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Tu, V. M.

Publications and source records attributed to Tu, V. M..

An evaporite sequence from ancient brine recorded in Bennu samples

Evaporation or freezing of water-rich fluids with dilute concentrations of dissolved salts can produce brines, as observed in closed basins on Earth and detected by remote sensing on icy bodies in the outer Solar System. The mineralogical evolution of these brines is well understood in regard to terrestrial environments, but poorly constrained for extraterrestrial systems owing to a lack of direct sampling. Here we report the occurrence of salt minerals in samples of the asteroid (101955) Bennu returned by the OSIRIS-REx mission. These include sodium-bearing phosphates and sodium-rich carbonates, sulfates, chlorides and fluorides formed during evaporation of a late-stage brine that existed early in the history of Bennu’s parent body. Discovery of diverse salts would not be possible without mission sample return and careful curation and storage, because these decompose with prolonged exposure to Earth’s atmosphere. Similar brines probably still occur in the interior of icy bodies Ceres and Enceladus, as indicated by spectra or measurement of sodium carbonate on the surface or in plumes.

58 GEOSCIENCES

Mineralogy of Vera Rubin Ridge in Gale Crater from the Mars Science Laboratory CheMin instrument

Gale crater was selected as the landing site for the Mars Science Laboratory Curiosity rover because of orbital evidence for a variety of secondary minerals in the lower slopes of Aeolis Mons (aka Mount Sharp) that indicate changes in aqueous conditions over time. Distinct units demonstrate orbital spectral signatures of hematite, phyllosilicate (smectite), and sulfate minerals, which suggest that ancient aqueous environments in Gale crater varied in oxidation potential, pH, and water activity. Vera Rubin ridge (VRR) is the first of these units identified from orbit to have been studied by Curiosity. Orbital near-infrared data from VRR show a strong band at 860 nm indicative of hematite. Before Curiosity arrived at VRR, the hypotheses to explain the formation of hematite included (1) precipitation at a redox interface where aqueous Fe2+ was oxidized to Fe3+, and (2) acidic alteration of olivine in oxic fluids. Studying the composition and sedimentology of the rocks on VRR allow us to test and refine these hypotheses and flesh out the depositional and diagenetic history of the ridge. Here, we focus on the mineralogical results of four rock powders drilled from and immediately below VRR as determined by CheMin.

Rampe, E. B.

Stability of Actinolite on Venus

Venus currently has a hostile surface environment with temperatures of ~460 ºC, pres-sures near 92 bars, and an atmosphere composed of super critical CO2 hosting a myriad of other potentially reactive gases (e.g., SO2, HCl, HF). However, it has been proposed that its surface may not have always been so harsh. Models suggest there may have been billions of years of clement conditions allowing an Earth-like environment with liquid water oceans. If such conditions existed, it is possible Venus formed a similar array of hydrous or aqueous minerals as seen on other planets with liquid surface water (e.g., Mars, Earth). Based on thermodynamic modeling, many of these phases would not be stable under the current atmospheric conditions on Venus, dehydrating due to the high temperatures and low concentration of H2O in the atmosphere. However, the rate of decomposition of these phases may allow them to remain present on the surface over geologic time. For example, experiments on the reaction rate of tremolite (Ca2Mg5Si8O22(OH)2) show a 50% decomposition time of 2.7 Gyr for micrometer sized grains in unreactive atmospheres (i.e., without SO2) at 740 K, and a 50% decomposition time of 70 Gyr for crystals several millimeters to centimeters in size. If hydrous minerals can remain on the surface of Venus over geologic time, it has implications for our detection of evidence of these past environments, and also for the overall water budget of the planet. If after surficial dehydration the planet was able to still store water in its crust, possible processes such as subduction or metamorphism could still have operated using stored water long after liquid surface water evaporated. Several previous studies have focused on experimental investigations of mineral stability on Venus. In particular, the works of studied the decomposition rate of tremolite under conditions relevant to Venus. As their focus was on decomposition of the mineral due to lack of water in the atmosphere, their experiments were undertaken using only CO2 or N2 gas at atmospheric pressure. Re-cent experiments have examined reactivity of other minerals with the Venusian atmosphere using more complex gas compositions at similar pressures to those seen on Venus. These studies show reaction of silicate minerals with atmospheric components on relatively short timescales (i.e., on the order of days). The reported reactions of silicate materials in both studies produced iron oxides, Ca sulfates, and Na sulfates. These ions are present in many amphiboles, and Ca was proposed by Johnson and Fegley to potentially have an important role in the decomposition mechanism for tremolite, with the Ca-O bond being the first to break during decomposition. The potential involvement of Ca in both processes raises the question of whether or not the reaction to form a secondary mineral phase will influence the rate of amphibole break-down (e.g., discussion in for tremolite). Additionally, reaction of Ca with atmospheric gases may result in a different secondary mineral assemblage than simple amphibole decomposition, which will need to be recognized when searching for evidence of past hydrated minerals on the Venusian surface. In order to understand the effect of this reaction on the overall preservation potential of amphibole on the surface of Venus, we are conducting experiments in both reactive and nonreactive atmospheres using the mineral actinolite (Ca2(Mg,Fe)5Si8O22(OH)2), an amphibole with similar crystal structure to tremolite that contains both Ca and Fe.

Santos, A. R.

The Mineralogical Record of Ancient Fluvio-Lacustrine Environments in Gale Crater as Measured by the MSL CheMin Instrument

The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to investigate early Hesperian-aged sedimentary rocks on the lower slopes of Aeolis Mons (i.e., Mount Sharp) that show variations in phyllosilicates, hematite, and sulfates from orbital reflectance spectroscopy, suggesting changes in ancient aqueous environments. During the Eighth International Conference on Mars in July 2014, Curiosity was still traversing the Bradbury group on the plains of Gale crater (Aeolis Palus) and had only analyzed four samples in its internal laboratories. Soon after Mars 8, Curiosity began its investigation of Mount Sharp and has since driven through ~350 m of vertical stratigraphy, the majority of which is part of the Murray formation. The Murray fm is comprised primarily of laminated mudstone with occasional sandstone and heterolithic facies and represents a long-lived fluvio-lacustrine environment. Curiosity has analyzed 13 drilled rock samples from the Murray formation and 4 from the ancient eolian Stimson fm with the Chemistry and Mineralogy (CheMin) instrument. Here, we discuss the mineralogy of all fluvio-lacustrine samples analyzed to date and what these results tell us about sources of the sediments, aqueous environments, and habitability of ancient Gale crater.

Rampe, E. B.

New Perspectives of Ancient Mars: Mineral Diversity and Crystal Chemistry at Gale Crater, Mars from the CheMin X-Ray Diffractometer

The Mars Science Laboratory Curiosity rover arrived at Mars in August 2012 with a primary goal of characterizing the habitability of ancient and modern environments. Curiosity landed in Gale crater to study a sequence of ~3.5 Ga old sedimentary rocks that, based on orbital visible/near-infrared reflectance spectra, contain secondary minerals that suggest deposition and/or alteration in liquid water. The sedimentary sequence that comprises the lower slopes of Mount Sharp within Gale crater may preserve a dramatic shift on early Mars from a relatively warm and wet climate to a cold and dry climate based on a transition from smectite-bearing strata to sulfate-bearing strata. The rover is equipped with cameras and geochemical and mineralogical instruments to examine the sedimentology and identify compositional changes within the stratigraphy. These observations provide information about variations in depositional and diagenetic environments over time. The Chemistry and Mineralogy (CheMin) instrument is one of two internal laboratories on Curiosity and includes a transmission X-ray diffractometer (XRD) and X-ray fluorescence (XRF) spectrometer with a Co-K source. CheMin measures loose sediment samples scooped from the surface and drilled rock powders. The XRD provides quantitative mineralogy of scooped and drilled samples to a detection limit of ~1 wt.%. Curiosity has traversed >20 km since landing and has primarily been exploring the site of a predominantly ancient lake environment fed by groundwater and streams emanating from the crater rim. Results from CheMin demonstrate an incredible diversity in the mineralogy of fluvio-lacustrine rocks that signify variations in source rock composition, sediment transport mechanisms, and depositional and diagenetic fluid chemistry. Abundant trioctahedral smectite and magnetite at the base of the section may have formed from low-salinity pore waters with a circumneutral pH within lake sediments. A transition to dioctahedral smectite, hematite, and Ca-sulfate going up section suggests a change to more saline and oxidative aqueous conditions within the lake waters themselves and/or within diagenetic fluids. The primary minerals detected in fluvio-lacustrine samples by CheMin also suggest diversity in the igneous source regions for the sediments, where abundant pyroxene and plagioclase in most samples suggest a basaltic protolith, but sanidine and pyroxene in one sample may have been sourced from a potassic trachyte, and tridymite and sanidine in another sample may have been transported from a rhyolitic source. Crystal chemistry of major phases in each sample have been calculated from refined unit-cell parameters, providing further constraints on aqueous alteration processes and igneous protoliths for the sediments. Perhaps one of the biggest mysteries revealed by the CheMin instrument is the high abundance of X-ray amorphous materials (15 to 73 wt.%) in all samples measured to date. X-ray amorphous materials were detected by CheMin based on the observation of broad humps in XRD patterns. How these materials formed, their composition, and why they persist near the martian surface remain a topic of debate. The sedimentology and composition of the rocks analyzed by Curiosity demonstrate that habitable environments persisted intermittently on the surface or in the subsurface of Gale crater for perhaps more than a billion years.

Rampe, E. B.

Partially Chloritized Smectites: Analogues of Smectites at Gale Crater, Mars

Characterizing the structure and composition of phyllosilicates is important for interpreting the aqueous history of Mars and identifying potential habitable environments. Smectites and chlorites are the most dominant clay types on Mars, and there is evidence of the presence of smectite/chlorite intergrades. Smectite has been detected at Gale Crater, Mars, via orbital observations and in-situ measurements, in abundances up to approximately 25 weight percentage of bulk rock. John Klein (JK) and Cumberland (CB) were analyzed by the Chemistry and Mineralogy (CheMin) and Samples Analysis at Mars (SAM) evolved gas analysis experiment (EGA) instruments, onboard Mars Science Laboratory (MSL), Curiosity, to distinguish clay mineralogy. John Klein has a collapsed 2:1 smectite with a d-spacing of 10 Angstroms, whereas Cumberland smectite did not fully collapse and has a d-spacing of approximately 13.2 Angstroms. It has been suggested that partial chloritization or ‘pillaring’ could be responsible for the expanded Cumberland smectite because pillaring inhibits the collapse of smectites down to 10 Angstrom, even under the desiccating conditions on the martian surface. Clay minerals have been detected in ancient fluvio-lacustrine rocks throughout Curiosity’s traverse and catalog the changes of the lake water chemistry and diagenetic conditions at Gale Crater, Mars. Investigating clay minerals is important for identifying them on the Martian surface, in particular as Curiosity proceeds into the upcoming Clay-bearing Unit.

Tu, V. M.

Amorphous Phase Characterization Through X-Ray Diffraction Profile Modeling: Implications for Amorphous Phases in Gale Crater Rocks and Soils

The CheMin X-ray diffraction instrument on the Mars Science Laboratory rover has analyzed 18 rock and soil samples in Gale crater. Diffraction data allow for the identification of major crystalline phases based on the positions and intensities of well-defined peaks and also provides information regarding amorphous and poorly-ordered materials based on the shape and positions of broad scattering humps. The combination of diffraction data, elemental chemistry from APXS (Alpha Particle X-ray Spectrometer) and evolved gas analyses (EGA) from SAM (Sample Analysis at Mars) help constrain possible amorphous materials present in each sample (e.g., glass, opal, iron oxides, sulfates) but are model dependent. We present a novel method to characterize amorphous material in diffraction data and, through this approach, aim to characterize the phases collectively producing the amorphous profiles in CheMin diffraction data. This method may be applied to any diffraction data from samples containing X-ray amorphous materials, not just CheMin datasets, but we re-strict our discussion to Martian-relevant amorphous phases and diffraction data measured by CheMin or CheMin-like instruments.

Achilles, C. N.