Sulfates on Mars as Markers of Aqueous Processes: An Integrated Multidisciplinary Study of Minerals, Mars Analog sites and Recent Mission Data

Our analyses of sulfate minerals, analog sites, and Martian spectra and spectral images is focused on characterization of the Martian surface and in particular identification of aqueous processes there

Crater Morphometry and Crater Degradation on Mercury: Mercury Laser Altimeter (MLA) Measurements and Comparison to Stereo-DTM Derived Results

Two types of measurements of Mercury's surface topography were obtained by the MESSENGER (MErcury Surface Space ENvironment, GEochemisty and Ranging) spacecraft: laser ranging data from Mercury Laser Altimeter (MLA) [1], and stereo imagery from the Mercury Dual Imaging System (MDIS) camera [e.g., 2, 3]. MLA data provide precise and accurate elevation meaurements, but with sparse spatial sampling except at the highest northern latitudes. Digital terrain models (DTMs) from MDIS have superior resolution but with less vertical accuracy, limited approximately to the pixel resolution of the original images (in the case of [3], 15-75 m). Last year [4], we reported topographic measurements of craters in the D=2.5 to 5 km diameter range from stereo images and suggested that craters on Mercury degrade more quickly than on the Moon (by a factor of up to approximately 10). However, we listed several alternative explanations for this finding, including the hypothesis that the lower depth/diameter ratios we observe might be a result of the resolution and accuracy of the stereo DTMs. Thus, additional measurements were undertaken using MLA data to examine the morphometry of craters in this diameter range and assess whether the faster crater degradation rates proposed to occur on Mercury is robust

Variation in XANES in biotite as a function of orientation, crystal composition, and metamorphic history

Microscale analysis of ferrous:ferric iron ratios in silicate minerals has the potential to constrain geological processes but has proved challenging because textural information and spatial resolution are limited with bulk techniques, and in situ methods have limited spatial resolution. Synchrotron methods, such as XANES, have been hampered by the sensitivity of spectra to crystal orientation and matrix effects. In an attempt to break this nexus, biotites from Tanzania were characterized with a combination of optical microscopy, electron microprobe, Mössbauer analysis, electron backscatter diffraction (EBSD) and X-ray absorption near edge structure (XANES) spectroscopy. Pre-edge and edge characteristics of the FeKa absorption feature were compared to orientation information derived by EBSD and ferric iron content derived from Mössbauer analysis. Statistically significant correlations between measured spectral features and optic/crystallographic orientation were observed for individual samples. However, orientation corrections derived from these correlations did not reduce the uncertainty in Fe3+/Fetot. The observations are consistent with matrix- and ordering-dependency of the XANES features, and further work is necessary if a general formulation for orientation corrections is to be devised

Inclusive Chemical Characterization of Tourmaline: Mossbauer Study of Fe Valence and Site Occupancy

We report here the results of a series of inclusive chemical characterizations, including all elements except oxygen, for a suite of 54 tourmaline samples. A combination of analytical techniques was used to analyze for major and light elements (electron microprobe), Fe3+ and Fe2+ (Mossbauer spectroscopy), H (U extraction), and B, Li, and F (ion microprobe, or SIMS). The B content of the tourmalines studied ranges from 2.86 to 3.26 B per formula unit (pfu) with 31 anions; excess boron is believed to reside in the Si site. Li ranges from 0.0 to 1.44 Li pfu and F contents are 0.0-0.91 pfu. H contents range from nearly anhydrous up to 3.76 H pfu and do not correlate simply with Fe3+ content. Mossbauer results show that tourmaline exhibits the entire range of Fe3+/Sigma Fe from 0.0-1.0. Fe2+ is represented in the spectra by three doublets, with occupancy in at least three distinct types of Y sites (with different types of nearest and next nearest neighbors). Fe3+ was found in 26 of the 54 samples studied. Although Mossbauer data do not allow the distinction between Fe-[Y](3+) and Fe-[Z](3+) site occupancies to be made, XRD data on these samples suggest that the majority of Fe3+ is also in Y. Of the samples studied, Fe-[4](3+) occurs in nine; five of those were either olenite or uvite with extensive Na substitution. A mixed valence doublet corresponding to delocalized electrons shared between adjacent octahedra was observed in 14 of the samples studied. Projection pursuit regression analysis shows that distribution of Fe among doublets is a function (albeit a complex one) of bulk composition of the tourmaline and supports the interpretation of doublets representing different populations of neighbors. Variations in Fe3+/Fe2+ ratio cannot be directly related to variations in charge in any single site of the structure. Fe3+/Fe2+ ratio is probably controlled by the prevailing oxidation state in the bull; rock assemblage, rather than by any particular crystal chemical substitution

Genetic Findings as the Potential Basis of Personalized Pharmacotherapy in Phelan-McDermid Syndrome

Phelan-McDermid syndrome (PMS) is a genetic disorder often characterized by autism or autistic-like behavior. Most cases are associated with haploinsufficiency of the SHANK3 gene resulting from deletion of the gene at 22q13.3 or from a pathogenic variant in the gene. Treatment of PMS often targets SHANK3, yet deletion size varies from 9 Mb, potentially encompassing dozens of genes and disrupting regulatory elements altering gene expression, inferring the potential for multiple therapeutic targets. Repurposed drugs have been used in clinical trials investigating therapies for PMS: insulin-like growth factor 1 (IGF-1) for its effect on social and aberrant behaviors, intranasal insulin for improvements in cognitive and social ability, and lithium for reversing regression and stabilizing behavior. The pharmacogenomics of PMS is complicated by the CYP2D6 enzyme which metabolizes antidepressants and antipsychotics often used for treatment. The gene coding for CYP2D6 maps to 22q13.2 and is lost in individuals with deletions larger than 8 Mb. Because PMS has diverse neurological and medical symptoms, many concurrent medications may be prescribed, increasing the risk for adverse drug reactions. At present, there is no single best treatment for PMS. Approaches to therapy are necessarily complex and must target variable behavioral and physical symptoms of PMS.

Reduction and Morphological Transformation of Synthetic Nanophase Iron Oxide Minerals by Hyperthermophilic Archaea

Fe(III) (oxyhydr)oxides are electron acceptors for some hyperthermophilic archaea in mildly reducing geothermal environments. However, the kinds of iron oxides that can be used, growth rates, extent of iron reduction, and the morphological changes that occur to minerals are poorly understood. The hyperthermophilic iron-reducing crenarchaea Pyrodictium delaneyi and Pyrobaculum islandicum were grown separately on six different synthetic nanophase Fe(III) (oxyhydr)oxides. For both organisms, growth on ferrihydrite produced the highest growth rates and the largest amounts of Fe(II), although P. delaneyi produced four times more Fe(II) (25 mM) than P. islandicum (6 mM). Both organisms grew on lepidocrocite and akaganéite and produced 2 and 3 mM Fe(II). Modest growth occurred for both organisms on goethite, hematite, and maghemite where ≤1 mM Fe(II) was produced. The diameters of the spherical mineral end-products following P. delaneyi growth increased by 30 nm for ferrihydrite and 50–150 nm for lepidocrocite relative to heated abiotic controls. For akaganéite, spherical particle sizes were the same for P. delaneyi-reacted samples and heated abiotic controls, but the spherical particles were more numerous in the P. delaneyi samples. For P. islandicum, there was no increase in grain size for the mineral end-products following growth on ferrihydrite, lepidocrocite, or akaganéite relative to the heated abiotic controls. High-resolution transmission electron microscopy of lattice fringes and selected-area electron diffraction of the minerals produced by both organisms when grown on ferrihydrite showed that magnetite and/or possibly maghemite were the end-products while the heated abiotic controls only contained ferrihydrite. These results expand the current view of bioavailable Fe(III) (oxyhydr)oxides for reduction by hyperthermophilic archaea when presented as synthetic nanophase minerals. They show that growth and reduction rates are inversely correlated with the iron (oxyhydr)oxide crystallinity and that iron (oxyhydr)oxide mineral transformation takes different forms for these two organisms

Understanding Surface Processes on Mars Through Study of Iron Oxides/Oxyhydroxides: Clues to Surface Alteration and Aqueous Processes

We are performing oxidation and reduction reactions on hydrated ferric oxide minerals in order to investigate how these might alter under a variety of conditions on the surface of Mars. Preliminary experiments on ferrihydrite and goethite showed that heating these minerals in a dry oxidizing environment produces fine-grained hematite, while heating these minerals in a reducing environment produces fine-grained magnetite. Under Mars-like oxidation levels this magnetite then oxidizes to maghemite. These reactions are dependent on the presence of water and organic material that can act as a reductant. We are using reflectance and Mossbauer spectroscopy to characterize the reaction products and TEM to analyze the sample texture. Our preliminary results indicate that magnetite and maghemite could be formed in the soil on Mars from ferrihydrite and goethite if organics were present on early Mars

Curie: Constraining Solar System Bombardment Using In Situ Radiometric Dating

The Curie mission would constrain the existence of the putative cataclysm by determining the age of samples directly sourced from the impact melt sheet of a major pre-Imbrium lunar basin. The measurements would also enable further understanding of lunar evolution by characterizing new lunar lithologies far from the Apollo and Luna landing sites, including the very low-Ti basalts in Mare Crisium and potential olivine rich lithologies in the margins of both Mare Nectaris and Mars Crisium. Equipped with a mass spectrometer and a LIBS, Curie would also be well-placed to survey volatile components of the lunar regolith, including surface-bound hydrogen

Fe(III) (oxyhydr)oxide reduction by the thermophilic iron-reducing bacterium Desulfovulcanus ferrireducens

Some thermophilic bacteria from deep-sea hydrothermal vents grow by dissimilatory iron reduction, but our understanding of their biogenic mineral transformations is nascent. Mineral transformations catalyzed by the thermophilic iron-reducing bacterium Desulfovulcanus ferrireducens during growth at 55°C were examined using synthetic nanophase ferrihydrite, akaganeite, and lepidocrocite separately as terminal electron acceptors. Spectral analyses using visible-near infrared (VNIR), Fourier-transform infrared attenuated total reflectance (FTIR-ATR), and Mössbauer spectroscopies were complemented with x-ray diffraction (XRD) and transmission electron microscopy (TEM) using selected area electron diffraction (SAED) and energy dispersive X-ray (EDX) analyses. The most extensive biogenic mineral transformation occurred with ferrihydrite, which produced a magnetic, visibly dark mineral with spectral features matching cation-deficient magnetite. Desulfovulcanus ferrireducens also grew on akaganeite and lepidocrocite and produced non-magnetic, visibly dark minerals that were poorly soluble in the oxalate solution. Bioreduced mineral products from akaganeite and lepidocrocite reduction were almost entirely absorbed in the VNIR spectroscopy in contrast to both parent minerals and the abiotic controls. However, FTIR-ATR and Mössbauer spectra and XRD analyses of both biogenic minerals were almost identical to the parent and control minerals. The TEM of these biogenic minerals showed the presence of poorly crystalline iron nanospheres (50–200 nm in diameter) of unknown mineralogy that were likely coating the larger parent minerals and were absent from the controls. The study demonstrated that thermophilic bacteria transform different types of Fe(III) (oxyhydr)oxide minerals for growth with varying mineral products. These mineral products are likely formed through dissolution-reprecipitation reactions but are not easily predictable through chemical equilibrium reactions alone

Probing Rock Type, Fe Redox State, and Transition Metal Contents with Six-Window VNIR Spectroscopy Under Venus Conditions

VEM-window data are shown to distinguish among key rock types on Venus, and evaluate redox state and transition metal contents of Venus surface rocks