Constraints on the early delivery and fractionation of Earth’s major volatiles from C/H, C/N, and C/S ratios

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

WIP: A Web-based program for indexing planar features in quartz grains and its usage

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

Composition of conglomerates analyzed by the Curiosity rover: Implications for Gale crater crust and sediment sources

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

Observation of >5 wt % zinc at the Kimberley outcrop, Gale crater, Mars

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

Frictional melting processes and the generation of shock veins in terrestrial impact structures: evidence from the Steen River impact structure, Alberta, Canada

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

Constraints on the composition and particle size of chloride salt‐bearing deposits on Mars

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

Associations of organic matter with minerals in Tagish Lake meteorite via high spatial resolution synchrotron-based FTIR microspectroscopy

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

Re-analysis of previous laboratory phase curves: 2. Connections between opposition effect morphology and spectral features of stony meteorites

1Estelle Déau, 1Linda J. Spilker, 2Alberto Flandes
1NASA Jet Propulsion Laboratory, California Institute of Technology, Pasadena 91109 CA United States
2Ciencias Espaciales, Instituto de Geofísica, Universidad Nacional Autónoma de México, México, D.F., C.P. 04510, México

We investigate connections between the opposition phase curves and the spectra from ultraviolet to near infrared wavelengths of stony meteorites. We use two datasets: the reflectance dataset of Capaccioni et al., 1990 (Icarus, 83, 325), which consists of optical phase curves (from 2 to 45°) of 17 stony meteorites (3 carbonaceous chondrites, 11 ordinary chondrites, and 3 achondrites), and the spectral dataset from the RELAB database consisting of near-ultraviolet to near-infrared spectra of the same meteorites. We re-analyzed the first dataset and fit it with two morphological models to derive the amplitude A, the angular width HWHM of the surge and the slope S of the linear part. Our re-analysis confirms that stony meteorites have a non-monotonic behavior of the surge amplitude with albedo, which is also observed in planetary surfaces (Déau et al. 2013, Icarus, 226, 1465), laboratory samples (Nelson et al., 2004, Proc. Lunar Sci. Conf. 35, p. 1089) and asteroids (Belskaya and Shevchenko, 2000, Icarus, 147, 94). We find a very strong correlation between the opposition effect morphological parameters and the slope of the spectra between 0.75 μm and 0.95 μm. In particular, we found that meteorites with a positive amplitude-albedo correlation have a positive spectral slope between 0.75 μm and 0.95 μm, while meteorites with a negative amplitude-albedo correlation have a negative spectral slope between 0.75 μm and 0.95 μm. We have ruled out the role of the meteorite samples’ macro-properties (grain size, porosity and macroscopic roughness) in the correlations found because these properties were constant during the preparation of the samples. If this hypothesis is correct, this implies that other properties like the composition or the micro-properties (grain inclusions, grain shape or microscopic roughness) could have a preponderant role in the non-monotonic behavior of the surge morphology with albedo at small and moderate phase angles. Further accurate characterization of carbonaceous chrondrites samples are necessary to draw conclusions about the role of the micro-properties.

Reference
Déau E, Spilker LJ, Flandes A (2016) Re-analysis of previous laboratory phase curves: 2. Connections between opposition effect morphology and spectral features of stony meteorites. Icarus (in Press)
Link to Article [doi:10.1016/j.icarus.2016.01.035]
Copyright Elsevier

Miniature lightweight X-ray optics (MiXO) for surface elemental composition mapping of asteroids and comets

1Jaesub Hong, 2Suzanne Romaine and The MiXO team
1Harvard University, 60 Garden Street, Cambridge 02138, MA, USA
2Smithsonian Astrophysics Observatory, 60 Garden Street, Cambridge 02138, MA, USA

We currently do not have a copyright agreement with this publisher and cannot display the abstract here

Reference
HongJ, Romaine S and The MiXO team (2016) Miniature lightweight X-ray optics (MiXO) for surface elemental composition mapping of asteroids and comets. Earth, Planets and Space 68:35
Link to Article [doi:10.1186/s40623-016-0409-1]

Deconvolution of mixtures with high plagioclase content for the remote interpretation of lunar plagioclase-rich regions

1Serventi Giovanna, 2Carli Cristian, 1Sgavetti Mariaamaria
1Department of Physics and Earth Sciences, University of Parma, Italy
2IAPS-Inaf, Tor Vergata, Roma, Italy

Anorthositic rocks are widespread on the lunar surface and have probably been formed by flotation of PL over a magma ocean. A large portion of pristine rocks are characterized by a low Mg/(Mg+Fe) ratio, and have been classified as ferroan anorthosite, and recently, after observation from SELENE Spectral Profiler,pure anorthosites regions with more than 98% PL have been recognized.
In this paper we analyze a set of mixtures with PL content similar to the ferroan anorthosites and to the pure anorthosite regions, using the Origin Software and the Modified Gaussian Model.We consider three plagioclases with varying FeOwt% contents (PL1, PL2 and PL3)andthree mafic end-members (1)100% orthopyroxene, (2) 56% orthopyroxene and 44% clinopyroxene, and (3) 100% olivine (OL). The spectral parameters considered here are: band depth, band center, band width, c0 (the continuum intercept) and c1 (the continuum offset).
Here we have shown that in pyroxene (PX)-bearing mixtures, the PX is distinguishable even in mixtures with only 1% PX and that PX band at ca. 900 nm is always deeper than PL1 band while PL2 and PL3are deeperthan OPX 900 nm band from95, 96% PL. In OL-bearing mixtures, OL detection limit is 2% when mixed with PL1, and 3% and 4% if mixed with PL2 and PL3.
We also demonstrated how spectral parameters vary with PL%, and, generally, increasing the PL content: (1) 1250 nm band depth decreases when mixed with OL, while it deepens in mixtures with PX; (2) 1250 nm band centers generally move towards longer wavelength for PL1-bearing mixtures, while do not show significant variationsconsidering PL2/PL3-mixtures; (3)1250 nm band width of PL1 in E1 and E5-mixtures substantially widens while in other mixtures itonly slightly varies.
Here we also proposed an application to a real case, from Proclus crater, revealing how studying terrestrial analogues is fundamental to infer hypothesis on the mineralogical composition of a planetary surface, but also how the spectral convergence of spectra characterized by different compositions can led to misleading interpretations.

Reference
Giovanna S, Cristian C, Mariaamaria S (2016) Deconvolution of mixtures with high plagioclase content for the remote interpretation of lunar plagioclase-rich regions. Icarus (in Press)
Link to Article [doi:10.1016/j.icarus.2016.01.020]
Copyright Elsevier