Effects of Geochemical and Environmental Parameters on Abiotic Organic Chemistry Driven by Iron Hydroxide Minerals

1L. M. Barge,1E. Flores,2D. VanderVelde,1J. M. Weber,3M. M. Baum,3A. Castonguay
Journal of Geophysical Research (Planets) (in Press) Link to Article [https://doi.org/10.1029/2020JE006423]
1NASA Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA, 91109 USA
2Department of Chemistry, California Institute of Technology, 1200 E. California Blvd., Pasadena, CA, 91125 USA
3Department of Chemistry, Oak Crest Institute of Science, 128‐132 W. Chestnut Ave., Monrovia, CA, 91016 USA
Published by arrangement with John Wiley & Sons

Geological conditions play a significant role in prebiotic / abiotic organic chemistry, especially when reactive minerals are present. Previous studies of the prebiotic synthesis of amino acids and other products in mineral‐containing systems have shown that a diverse array of compounds can be produced, depending on the experimental conditions. However, these previous experiments have not simulated the effects of varying geochemical conditions, in which factors such as pH, iron redox state, or chemical concentrations may vary over time and space in a natural environment. In geochemical systems that contain overlapping gradients, many permutations of individual conditions could exist and affect the outcome of an organic reaction network. We investigated reactions of pyruvate and glyoxylate, two compounds that are central to the emergence of metabolism, in simulated geological gradients of redox, pH, and ammonia concentration. Our results show that the positioning of pyruvate/glyoxylate reactions in this environmental parameter space determines the organic product distribution that results. Therefore, the distribution pattern of amino acids and alpha‐hydroxy acids produced prebiotically in a system reflects the specific reaction conditions, and would be distinct at various locations in an environment depending on local geochemistry. This is significant for origin of life chemistry in which the composition and function of oligomers could be affected by the environmentally‐driven distribution of monomers available. Also, for astrobiology and planetary science where organic distribution patterns are sometimes considered as a possible biosignature, it is important to consider environmentally‐driven abiotic organic reactions that might produce similar effects.

The formation and alteration history of a forsterite-bearing Type C CAI from Allende: Evidence for a Type B CAI precursor, and implications for fluid-assisted metasomatism on the CV chondrite parent body

1Shaofan Che,1Adrian J.Brearley
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2020.10.031]
1Department of Earth and Planetary Sciences, MSC03-2040, 1 University of New Mexico, Albuquerque, NM 87131-0001, USA
Copyright Elsevier

Type C CAIs are a rare group of refractory inclusions in carbonaceous chondrites that are compositionally and isotopically distinct from the more commonly observed igneous CAIs (i.e., Type As and Type Bs). We have investigated a forsterite-bearing Type C CAI ALNH-04 from the Allende CV3 chondrite. This CAI has both textural and compositional similarities to some of the Type C CAIs previously reported; however, there are notable differences that imply that ALNH-04 may have formed from a different precursor from other Type C inclusions. Based on the bulk composition of ALNH-04 and the minor element contents of forsterite, we suggest that the forsterite grains were inherited from a Forsterite-bearing Type B CAI (FoB) precursor. The presence of augite on the periphery of ALNH-04 implies a re-melting event that probably occurred in a chondrule-forming region.

Another interesting feature of ALNH-04 is the secondary iron-alkali-halogen zoning sequence as manifested by varying proportions of nepheline, sodalite, fayalitic olivine, and sulfides in different regions of the CAI. Nepheline ± sodalite have replaced anorthite in the outer part of the inclusion, giving way to the presence of ubiquitous sodalite with minor nepheline, partially replacing anorthite at grain boundaries and fractures in the interior of the inclusion. Sulfides and Fe-bearing olivine form an iron-rich alteration zone. The textural relationships between nepheline and sodalite show no evidence of a direct replacement relationship between the two phases. Combined with the SEM observations, the microstructures are most consistent with a two-stage fluid alteration process: (1) nepheline replaced anorthite in the outer part of the CAI via a fluid with within the stability range of nepheline; (2) a later-stage fluid, with elevated that could preferentially stabilize sodalite, penetrated further into the CAI interior, replacing anorthite with sodalite. The lack of a nepheline-sodalite replacement relationship indicates that the conditions and fluid chemistry were suitable for nepheline and/or sodalite to be stable. Together with other Fe-rich secondary phases, fayalitic olivine may have recorded an increase in pH and of the fluid. These changes were probably induced by the extensive alteration of the outer part of the CAI by feldspathoids. The observed alteration microstructures are consistent with a coupled dissolution-precipitation alteration mechanism. The fluid alteration was also responsible for the formation of Na- and Ca-rich halos in the matrix surrounding the CAI.

We compared ALNH-04 with other CAIs and chondrules showing alkali-halogen-(iron) zoning sequences in Allende, and found that the observed zoning structures are consistent with the two-stage fluid-assisted metasomatic process mentioned above. The different distribution patterns of nepheline and sodalite in plagioclase-rich CAIs, chondrules, and melilite-rich CAIs may be explained by different chemical potential gradients in SiO2 in the fluid. Precipitation of nepheline and sodalite may require a higher SiO2 activity compared to grossular and dmisteinbergite (±secondary anorthite), which controlled the formation location of sodalite during the second fluid alteration event. Fluids with different compositions may be produced by fluid percolation along different directions and pathways, changing convection patterns, or release of water from a differentiated asteroidal interior.

Donwilhelmsite, [CaAl4Si2O11], a new lunar high-pressure Ca-Al-silicate with relevance for subducted terrestrial sediments

1,2Jörg Fritz,3Ansgar Greshake,4Mariana Klementova,5Richard Wirth,4Lukas Palatinus,6Reidar G. Trønnes,3,7,8Vera Assis Fernandes,9Ute Böttger,10Ludovic Ferrière
American Mineralogist 105, 1704–1711 Link to Article [http://www.minsocam.org/msa/ammin/toc/2020/Abstracts/AM105P1704.pdf]
1Zentrum für Rieskrater und Impaktforschung, Nördlingen, Vordere Gerbergasse 3, D-86720 Nördlingen,
Germany. ORCID 0000-0002-6333-4775
2Saalbau Weltraum Projekt, Liebigstraße 6, D-64646 Heppenheim, Germany
3Museum für Naturkunde Berlin, Invalidenstrasse 43, D-10115 Berlin, Germany. ORCID 0000-0001-6475-9751
4Institute of Physics of the Czech Academy of Science, v.v.i., Na Slovance 2, 182 21 Prague, Czech Republic. † ORCID 0000-0002-8987-8164
5Helmholtz-Zentrum Potsdam–Deutsches GeoForschungsZentrum, Sektion 3.5 Grenzflächen-Geochemie, Telegrafenberg, D-14473 Potsdam, Germany
6Natural History Museum and Centre for Earth Evolution and Dynamics (CEED), University of Oslo, N-0315 Oslo,
Norway. ORCID 0000-0002-4458-5624
7Department of Earth and Environmental Sciences, University of Manchester, Williamson Building, Oxford Road, M13 9PL Manchester, U.K.
ORCID 0000-0003-0848-9229
8Instituto Dom Luiz (IDL), Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016, Lisboa, Portugal
9Institut für Optische Sensorsysteme, Deutsches Zentrum für Luft und Raumfahrt Berlin, Rutherfordstrasse 2, D-12489 Berlin, Germany
10Natural History Museum, Burgring 7, A-1010 Vienna, Austria. ORCID 0000-0002-9082-6230
Copyright: The Mineralogical Society of America

We report on the occurrence of a new high-pressure Ca-Al-silicate in localized shock melt pockets found in the feldspatic lunar meteorite Oued Awlitis 001 and discuss the implications of our discovery.
The new mineral crystallized as tiny, micrometer-sized, acicular grains in shock melt pockets of roughly anorthitic bulk composition. Transmission electron microscopy based three-dimensional electron diffraction (3D ED) reveals that the CaAl4Si2O11 crystals are identical to the calcium aluminum silicate (CAS) phase first reported from static pressure experiments. The new mineral has a hexagonal structure, with a space group of P63/mmc and lattice parameters of a = 5.42(1) Å; c = 12.70(3) Å; V = 323(4) Å3;Z = 2. This is the first time 3D ED was applied to structure determination of an extraterrestrial mineral.
The International Mineralogical Association (IMA) has approved this naturally formed CAS phase as the new mineral “donwilhelmsite” [CaAl4Si2O11], honoring the U.S. lunar geologist Don E. Wilhelms.
On the Moon, donwilhelmsite can form from the primordial feldspathic crust during impact cratering events. In the feldspatic lunar meteorite Oued Awlitis 001, needles of donwilhelmsite crystallized in ~200 mm sized shock melt pockets of anorthositic-like chemical composition. These melt pockets quenched within milliseconds during declining shock pressures. Shock melt pockets in meteorites serve as natural crucibles mimicking the conditions expected in the Earth’s mantle. Donwilhelmsite forms in the Earth’s mantle during deep recycling of aluminous crustal materials, and is a key host for Al and Ca of subducted sediments in most of the transition zone and the uppermost lower mantle (460–700 km). Donwilhelmsite bridges the gap between kyanite and the Ca-component of clinopyroxene at low pressures and the Al-rich Ca-ferrite phase and Ca-perovskite at high-pressures. In ascending buoyant mantle plumes, at about 460 km depth, donwilhelmsite is expected to break down into minerals such as garnet, kyanite, and clinopyroxene. This process may trigger minor partial melting, releasing
a range of incompatible minor and trace elements and contributing to the enriched mantle (EM1 and EM2) components associated with subducted sedimentary lithologies.

Vanadium micro-XANES determination of oxygen fugacity in olivine-hosted glass inclusion and groundmass glasses of martian primitive shergottite Yamato 980459

1,2Ryoichi Nakada,2Tomohiro Usui,3Masashi Ushioda,4Yoshio Takahashi
American Mineralogist 105, 1695–1703 Link to Article [http://www.minsocam.org/msa/ammin/toc/2020/Abstracts/AM105P1695.pdf]
1Kochi Institute for Core Sample Research, Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Monobe 200, Nankoku, Kochi 783-8502, Japan
2Earth-Life Science Institute, Tokyo Institute of Technology, Meguro, Tokyo 152-8550, Japan
3Geological Survey of Japan, National Institute of Advanced Industrial Science and Technology (AIST), Central 7, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8567, Japan
4Department of Earth and Planetary Science, The University of Tokyo, Hongo 7-3-1, Bunkyo, Tokyo 113-0033, Japan
Copyright: The Mineralogical Society of America

The redox condition of magma determines the stability and composition of crystallizing and volatile phases in martian meteorites, reflecting the evolution of the martian interior. In the current study, direct analyses on the oxidation states of V, Cr, and Fe were performed based on the X-ray absorption near- edge structure (XANES) measurements equipped with a micro-sized X-ray beam. We first applied the micro-XANES (μ-XANES) technique to the olivine-hosted glass inclusion and groundmass glass of martian meteorite Yamato 980459 (Y98), which is interpreted as representing a primary melt composi- tion. Mass-balance calculations and XANES spectra comparisons indicated that, while chromite and pyroxene affected Cr and Fe K-edge XANES spectra, the contribution of these minerals was minimal for V. The pre-edge peak intensity of V K-edge XANES enabled the estimation of the oxygen fugac- ity for inclusion and groundmass glasses. The calculated oxygen fugacity (fO2) of the glass inclusions was near the Iron-Wüstite (IW) buffer (IW-0.07 ± 0.32) for the glass inclusion, whereas it was 0.9 log units more oxidized (IW+0.93 ± 0.56) for the groundmass glasses. This result suggests that the redox condition of the parent magma of Y98 evolved during magma ascent and emplacement. Since Y98 is interpreted to have evolved in a closed system, our finding suggests that fractional crystallization and/or ascent of magma potentially induces the fO2 increase. This study shows that the μ-XANES technique enables us to determine the fO2 by only measuring a single phase of glassy compounds, and thus, it is useful to discuss the redox condition of volcanic rocks even if they do not crystallize out several equilibrium phases of minerals.

Evidence for dielectric breakdown weathering on the Moon

1,2A.P.Jordan
Icarus (in Press) Link to Article [https://doi.org/10.1016/j.icarus.2020.114199]
1Institute for the Study of Earth, Oceans, and Space, University of New Hampshire, Durham, NH, USA
2Solar System Exploration Research Virtual Institute, NASA Ames Research Center, Moffett Field, CA, USA
Copyright Elsevier

Soil on the Moon is darkened by space weathering, a process generally assumed to be dominated by the solar wind and/or micrometeoroid impacts. Recent work, however, predicts that another process darkens the soil: large solar energetic particle events may cause dielectric breakdown (or “sparking”), melting, and vaporizing soil at a rate comparable to that of micrometeoroids. Unlike the solar wind and/or micrometeoroids, a combination of dielectric breakdown and micrometeoroid weathering can explain how the reflectance of the lunar maria varies with latitude at 750 and 1064 nm, and this combination provides a reasonable mechanism to explain how magnetic anomalies form prominent swirls in the maria. Consequently, space weathering in the lunar maria seems to be dominated by micrometeoroid impacts and dielectric breakdown.

Effects of small crystallite size on the thermal infrared (vibrational) spectra of minerals

1Victoria E. Hamilton,2Christopher W. Haberle,3,4Thomas G. Mayerhöfer
American Mineralogist 105, 1756–1760 Link to Article [http://www.minsocam.org/msa/ammin/toc/2020/Abstracts/AM105P1756.pdf]
1Department of Space Studies, Southwest Research Institute, 1050 Walnut Street, no. 300, Boulder, Colorado 80302, U.S.A 2School of Earth and Space Exploration, Arizona State University, Tempe, Arizona 85287, U.S.A.
3Leibniz Institute of Photonic Technology (IPHT), Albert-Einstein-Str. 9, D-07745 Jena, Germany 4
4Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich Schiller University, Helmholtzweg 4, D-07743 Jena, Germany
Copyright: The Mineralogical Society of America

The thermal infrared (TIR, or vibrational) emission spectra of a suite of synthetic Mg-Fe olivines exhibit notable differences from their natural igneous counterparts in terms of their band shapes, relative depths, and reduced shifts in some band positions with Mg-Fe solid solution. Comparable reflectance spectra acquired from olivine-dominated matrices and fusion crusts of some carbonaceous chondrite meteorites exhibit similar deviations. Here we show that these unusual spectral characteristics are consistent with crystallite sizes much smaller than the resolution limit of infrared light. We hypothesize that these small crystallites denote abbreviated crystal growth and also may be linked to the size of nucleation sites. Other silicates and non-silicates, such as carbonates, exhibit similar spectral behaviors. Because the spectra of mineral separates are commonly used in the modeling and analysis of comparable bulk rock, meteorite, and remote sensing data, understanding these spectral variations is important to correctly identifying the
minerals and interpreting the origin and/or secondary processing histories of natural materials.


New constraints from 26Al-26Mg chronology of anorthite bearing chondrules in unequilibrated ordinary chondrites

1Guillaume Siron,1Kohei Fukuda,2Makoto Kimura,1Noriko T. Kita
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2020.10.025]
1WiscSIMS, Department of Geoscience, University of Wisconsin-Madison, Madison, WI 53706, USA
2National Institute of Polar Research, Meteorite Research Center, Midoricho 10-3, Tachikawa, Tokyo 190-8518, Japan
Copyright Elsevier

26Al-26Mg ages were determined for 14 anorthite-bearing chondrules from five different unequilibrated ordinary chondrites (UOCs) with low petrologic subtypes (3.00-3.05). In addition, oxygen three isotopes of these chondrules were also measured. The selected chondrules are highly depleted in alkali elements, and anorthite is the only mesostasis phase, though they show a range of mafic mineral compositions (Mg# 76-97 mole%) that are representative of chondrules in UOCs. The mean Δ17O values in these chondrules range from –0.44 ± 0.23‰ to 0.49 ± 0.15‰, in good agreement with previous studies of plagioclase-bearing chondrules from UOCs. Anorthite in all chondrules exhibit resolvable excess 26Mg (> 1.0 ± 0.4‰). Their inferred (27Al/26Al)0 range from (6.3 ± 0.7)×10–6 to (8.9 ± 0.3)×10–6 corresponding to a timescale for chondrule formation of 1.8 ± 0.04 Ma to 2.16 ± 0.12/0.11 Ma after CAIs using a canonical (27Al/26Al)0 value of 5.25×10–5. The ages from six chondrules in LL chondrites are restricted to between 1.8 Ma and 1.9 Ma, whereas eight chondrules in L chondrites show ages from 1.8 Ma to 2.2 Ma, including three chondrules at ∼2.0 Ma and two chondrules at ∼2.15 Ma.

The inferred chondrule formation ages from this study are at the peak of those previously determined for UOC chondrules, though with much shorter durations. This is potentially due to the time difference between formation of anorthite-bearing chondrules and typical UOC chondrules with alkali-rich compositions. Alternatively, younger chondrules ages in previous studies could have been the result of disturbance to the Al-Mg system in glassy mesostasis even at the low degree of thermal metamorphism in the parent bodies. Nevertheless, the high precision ages from this study (with uncertainties from 0.04 Ma to 0.15 Ma) indicate that there was potentially more than one chondrule forming event represented in the studied population. Considering data from LL chondrites only, the restricted duration (≤0.1 Ma) of chondrule formation ages suggests an origin in high density environments that subsequently lead to parent body formation. However, the unusually low alkali contents of the studied chondrules compared to common alkali-rich chondrules could also represent earlier chondrule formation events under relatively lower dust densities in the disk. Major chondrule forming events for UOCs might have postdated or concurrent with the younger anorthite-bearing chondrule formation at 2.15 Ma after CAIs, which are very close to the timing of accretion of ordinary chondrite parent bodies that are expected from thermal evolution of ordinary chondrite parent bodies.