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Samples of Allende have been altered hydrothermally under oxidizing conditions at 200 C. TEM studies show that within 30 days evidence of replacement of matrix olivines by fine-grained serpentine is present and by 90 days complete alteration of many grains has occurred.
Methodology and calibrations are being developed to identify specific clay mineral species in the CCD spectra of dark asteroids. This will constrain the geologic processes within their parent bodies and the production or alteration of organic molecules within such asteroids. Additional information is contained in the original extended abstract.
Based on petrologic and isotopic observations, the CR chondrites represent one of the most primitive carbonaceous chondrite groups. The organic matter in CR chondrite matrices is considered to be among the most ancient carbonaceous matter known, potentially providing a link between organic matter in the interstellar medium and our solar system [1]. However, the organic chemistry of CR chondrites may be complicated by the fact that these meteorites have undergone moderate secondary alteration, which potentially overprints primordial features [2]. Although the general effects of this alteration have been documented [2], the details of the fine-grained mineralogy and alteration styles of CR matrices are not fully understood. Here we present TEM observations of matrix in EET 92042, a CR chondrite that contains particularly primitive insoluble organic matter [1]. Preliminary studies [3] determined that EET 92042 matrix is heterogeneous in terms of mineralogy, texture, and petrographic fabric on the micron scale. EET 92042 contains magnetite-rich regions, foliated matrix and dark inclusions (DIs). Some chondrules show fine-grained rims, similar to those described by [4].
The CheMin minerological instrument on Mars Science Laboratory (MSL'09) [1] will return quantitive Xray diffraction data (XRD) and quantative X-ray fluorescence data (XRF;14<Z<92) from scooped soil samples and drilled rock powders collected from the Mars surface. Samples of 45-65 mm 3 from material sieved to less than 150 micrometers will be delivered through a funnel to one of 27 reusable sample cells (five additional cells on the sample wheel contain diffraction of fluorescence standards). Sample cells are 8-mm diamater discs with 7-micrometer thick Mylar or Kapton windows spaced 170 micrometers apart. Within this volume, the sample is shaken by piezoelectric vibration at sonic frequencies, causing the powder to flow past a narrow, collimated -ray beam in random orientation can be obtained even from minnerals exhibiting strong preferred orientation such as phylosilicates.
Meteorites provide us with valuable insights into the conditions of the early solar system. Collisions often occur in our solar system that can result in materials accreting to other bodies as foreign clasts. These foreign pieces may have multiple origins that can sometimes be easily identified as a particular type of meteorite. It is important to interpret the origins of these clasts in order to understand dynamics of the solar system, especially throughout its early history. The Nice Model, as modified, proposes a reordering of planetary orbits that is hypothesized to have triggered the Late Heavy Bombardment. Clasts found within meteorites that came from objects in the solar system not commonly associated as an impactor could be indicative of such an event suggested by the Nice Model. Impacts also redistribute material from one region of an asteroid to another, and so clasts are found that reveal portions of the geological history of a body that are not recorded by typical samples. These would be cognate clasts. The goal of this investigation was to examine meteorites that had particularly interesting foreign and cognate clasts enclosed in them. We focus here on an unusual clast located in the ordinary chondrite, NWA 6925. This is one of three clasts analyzed during the LPI summer internship of Jessica Johnson.
Analyses of X-ray diffraction (XRD) patterns taken by the CheMin instrument on the Curiosity Rover in Gale crater have documented the presence of clay minerals interpreted as smectites and a suite of amorphous to short-range order materials termed X-ray amorphous materials. These X-ray amorphous materials are commonly ironrich and aluminum poor and likely some of them are weathering products rather than primary glasses due to the presence of volatiles. Outstanding questions remain regarding the chemical composition and mineral structure of these X-ray amorphous materials and the smectites present at Gale crater and what they indicate about environmental conditions during their formation. To gain a better understanding of the mineral transitions that occur within ferromagnesian parent materials, we have investigated the development of secondary clay minerals and shortrange order materials in two soil chronosequences with varying climates developing on ultramafic bedrock. Field Sites: We investigated soil weathering within two field locations, the Klamath Mountains of Northern California, and the Tablelands of Newfoundland, Canada. Both sites possess age dated or correlated recently deglaciated soils and undated but substantially older soils. In the Klamath mountains the Trinity Ultramafic Body was deglaciated roughly 15,000 years bp while in the Tablelands a moraine was dated to about 17,600 years bp. The Klamath Mountains feature a seasonally wet and dry climate while the Tablelands are wet year-round with saturated soil conditions observed during sampling and standing water observed within 3 of 4 soil pit sampling locations.
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In the past, > 200,000 kg of U was released to the Hanford Site vadose zone from disposal and leakage of waste byproducts from plutonium production during World War II and the Cold War (Zachara et al., 2007). U is highly mobile due to the presence of carbonates and oxidizing conditions, with K{sub d} of 0.1 - 8 mL/g at the site (Zachara et al., 2007; Szecsody et al., 2013; Serne et al., 2008). NH{sub 3} (gas) injection is being investigated as a remediation technique as it is an in situ method that will not introduce additional liquid that could drive contaminants deeper into vadose zone towards groundwater. Objectives: To understand the impact of alkaline injection on geochemical processes in the Hanford Site vadose zone, including: 1)Long-term fate of uranium (U); 2)Dissolution and re-precipitation of secondary minerals. Apparent K{sub d}'s increase significantly with NH{sub 3} gas treatment, especially for six-month aging. - K{sub d} decreases after aeration, primarily due to U desorption at lower pH. U removal is still significantly greater than natural conditions (K{sub d} < 8 vs. > 100 mL/g). - Three-day aeration has higher loading than six-month after ammonia gas treatment and aeration. However, significantly greater desorption of U occurs with aeration in the six-month aged sample potentially due to transformation into different, more soluble solid phases with longer term aging. - U removal is primarily due to (1) co-precipitation of U with secondary minerals and (2) adsorption to minerals' surface, although further research is required to identify dominant mechanisms. Future experiments will focus on garnering a better understanding of the solid phase U speciation. Solids will be characterized using SEM-EDS, EMPA, XPS, XAFS, and TEM to better understand the effects of basic treatments on initial minerals and formation of secondary precipitates.
Most phyllosilicates on Mars are thought to have formed during the planet's earliest Noachian era, then Mars underwent a global change making the planet's surface more acidic [e.g. 1]. Prevailing acidic conditions may have affected the already existing phyllosilicates, resulting in the formation of sulfates. Both sulfates and phyllosilicates have been identified on Mars in a variety of geologic settings [2] but only in a handful of sites are these minerals found in close spatial proximity to each other, including Mawrth Vallis [3,4] and Gale Crater [5]. While sulfate formation from the acidic weathering of basalts is well documented in the literature [6,7], few experimental studies investigate sulfate formation from acid-weathered phyllosilicates [8-10]. The purpose of this study is to characterize the al-teration products of acid-weathered phyllosilicates in laboratory experiments. We focus on three commonly identified phyllosilicates on Mars: nontronite (Fe-smectite), saponite (Mg-smectite), and montmorillonite (Al-smectite) [1, and references therein]. This information will help constrain the formation processes of sulfates observed in close association with phyllosilicates on Mars and provide a better understanding of the aqueous history of such regions as well as the planet as a whole.
Major occurrences of hydrous alteration minerals on Mars have been found in Noachian impact craters formed in basaltic targets and detected using visible/near infrared (VNIR) spectroscopy. Until recently phyllosilicates were detected only in craters in the southern hemisphere [1, 2]. However, it has been reported that at least nine craters in the northern plains apparently excavated thick layers of lava and sediment to expose phyllosilicates [3] as well. The MER (Mars Exploration Rovers) rovers previously reported results of in situ measurement indicating the presence of alteration minerals on Mars [4,5] and it was recently reported that the Mars Curiosity rover has detected alteration phases in situ at Yellowknife Bay in Gale crater as well [6,7]. An important discovery for Mars geochronology is that the Chemistry and Mineralogy (CheMin) x-ray diffraction (XRD) instrument on Curiosity detected phyllosilicates indicating that phyllosilicate formation on Mars extended beyond the Noachian Epoch [8]. These discoveries indicate that Mars was globally altered by water in the past but does not constrain formation conditions for alteration phase occurrences, which have important implications for the evolution of the surface and the biological potential on Mars. Understanding the alteration assemblages produced by a range of conditions is vital for the interpretation of phyllosilicate spectral signatures as well as in situ measurements and to decipher the environment and evolution of early Mars. The martian surface has been intensely altered by meteorite impacts whose effects include brecciation and melting of target materials as well as the initiation of hydrothermal circulation in a hydrous target [9,10,11,12]. Impact effects may facilitate aqueous alteration of a basaltic target because the rate of silicate dissolution is a function of the degree of crystallinity, surface area, and temperature. The resultant alteration mineralogies from shocked basaltic target material are a function of the original mineral assemblage in the parent rocks, the chemistry of fluids that interacted with the rocks, and physico-chemical conditions (pH, temperatures, and pressure) during the time of mineral formation. Understanding the alteration assemblages produced by a range of conditions is vital for the interpretation of phyllosilicate spectral signatures and to decipher the environment and evolution of early Mars, and especially for identifying habitable niches in which life could be initiated and sustained. No experimentally controlled and well characterized analog materials that simulate martian shock metamorphism and alteration conditions currently exist for calibrating either remote sensing or in situ measurements of Mars. A series of experiments was initiated to assess the effects of systematic changes in the physico-chemical conditions on Mars analog materials thereby providing samples to ground-truth Mars remote sensing observations from CRISM (Compact Reconnaissance Imaging Spectrometer for Mars) and in situ measurements from Opportunity's Mössbauer and Curiosity's CHEMIN (Chemistry and Mineralogy X-Ray Diffraction/XRay Fluorescence) instruments. Results of initial experimental runs as analysed by SEM-EDS (Secondary Electron Microscopy -Energy Dispersive Spectroscopy) and X-ray Diffraction (XRD) analysis are reported here and lay the foundation for comparison with shocked and altered samples that will be characterized in the next phase of this work.
Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed phyllosilicates were examined by XRD analysis. Mineralogical changes were significant in Adirondack incubated with 10 mM MgCl2 at pH 4 and heated at 200 C. X-ray diffraction analysis revealed formation of phyllosilicate during 14 day incubation (Figure 1). Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. The position of 02l (4.60 A) and 060 (1.54 A) diffraction bands were indicative of trioctahedral smectite such as saponite. Analysis of solution composition demonstrated that aqueous concentration of Mg decreased from 10 mM to approx.4 mM after 7 day incubation likely due to saponite formation. Smectite also formed in Adirondack incubated with 0 mM MgCl2 at pH 4 and heated at 200 C. However, diffraction peak positions of 02l (4.52 A) and 060 (1.51 A) suggested formation of dioctahedral nontronite. The 100degC Mg and Fe(II) treated basaltic glass experiments are ongoing and results will be presented.
The Mars Science Laboratory rover Curiosity investigated sedimentary rocks that were deposited in a diversity of fluvio-lacustrine settings. The entire science payload was employed to characterize the mineralogy and chemistry of the Sheepbed mudstone at Yellowknife Bay and the Windjana sandstone at the Kimberley. Data from the CheMin instrument, a transmission Xray diffractometer, were used to determine the quantitative mineralogy of both samples. The Sheepbed mudstone contains detrital basaltic minerals, calcium sulfates, iron oxides or hydroxides, iron sulfides, trioctahedral smectite, and amorphous material. The mineral assemblage and chemical data from APXS suggest that the trioctahedral smectite and magnetite formed authigenically as a result of alteration of olivine. The apparent lack of higher-grade phyllosilicates (e.g., illite and chlorite) and the presence of anhydrite indicate diagenesis at ~50- 80 ºC. The mineralogy of the Windjana sandstone is different than the Sheepbed mudstone. Windjana contains significant abundances of K-feldspar, low- and high-Ca pyroxenes, magnetite, phyllosilicates, and amorphous material. At least two distinct phyllosilicate phases exist: a 10 Å phase and a component that is expanded with a peak at ~11.8 Å. The identity of the expanded phase is currently unknown, but could be a smectite with interlayer H2O, and the 10 Å phase could be illite or collapsed smectite. Further work is necessary to characterize the phyllosilicates, but the presence of illite could suggest that Windjana experienced burial diagenesis. Candidates for the cementing agents include fine-grained phyllosilicates, Fe-oxides, and/or amorphous material. Interpretations of CheMin data from the Windjana sandstone are ongoing at the time of writing, but we will present an estimate of the composition of the amorphous material from mass balance calculations using the APXS bulk chemistry and quantitative mineralogy from CheMin.
Introduction: The physical and chemical response of hydrated carbonaceous chondrite materials to space weathering processes is poorly understood. Improving this understanding is a key part of establishing how regoliths on primitive carbonaceous asteroids respond to space weathering processes, knowledge that supports future sample return missions (Hayabusa 2 and OSIRISREx) that are targeting objects of this type. We previously reported on He+ irradiation of Murchison matrix and showed that the irradiation resulted in amorphization of the matrix phyllosilicates, loss of OH, and surface vesiculation. Here, we report electron energy-loss spectroscopy (EELS) measurements of the irradiated material with emphasis on the Fe and O speciation. Sample and Methods: A polished thin section of the Murchison CM2 carbonaceous chondrite was irradiated with 4 kilovolts He(+) (normal incidence) to a total dose of 1 x 10(exp 18) He(+) per square centimeter. We extracted thin sections from both irradiated and unirradiated regions in matrix using focused ion beam (FIB) techniques with electron beam deposition for the protective carbon strap to minimize surface damage artifacts from the FIB milling. The FIB sections were analyzed using a JEOL 2500SE scanning and transmission electron microscope (STEM) equipped with a Gatan Tridiem imaging filter. EELS spectra were collected from 50 nanometer diameter regions with an energy resolution of 0.7 electronvolts FWHM at the zero loss. EELS spectra were collected at low electron doses to minimize possible artifacts from electron-beam irradiation damage. Results and Discussion: Fe L (sub 2,3) EELS spectra from matrix phyllosilicates in CM chondrites show mixed Fe(2+)/Fe(3+) oxidation states with Fe(3+)/Sigma Fe approximately 0.5. Fe L(sub 2,3) spectra from the irradiated/ amorphized matrix phyllosilicates show higher Fe(2+)/Fe(3+) ratios compared to spectra obtained from pristine material at depths beyond the implantation/amorphization layer. We also obtained O Ka spectra from phyllosilicates in both regions of the sample. The O Ka spectra show a pre-edge feature at approximately 530.5 electronvolts that is related to O 2p states hybridized with Fe 3d states. The intensity ratio of the O Ka pre-edge peak relative to the main part of the O Ka edge (that results from transitions of O 1s to 2p states) is lower in the irradiated layer compared to the pristine material and may reflect the loss of O (as OH) as was observed by IR spectroscopy. Conclusions: In addition to amorphization and OH loss, EELS spectra of He(+) irradiated matrix phyllosilicates in Murchison show that some of the Fe(3+) is reduced to Fe(2+). Spectral deconvolution is underway to extract quantitative ratios from the EELS spectra.
The primitive carbonaceous chondrites are of interest to cosmochemical science because they contain relatively large amounts of ‘water’ (H 2 O and/or OH – ) within phyllosilicate minerals. This water is evidence for the accretion of ices by their parent planetesimals, and thus represents an archive of the isotopic compositions of H 2 O in the protoplanetary environments. Here, in this study, we used thermogravimetry-enabled laser spectroscopy (TGA-IRIS) analyses of the Orgueil and Tagish Lake meteorites to make δ 2 H, δ 18 O, and Δ′ 17 O measurements of the H 2 O and OH – contained in the different hydrous minerals that comprise each meteorite. In Orgueil, we measured mass-weighted averages of OH – in the saponite and serpentine phyllosilicate matrix to be δ 2 H = 192 ‰, δ 18 O = 1.5 ‰, which are unquestionably of extraterrestrial origin with Δ′ 17 O = 1.0 ‰. For Tagish Lake, analogous values of OH– in the saponite and serpentine phyllosilicate matrix are δ 2 H = 704 ‰, δ 18 O = 11.3 ‰, and are similarly unambiguously extraterrestrial with Δ′ 17 O = 0.82 ‰. We estimate that the parent H 2 O involved in aqueous alteration of Orgueil had δ 18 O value ≥ +23 ‰. In Orgueil, we interpret the phyllosilicate petrographic relationships, and the δ 18 O values of OH – in saponite and serpentine to indicate that saponite formed first, at a lower temperature by 35 to 53 °C than serpentine. This suggests that the Orgueil parent body experienced increasing temperature during the phase of active aqueous alteration (prograde) which set the δ 18 O OH values of the serpentine and saponite. In the case of Tagish Lake, serpentine formed at a lower temperature by 32 to 60 °C than saponite, for the simplest case with constant δ 18 O H2O values. If serpentine formed first, followed by saponite formation at 32 to 60 °C °C higher temperature, this suggests that Tagish Lake sample TL1 underwent prograde aqueous alteration as the parent body heated up. We find evidence that the parent H 2 O for Orgueil, Tagish Lake sample TL1, and Murchison (based on data from a previous study) may have had Δ′ 17 O values of >0.64 ‰.