O < 2. The variety of chemistry and igneous textures (when identifiable) of individual clasts suggest that each conglomerate type is a mixture of multiple source rocks. Conglomerate compositions are in agreement with most of the felsic alkali-rich float rock compositions analyzed in the hummocky plains (as reported in Sautter et al., 2015). The average composition of conglomerates can be taken as a proxy of the average igneous crust composition at Gale crater. Differences between the composition of conglomerates and that of finer-grained detrital sediments analyzed by the rover suggest modifications by diagenetic processes (especially for Mg-enrichments in fine grained rocks), physical sorting and mixing with finer-grained material of different composition.

Reference
Mangold N et al. (2016) Composition of conglomerates analyzed by the Curiosity rover: Implications for Gale crater crust and sediment sources. Journal of Geophysical Research, Planets (in Press)
Link to Article [DOI: 10.1002/2015JE004977]
Published by arrangement with John Wiley & Sons

¹J. Lasue et al. (>10)*
¹IRAP, OMP, CNRS, Toulouse, France
*Find the extensive, full author and affiliation list on the publishers Website

Zinc-enriched targets have been detected at the Kimberley formation, Gale crater, Mars, using the Chemistry Camera (ChemCam) instrument. The Zn content is analyzed with a univariate calibration based on the 481.2 nm emission line. The limit of quantification for ZnO is 3 wt.% (at 95% confidence level) and 1 wt.% (at 68% confidence level). The limit of detection is shown to be around 0.5 wt.%. As of sol 950, 12 targets on Mars present high ZnO content ranging from 1.0 wt.% to 8.4 wt.% (Yarrada, sol 628). Those Zn-enriched targets are almost entirely located at the Dillinger member of the Kimberley formation, where high Mn and alkali contents were also detected, probably in different phases. Zn enrichment does not depend on the textures of the rocks (coarse-grained sandstones, pebbly conglomerates, resistant fins). The lack of sulfur enhancement suggests that Zn is not present in the sphalerite phase. Zn appears somewhat correlated with Na2O and the ChemCam hydration index, suggesting that it could be in an amorphous clay phase (such as sauconite). On Earth, such an enrichment would be consistent with a supergene alteration of a sphalerite gossan cap in a primary siliciclastic bedrock or a possible hypogene non-sulfide zinc deposition where Zn, Fe, Mn, would have been transported in a reduced sulfur-poor fluid and precipitated rapidly in the form of oxides.

Reference
Lasue J et al. (2016) Observation of >5 wt % zinc at the Kimberley outcrop, Gale crater, Mars. Journal of Geophysical Research, Planets (in Press)
Link to Article [DOI: 10.1002/2015JE004946]
Published by arrangement with John Wiley & Sons

^1,2Erin L. Walton, ³Thomas G. Sharp, ³Jinping Hu
¹MacEwan University, Department of Physical Sciences, Edmonton, AB, T5J 4S2, Canada
²University of Alberta, Department of Earth & Atmospheric Sciences, Edmonton, AB, T6G 2E3, Canada
³Arizona State University, School of Earth & Space Exploration, Tempe, AZ, 85287-1404, USA

Shock-produced melt within crystalline basement rocks of the Steen River impact structure (SRIS) are observed as thin (1 – 510 μm wide), interlocking networks of dark veins which cut across and displace host rock minerals. Solid-state phase transformations, such as ferro-pargasite to an almandine-andradite-majorite garnet and amorphization of quartz and feldspar, are observed in zones adjacent to comparatively wider (50─500 μm) sections of the shock veins. Shock pressure estimates based on the coupled substitution of Na+, Ti4+ and Si4+ for divalent cations, Al3+ and Cr3+ in garnet (14─19 GPa) and the pressure required for plagioclase (Ab62-83) amorphization at elevated temperature (14−20 GPa) are not appreciably different from those recorded by deformation effects observed in non-veined regions of the bulk rock (14─20 GPa). This spatial distribution is the result of an elevated temperature gradient experienced by host rock minerals in contact with larger volumes of impact-generated melt and large deviatoric stresses experienced by minerals along vein margins.
Micrometer-size equant crystals of almandine-pyrope-majorite garnet define the shock vein matrix, consistent with rapid quench (100─200 ms) at 7.5─10 GPa. Crystallization of the vein occurred during a 0.1─0.15 s shock pressure pulse. Majoritic garnet, formed during shock compression by solid state transformation of pargasite along shock vein margins, is observed in TEM bright field images as nanometer-size gouge particles produced at strain rates in the supersonic field (106─108). These crystals are embedded in vesiculated glass, and this texture is interpreted as continued movement and heating along slip planes during pressure release. The deformation of high-pressure minerals formed during shock compression may be the first evidence of oscillatory slip in natural shock veins, which accounts for the production of friction melt via shear when little or no appreciable displacement is observed. Our observations of the mineralogy, chemistry and microtextures of shock veins within crystalline rocks of the SRIS allow us to propose a model for shock vein formation by shear-induced friction melting during shock compression.

Reference
Walton EL, Sharp TG, Hu J (2016) Frictional melting processes and the generation of shock veins in terrestrial impact structures: evidence from the Steen River impact structure, Alberta, Canada. Geochimica et Cosmochimica Acta (in Press)
Link to Article [doi:10.1016/j.gca.2016.02.024]
Copyright Elsevier

¹Timothy D. Glotch, ²Joshua L. Bandfield, ¹Michael J. Wolff, ³Jessica A. Arnold, ¹Congcong Che
¹Department of Geological Sciences, Stony Brook University, Stony Brook, NY
²Space Science Institute
³University of Oxford, Oxford, UK

Chloride salt-bearing deposits on Mars were discovered using the Mars Odyssey Thermal Emission Imaging System (THEMIS) and have been characterized by both mid-infrared (MIR) and visible-to-near-infrared (VNIR) remote sensing instruments. The chloride salt-bearing deposits exhibit a blue slope at MIR wavelengths and a featureless red slope at VNIR wavelengths. These deposits also lack strong 3 µm bands in VNIR spectra, indicating that they are desiccated compared to the surrounding regolith. The lack of VNIR spectral features suggest that an anhydrous chloride salt, the most likely of which is halite, is responsible for the observed spectral slope.
In this work, we use laboratory spectra and a hybrid T-matrix/Hapke light scattering model to constrain the particle sizes and salt abundances of the Martian chloride salt-bearing deposits. Our work shows that the two broad spectral classes of these deposits observed by THEMIS can be explained by a difference in the particle size of the admixed silicate regolith. In all cases, chloride salt abundances of 10-25% are required to match the THEMIS data. The chloride salt abundances determined in this work suggest deposition in a lacustrine/playa setting or in association with late-stage groundwater upwelling.

Reference
Glotch TD, Bandfield JL, Wolff MJ, Arnold JA, Che C (2016) Constraints on the composition and particle size of chloride salt‐bearing deposits on Mars. Journal of Geophysical Research, Planets (in Press)
Link to Article [DOI: 10.1002/2015JE004921]
Published by arrangement with John Wiley & Sons

¹Mehmet Yesiltas, ²Yoko Kebukawa
¹Department of Geosciences, Stony Brook University, Stony Brook, New York, USA
²Faculty of Engineering, Yokohama National University, Yokohama, Japan

We have investigated spatial and spectral associations between mineral species and organic matter in the Tagish Lake meteorite. Synchrotron-based infrared microspectroscopy allowed us to spatially locate specific organic and inorganic compounds within multiple Tagish Lake grains with high spatial resolution. Generated two-dimensional infrared maps present strong spatial association between aliphatic C-H and OH in phyllosilicates in Tagish Lake grains. These observations indicate possible roles of phyllosilicates for the formation, evolution, and preservation of organic matter. Infared spectra of all studied Tagish Lake grains show a strong carbonate band, which also shows a weak but positive correlation with organic matter in some grains. However, intergrain correlation was not observed between carbonates and organics, which is likely due to the difference of carbonate occurrence, e.g., presence of larger grains or intergrowth of carbonates on phyllosilicates. Possible scenarios further explaining the observed associations of organics with phyllosilicates and carbonates are presented.

Reference
Yesiltas M, Kebukawa Y (2016) Associations of organic matter with minerals in Tagish Lake meteorite via high spatial resolution synchrotron-based FTIR microspectroscopy. Meteoritics & Planetary Science (in Press)
Link to Article [DOI: 10.1111/maps.12609]
Published by arrangement with John Wiley & Sons