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At least 91 records · Page 5

Microbially mediated iron redox cycling of subsurface sediments from Hanford Site, Washington State, USA

Iron-bearing clay minerals are predominant in soils and sediments, and they undergo oxidation-reduction cycles as a result of natural processes such as wetting/drying cycles and plant root respiration. However, the kinetics and mechanisms of multiple redox cycles of iron in clay-rich sediments and consequences of such cycling on sediment properties are poorly understood. The objective of this study was to understand how multiple redox cycles of Fe in clay-rich sediment affect the rate and extent of Fe bioreduction and the physicochemical properties of the sediment. A natural sediment sample containing Fe-bearing montmorillonite from Hanford, Washington, USA was size-fractionated [2.0 to 0.5 μm (Hanford-C) and 0.5 to 0.02 μm (Hanford-F)] and redox-cycled for four times. Bioreduction was achieved utilizing Geobacter sulfurreducens and re-oxidization was performed with sparged air. Time-course change of total Fe (II) was monitored to measure the rate and extent of Fe (III) bioreduction. Redox-cycled sediments were characterized to determine the physicochemical changes. Both the initial rate and extent of bioreduction fluctuated across the four redox cycles, but they ultimately decreased from 5.3 μmol g -1 h -1 and 22.9% to nearly zero by the fourth cycle. These fluctuation patterns were likely due to a combined effect of reductive dissolution of small/poorly crystalline clay particles (by 3–5%) and clay mineral structural changes, as evidenced by redox induced changes of aqueous chemistry, surface area, cation exchange capacity, mineralogy, and Mössbauer parameters. Once these small/poorly crystalline clay particles were dissolved, structural Fe in residual larger and more crystalline clay particles was largely reversible across additional redox cycles, as revealed by Mössbauer spectroscopy through the first three cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of Coupled Processes in Fractures and the Bordering Matrix via a Micro‐Continuum Reactive Transport Model

Abstract In multi‐mineral fractured rocks, the altered porous layer on the fracture surface resulting from preferential dissolution of the fast‐reacting minerals can have profound impacts on subsequent chemical‐physical alteration of the fractures. This study adopts the micro‐continuum approach to provide further understanding of reactive transport processes in the altered layer (AL), and mass exchanges with the bordering matrix and fracture. The modeling framework couples the Darcy‐Brinkman‐Stokes (DBS) solver in COMSOL Multiphysics and the geochemical modeling capability of CrunchFlow. Three‐dimensional steady state simulations with systematically varied chemical‐physical parameters of the AL were performed to examine the impacts of individual factors and processes. Our simulation results confirm previous observations that dissolution of the fast‐reacting mineral (i.e., calcite) is largely controlled by diffusion across the AL. We also show that dissolution of the slow‐reacting mineral (i.e., dolomite), which controls AL development and fracture enlargement, increases with surface area and has a complex dependence on different local rate‐limiting processes. In particular, advection can result in evident spatial variations in the local dissolution rates of dolomite, although it does not affect the bulk chemistry significantly. The difference in the spatial patterns between simulations with and without advection in the AL is more noticeable in the locations with smaller apertures, with up to 20% difference in local reaction rates. Therefore, it is important to include a full depiction of advection, diffusion, and reactions for accurately capturing local dynamics that control long‐term fracture evolution.

58 GEOSCIENCES↗

Argon adsorption and the lunar atmosphere

The results of Ar adsorption experiments on a terrestrial labradorite and lunar rock 15415 crushed in vacuo are reported. The experiments were designed to test lunar atmosphere simulation models for the behavior of Ar on the lunar surface, as determined from the Apollo 17 mass spectrometer results. These models (Hodges, 1980, 1982) used a single adsorption potential to characterize the surfaces of lunar soil grains, with the result that high (6-7 kcal/mol) heats of adsorption were inferred. The present experimental results show that very high adsorption potentials are indeed associated with fresh mineral surfaces, but that these energetic surfaces occupy only small fractions of the total surface area. Nonetheless, these small fractions of surface, if they can be maintained in the lunar regolith in steady-state condition, could be sufficient to account for the Apollo 17 mass spectrometer observations.

Bernatowicz, T. J.↗

Mineral Mapping Using AVIRIS Data at Ray Mine, AZ

Imaging Spectroscopy enables the identification and mapping of surface mineralogy over large areas. This study focused on assessing the utility of Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data for environmental impact analysis over the Environmental Protection Agency's (EPA) high priority Superfund site Ray Mine, AZ. Using the Spectral Angle Mapper (SAM) algorithm to analyze AVIRIS data makes it possible to map surface materials that are indicative of acid generating minerals. The improved performance of the AVIRIS sensor since 1996 provides data with sufficient signal to noise ratio to characterize up to 8 image endmembers. Specifically we employed SAM to map minerals associated with mine generated acid waste, namely jarositc, goethite, and hematite, in the presence of a complex mineralogical background.

McCubbin, Ian↗

Aperture and roughness govern iron oxide passivation in olivine fractures during carbon mineralization

Efficient carbon dioxide mineralization in silicate-rich formations depends on reaction rates within fracture networks, yet the role of fracture microstructure remains poorly constrained. We investigated how fracture aperture and surface roughness influence mineralization by reacting synthetic forsteritic olivine fractures with controlled apertures (0.5–1.6 millimeters) and roughness (6–16 micrometers) with supercritical carbon dioxide at 13.7 megapascals and 185 degrees Celsius. Optical microscopy and Raman spectroscopy showed that rougher fracture surfaces promoted iron oxide precipitation, which passivated olivine surfaces, limiting magnesium availability for carbonate formation while removing iron as a reactant. These effects were more pronounced in smaller-aperture fractures. A geochemical model incorporating surface topography and passivation reproduced the observed trends, confirming that increased roughness can reduce reactivity despite greater surface area. Our results demonstrate that fracture microstructure strongly influences iron oxide passivation and carbon dioxide mineralization, with important implications for predicting long-term performance of engineered carbon dioxide storage systems.

54 ENVIRONMENTAL SCIENCES↗

The Mineralogy of Martian Dust: Design and Analysis Considerations for an X-Ray Diffraction/X-Ray Fluorescence (XRD/XRF) Instrument for Exobiological Studies

A principal objective of Mars exploration is the search for evidence of past life which may have existed during an earlier clement period of Mars history. We would like to investigate the history of surface water activity (which is a requirement for all known forms of life) by identifying and documenting the distribution of minerals which require water for their formation or distribution. A knowledge of the mineralogy of the present Martian surface would help to identify areas which, due to the early activity of water, might have harbored ancient life. It would be desirable to establish the presence and characterize the distribution of hydrated minerals such as clays, and of minerals which are primarily of sedimentary origin such as carbonates, silica and evaporites. Mineralogy, which is more critical to exobiological exploration than is simple chemical analysis (absent the detection of organics), will remain unknown or will at best be imprecisely constrained unless a technique sensitive to mineral structure such as powder X-ray diffraction (XRD) is employed. Additional information is contained in the original extended abstract.

Blake, David↗

The nanophase iron mineral(s) in Mars soil

A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.

NASA Program Exobiology↗

Osteoporosis Treatments Affect Bone Matrix Maturation in a Rat Model of Induced Cortical Remodeling

ABSTRACT To test how osteoporosis drugs affect bone matrix maturation during cortical bone remodeling, 72 pregnant rats were switched from a 0.4% to a 0.01% calcium diet at parturition for a 23‐day lactation period. At weaning, eight dams were sacrificed to establish baseline values, while the remaining dams were returned to 0.4% calcium and treated with vehicle (saline), sodium fluoride (NaF), zoledronic acid (ZA), or sclerostin antibody (Scl‐Ab) for either 7 or 28 days (eight animals per group per time point). Femora were examined by μCT, dynamic histomorphometry, Fourier transform infrared imaging, and three‐point bending of notched specimens. Cortical porosity decreased in all groups from baseline to day 28. Intracortical mineralizing surface (MS/BS) and mineral apposition rate (MAR), as well as the mineral‐to‐matrix ratio were unaffected by treatment, but intracortical crystallinity was increased in the ZA group at day 10 compared with vehicle. Cortical area increased in all groups over 28 days mainly because of an addition of bone at the endocortical surface. Endocortical MS/BS did not vary among the groups, but endocortical MAR was suppressed in the NaF group at day 2 and elevated in the Scl‐Ab group at day 4 compared with vehicle. Endocortical mineral‐to‐matrix ratio was increased at days 5 and 10 following NaF treatment and endocortical crystallinity was increased at day 5 following ZA treatment compared with vehicle. Fracture toughness did not differ among the groups. Thus, the treatments affected matrix maturation more strongly at the endocortical then intracortical envelope. In this model of induced remodeling, the bone formation phase is synchronized at multiple sites, facilitating study of the effects of drugs or other bone‐targeting agents on matrix maturation independent of their effects on the initiation of remodeling. © 2020 The Authors. JBMR Plus published by Wiley Periodicals, Inc. on behalf of American Society for Bone and Mineral Research.

59 BASIC BIOLOGICAL SCIENCES↗

Surface compositional mapping by spectral ratioing of ERTS-1 MSS data in the Wind River Basin and Range, Wyoming

The author has identified the following significant results. ERTS data collected in August and October 1972 were processed on digital and special purpose analog recognition computers using ratio enhancement and pattern recognition. Ratios of band-averaged laboratory reflectances of some minerals and rock types known to be in the scene compared favorably with ratios derived from the data by ratio normalization procedures. A single ratio display and density slice of the visible channels of ERTS MSS data, Channel 5/Channel 4 (R5,4), separated the Triassic Chugwater formation (redbeds) from other formations present and may have enhanced iron oxide minerals present at the surface in abundance. Comparison of data sets collected over the same area at two different times of the year by digital processing indicated that spectral variation due to environmental factors was reduced by ratio processing.

Vincent, R. K.↗

Martian volatiles - Their degassing history and geochemical fate

Implications of the Ar-40 content of the Martian atmosphere for Martian volatile history are considered. It is assumed that the potassium content of both Mars and earth is similar to that of normal chondrites, that Mars possesses a water content similar to that of normal chondrites, and that earth's water content is equal to or somewhat less than Mars'. A simple earth-analogous Mars degassing model is outlined in which the Martian surface volatile inventory is presumed to be identical to earth's, but scaled to the smaller mass and surface area of Mars. Physical storage of volatiles in the Martian regolith is examined along with the occurrence of volatile-containing mineral phases in the regolith, exospheric escape as a massive volatile sink, and the effect of the time history of degassing on the surface volatile inventory. Implications of earth's degassing history for Mars are assessed, and models describing the overall intensity of Mars degassing are presented. It is concluded that the maximum amounts of water and other volatiles that could be stored in the Martian regolith are marginally compatible with those required by the earth-analogous model, although a lower atmospheric Ar-40 concentration and regolith volatile inventory would be easier to reconcile with observational constraints.

Fanale, F. P.↗

Extending Grid Computing to Remote Locations

NASA Glenn Research Center, in cooperation with NASA Ames and geologists from the University of Cincinnati and Bowling Green State University has extended the computational capabilities of the information Power Grid to remote research sites. The combination of satellite (EOS) data acquisition and the IPG processing provides geologists with the ability to identify the key mineralogical features at the research site. The underlying connectivity for this research environment is provided by the Numerical Research and Education Network (NREN) using a combination of terrestrial and mobile satellite-based networking solutions. Our approach not only speeds the process of scientific discovery, but also serves as a simple demonstration of NASA's capacity for geological classification and exploration of remote sites such as the Martian surface. The NASA Glenn Demonstrations combines satellite (EOS) data acquisition and the computational capabilities or the Information Power Grid (IPG) to provide geologists with the ability to identify key mineralogical features in near real-time of an area in study. This capability could someday allow geological classification of rocks and minerals of remote sites such as the Martian surface.

Griffin, Robert↗

Decoupling of redox processes from soil saturation in Arctic tundra

Permafrost thaw in warming Arctic landscapes alters hydrology and saturation-driven biogeochemical processes. Models assume that aerobic respiration occurs in drained soils while saturated soils support methanogenesis; however, saturated soils maintain redox gradients that host a range of anaerobic metabolisms. We evaluated how redox potential and redox-active solutes vary with soil moisture in the active layer of permafrost-affected acidic and non-acidic tundra hillslopes. Oxidizing conditions persisted in highly permeable organic horizons of both unsaturated tussock tundra and saturated wet sedge meadows. Redox potential decreased with depth in all soils as increasing soil bulk density restricted groundwater flow and oxygen diffusion. High concentrations of dissolved iron, phosphate, and organic carbon coincided with redox boundaries below the soil surface in acidic tundra, indicating active iron redox cycling and potential release of adsorbed phosphate during iron (oxyhydr)oxide dissolution. In non-acidic tundra, weatherable minerals affected nutrient dynamics more than redox-driven iron cycling, especially in low-lying, saturated areas where thaw reached mineral soils. The role of thaw depth and the ability of saturated soils to maintain oxidizing conditions in organic surface layers highlight the importance of soil physical properties and hydrology in predicting biogeochemical processes and greenhouse gas emissions.

54 ENVIRONMENTAL SCIENCES↗

Probing Carbon Mineralization Mechanisms in Pore and Bulk Fluids by Harnessing Architected Calcium Silicates

The ability to synthesize materials with well-controlled pore structures gives us unprecedented control over probing fluid interactions with reactive interfaces and advancing calibrated insights into coupled chemo-morphological interactions. One of the primary challenges in developing crystalline silicate materials lies in achieving ordered pore structures. Existing approaches of producing amorphous mesoporous metal silicates via sol–gel methods and heat-treatment of these materials to produce crystalline phases cause the pore structures in the amorphous phases to collapse. To overcome this challenge, carbon coating of amorphous mesoporous calcium silicate particles is carried out to retain the pore structure, while the material is heated to produce crystalline calcium silicate with calcium sulfate inclusions. The pore diameter in these materials is about 3.9 nm, with a surface area and a pore volume of 28.75 m 2 /g and 0.092 cm 2 /g, respectively. The mechanisms of carbon mineralization are investigated by reacting architected calcium silicate with 1 M Na 2 CO 3 and monitoring the evolution in the structural phases using operando wide-angle X-ray scattering (WAXS) measurements. Formation of stable calcium carbonate polymorph or calcite and metastable calcium carbonate polymorph or vaterite in pore and bulk fluids, respectively, resulting from the reaction between Na 2 CO 3 and CaSiO 3 , are noted. The mechanisms associated with carbon mineralization are delineated using ReaxFF molecular dynamics (MD) simulations. The surface dissolution reaction is initiated by 2H + ions that replace a Ca 2+ ion in the Ca–silicate matrix. Ca 2+ ions in the solution initially react with water to form calcium hydroxide and eventually form calcium (bi)carbonate. A slow and gradual increase in the formation of sodium silicate in the solution resulting from the reactions of silicic acid or the silicon dioxide reaction with sodium hydroxide is noted. When carbon mineralization occurs in environments bearing interfacial fluids, calcite is the dominant calcium carbonate polymorph, as determined using experiments with pore fluids and molecular-scale simulations. In conclusion, these studies provide fundamental insights into the mechanisms underlying the carbon mineralization of calcium silicate informed by experiments and molecular-scale simulations.

Calcium↗

Integration of optical and microwave images for geologic mapping and resource explorations

Multispectral images in the visible, near-IR, short-wave IR, thermal IR, and microwave regions, obtained during the Geologic Remote Sensing Field Experiment were combined with data from Landsat TM, laboratory, and field spectral measurements, as well as traditional geologic mapping and were used to produce thematic image maps showing details of the surface geology for an area at the north end of Death Valley (California/Nevada). The integrated multispectral images provide new geologic information which can be used in mineral deposit models to provide exploration targets. The data demonstrated the relationship between the surface composition of materials and remote sensing in the visible and infrared.

Kruse, Fred A.↗

Mineral equilibria and the high radar reflectivity of Venus mountaintops

The relationship between altitude and microwave emissivity in 10 highland regions of Venus is investigated on the basis of the Magellan data set. Highlands on Venus are found to display high radar reflectivity. The required change in surface electrical properties occurs abruptly at a 'critical altitude,' whose value varies from one highland area to another. Critical altitudes range from 4.75 km to 2.49 km. Differences in reflectivity are caused by differences in the surface mineral assemblage, which determines the dielectric constant of surface material. The mineral responsible for high radar reflectivity on mountaintops is pyrite, which occurs in weathered mineral assemblages at high altitudes. Conductive pyrite occurs dispersed in insulating materials, forming a loaded dielectric material.

Klose, K. B.↗

Ab initio molecular dynamics free energy study of enhanced copper (II) dimerization on mineral surfaces

Understanding the adsorption of isolated metal cations from water on to mineral surfaces is critical for toxic waste retention and cleanup in the environment. Heterogeneous nucleation of metal oxyhydroxides and other minerals on material surfaces is key to crystal growth and dissolution. The link connecting these two areas, namely cation dimerization and polymerization, is far less understood. In this work we apply ab initio molecular dynamics calculations to examine the coordination structure of hydroxide-bridged Cu(II) dimers, and the free energy changes associated with Cu(II) dimerization on silica surfaces. The dimer dissociation pathway involves sequential breaking of two Cu 2+ -OH – bonds, yielding three local minima in the free energy profiles associated with 0-2 OH – bridges between the metal cations, and requires the design of a (to our knowledge) novel reaction coordinate for the simulations. Cu(II) adsorbed on silica surfaces are found to exhibit stronger tendency towards dimerization than when residing in water. Cluster-plus-implicit-solvent methods yield incorrect trends if OH – hydration is not correctly depicted. The predicted free energy landscapes are consistent with fast equilibrium times (seconds) among adsorbed structures, and favor Cu 2+ dimer formation on silica surfaces over monomer adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deformation at the Decaturville impact structure, Missouri

The Decaturville structure is a small area of intense disturbance marked by surface exposure of Precambrian rock and minor lead-zinc mineralization. The present paper gives a detailed analysis of the associated deformation processes on the basis of detailed mapping and study of drill core. The presence of shock-deformation features and the complex structural pattern revealed from the analysis are strong indications that the Decaturville structure was formed by impact of an extraterrestrial body.

Offield, T. W.↗

Utility of Lava Tubes on Other Worlds

On Mars, as on Earth, lava tubes are found in the extensive lava fields associated with shield volcanism. Lunar lava-tube traces are located near mare-highland boundaries, giving access to a variety of minerals and other resources, including steep slopes, prominent heights for local area communications and observation, large-surface areas in shade, and abundant basalt plains suitable for landing sites, mass-drivers, surface transportation, regolith harvesting, and other uses. Methods for detecting lava tubes include visual observations of collapse trenches and skylights, ground-penetrating radar, gravimetry, magnetometry, seismography, atmospheric effects, laser, lidar, infrared, and human or robotic exploration.

Walden, Bryce E.↗