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At least 181 records · Page 10

Silicate coprecipitation reduces green rust crystal size and limits dissolution-precipitation during air oxidation

Green rusts (GR) are mixed-valence iron (Fe) hydroxides which form in reducing redox environments like riparian and wetland soils and shallow groundwater. In these environments, silicon (Si) can influence Fe oxides’ chemical and physical properties but its role in GR formation and subsequent oxidative transformation have not been studied starting at initial nucleation. Green rust sulfate [GR(SO 4 )] and green rust carbonate [GR(CO 3 )] were both coprecipitated from salts by base titration in increasing % mol Si (0, 1, 10, and 50). The minerals were characterized before and after rapid (24 h) aqueous air-oxidation by x-ray diffraction (XRD), scanning electron microscopy (SEM), Fe extended x-ray absorption fine structure spectroscopy (EXAFS), and N 2 -BET surface area. Results showed that only GR(SO4) or GR(CO3) was formed at every tested Si concentration. Increasing % mol Si caused decreased plate size and increased surface area in GR(CO3) but not GR(SO4). GR plate basal thickness was not changed at any condition indicating a lack of Si interlayering. Air oxidation of GR(SO4) at all % mol Si contents transformed by dissolution and reprecipitation into lepidocrocite and goethite, favoring ferrihydrite with higher % Si content. Air oxidation of GR(CO3) transformed into magnetite and goethite but increasing Si caused GR to oxidize while retaining its hexagonal plate structure via solid-state oxidation. Our results indicate that Si has the potential to cause GR to form in smaller particles and upon air oxidation, Si can either stabilize the plate structure or alter transformation to ferrihydrite.

36 MATERIALS SCIENCE↗

Uranium and Nickel Partitioning in a Contaminated Riparian Wetland

Uranium (U) and nickel (Ni) released 50 years ago have been immobilized in the Tims Branch wetlands located on the Savannah River Site in the United States. Sediments were collected from seven locations to identify the factors responsible for this attenuation. Ni and U contents in the solids were significantly correlated, suggesting that depositional as opposed to chemical processes contributed to their spatial distribution. Based on sequential extractions, 63 ± 16% of the U was partitioned into the organic fraction, whereas Ni was distributed between several sediment fractions. An inverse pH-organic matter (OM) correlation and positive correlations of OM with total U and organic-bound U/Ni suggest that increased OM preservation and binding to the mineral surfaces were likely responsible for Ni- and especially U-sediment retention (Tims Branch pH = 4.84 ± 0.68). EXAFS analysis indicated the predominance of U(VI) coordinated with clay minerals (~65%), together with ~35% coordinated to either OM (in areas with elevated OM levels) or iron oxides. The desorption-Kd coefficients of U (3972 ± 1370 L/kg) and Ni (30 ± 8 L/kg) indicate that dissolved Ni poses a greater long-term risk than dissolved U for migrating downstream. This study suggests that a delicate balance of geochemical properties controls whether wetlands behave as sinks or sources of contaminants.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Destruction of the recreational, asthetic, agricultural, wildlife conservation and preservation, and residential uses of the land as a result of the abuses of the manufacturing, commercial, extractive, construction, and transportation industries

Explicit concern over land use and abuse stems from the recognition of the negative impacts of unrestrained and unregulated economic, industrial, and population growth upon finite land resources. Only one quarter of the total surface area of the earth is land, and of that a large portion is uninhabitable. The present stresses upon the land include urbanization, urban sprawl and urban congestion; electrical, nuclear industrial park siting requirements; land degradation through stripping surface minerals; land degradation through disposal of radioactive wastes, sewage sludge, solid waste and other industrial wastes; rising demand for agricultural land; and the erosion and destruction of land through elimination of protective coverings such as forests, grasslands, and wetlands.

Source record↗

Near-Surface Geologic Units Exposed Along Ares Vallis and in Adjacent Areas: A Potential Source of Sediment at the Mars Pathfinder Landing Site

A sequence of layers, bright and dark, is exposed on the walls of canyons, impact craters and mesas throughout the Ares Vallis region, Chryse Planitia, and Xanthe Terra, Mars. Four layers can be seen: two pairs of alternating dark and bright albedo. The upper dark layer forms the top surface of many walls and mesas. The upper dark-bright pair was stripped as a unit from many streamlined mesas and from the walls of Ares Valles, leaving a bench at the top of the lower dark layer, approximately 250 m below the highland surface on streamlined islands and on the walls of Ares Vallis itself. Along Ares Vallis, the scarp between the highlands surface and this bench is commonly angular in plan view (not smoothly curving), suggesting that erosion of the upper dark-bright pair of layers controlled by planes of weakness, like fractures or joints. These near-surface layers in the Ares Vallis area have similar thicknesses, colors, and resistances to erosion to layers exposed near the tops of walls in Valles Marineris (Treiman et al.) and may represent the same pedogenic hardpan units. From this correlation, and from analogies with hardpans on Earth, the light-color layers may be cemented by calcite or gypsum. The dark layers are likely cemented by an iron-bearing mineral. Mars Pathfinder instruments should permit recognition and useful analyses of hardpan fragments, provided that clean uncoated surfaces are accessible. Even in hardpan-cemented materials, it should be possible to determine the broad types of lithologies in the Martian highlands. However, detailed geochemical modeling of highland rocks and soils may be compromised by the presence of hardpan cement minerals.

Treiman, Allan H.↗

Synergetic Effects of Soil Organic Matter Components During Interactions with Minerals

Mineral-associated soil organic matter (SOM) is critical for stabilizing organic carbon and mitigating climate change. However, mineral-SOM interactions at the molecular scale, particularly synergetic adsorption through organic-organic interaction on the mineral surface known as organic multilayering, remain poorly understood. This study investigates the impact of organic multilayering on mineral-SOM interactions, by integrating macroscale experiments and molecular-scale simulations that assess the individual and sequential adsorption of major SOM compounds – lauric acid (lipid), pentaglycine (amino acid), trehalose (carbohydrate), and lignin onto soil minerals. Ferrihydrite, Al-hydroxide, and calcite are exposed to SOM compounds to determine adsorption affinities and binding energies. Results show that lauric acid has 20-40 times higher K d than pentaglycine, following the order K d (ferrihydrite) > K d (Al-hydroxide) >> K d (calcite). Molecular-scale simulations confirm that lauric acid has a higher binding energy (30.8 kcal/mol) on ferrihydrite than pentaglycine (6.0 kcal/mol), attributed to lipid hydrophobicity. The lower binding energy of pentaglycine results from its hydrophilic amide groups, facilitating partitioning into water. Sequential experiments examine how the first layer of lipid or amino acid affects the adsorption of carbohydrate/lignin, which show little or no individual adsorption affinities. Macroscale results reveal that lipid and amino acid adsorption induce ferrihydrite particle repulsion increasing reactive surface area and enhancing carbohydrate/lignin adsorption independently and synergistically through organic multilayering. Molecular-scale results reveal that amino acid adsorbed on ferrihydrite interacts more readily with lignin macroaggregates (preformed in solution) than with individual lignin units, indicating organic multilayering via H-bonding. Further, these findings reveal the molecular mechanisms of SOM-mineral interactions, crucial for enhancing soil carbon stabilization.

54 ENVIRONMENTAL SCIENCES↗

SSGF Mineral Major Elements and Lithium Concentration

Presented are major element and lithium concentrations of minerals from the Salton Sea Geothermal Field (SSGF), located in the Imperial Valley, California. With a recent increase in demand for lithium, the area is now being studied as a source of geothermal brine for lithium extraction. This study was performed to help quantify lithium storage in the SSGF brine and surrounding minerals. Rocks and brines sampled in this study are from surface rhyolitic domes on the South Eastern shore of the Salton Sea, the sedimentary and evaporitic rocks in the Durmid Hills, rhyolitic drill clippings previously studied by Schmitt & Hulen, commercial drill wells, and CA State 2-14 well.

15 GEOTHERMAL ENERGY↗

A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration

Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.

NASA Discipline Exobiology↗

Wheat response to CO2 enrichment: CO2 exchanges transpiration and mineral uptakes

When simulating canopies planted in varied densities, researchers were able to demonstrate that increase of dry matter production by enhancing CO2 quickly becomes independant of increase of leaf area, especially above leaf area index of 2; dry matter gain results mainly from photosynthesis stimulation per unit of surface (primary CO2 effect). When crop density is low (the plants remaining alone a longer time), the effects of increasing leaf surface (tillering, leaf elongation here, branching for other plants etc.) was noticeable and dry matter simulation factor reached 1.65. This area effect decreased when canopy was closed in, as the effect of different surfaces no longer worked. The stimulation of photosynthesis reached to the primary CO2 effect. The accumulation in dry matter which was fast during that phase made the original weight advantage more and more neglectible. Comparison with short term measurements showed that first order long term effect of CO2 in wheat is predictible with short term experiment, from the effect of CO2 on photosynthesis measured on reference sample.

Andre, M.↗

Controls on the 36 Cl/Cl input ratio of paleo-groundwater in arid environments: New evidence from 81 Kr/Kr data

In this study, measurements of the long-lived 81 Kr and 36 Cl radioisotopes in groundwater from the Negev Desert (Israel) were used to assess the 36 Cl/Cl input ratios and Cl – contents for paleorecharge into the Nubian Sandstone Aquifer (NSA). The reconstructed Cl – content of the recharge flux was on the order of 300–400 mg/L. An initial 36 Cl/Cl ratio of 50 × 10 –15 was assessed for the groundwater replenishment in the Negev Desert since the late Pleistocene, in agreement with the 36 Cl/Cl ratios in recent local rainwater. This is despite possible changes in the climatic conditions and the 36 Cl production rates in the atmosphere over this timeframe. This similarity in values is explained by the major role played by the erosion and weathering of near-surface materials in the desert environment that dominate the hydrochemistry of rains, floods, and the consequent groundwater recharge. Spatial variation in the reconstructed initial 36 Cl/Cl ratio is accounted for by the differences in the mineral aerosol sources for specific recharge areas of the NSA. Accordingly, regional variations in the 36 Cl/Cl input in groundwater reservoirs surrounding the Mediterranean Sea indicate various processes that govern the 36 Cl/Cl system. Finally, the results of this study highlight the great advantage of integrating 81 Kr age information in evaluating the initial 36 Cl/Cl and Cl – input, which is essential for the calibration of 36 Cl radioisotope as an available long-term dating tool for a given basin.

54 ENVIRONMENTAL SCIENCES↗

The diversity of aluminum-based drinking water treatment residuals for use in environmental remediation

Drinking water treatment residuals (DWTRs) are complex mixtures of organic and inorganic phases generally disposed of as waste materials. However, their strong sorptive properties could be further exploited to immobilize contaminants. To characterize these materials, we applied a range of analytical techniques to a set of aluminum-based DWTRs. Here we determined surface areas, elemental compositions using CHNS analysis and X-ray fluorescence (XRF), performed thermogravimetric analyses paired with mass spectrometry (TGA-MS), and used synchrotron-based methods: X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Elemental analyses and specific surface area measurements – that vary between 7.23 ± 0.03 and 197.6 ± 0.9 m 2 g –1 – indicate that non-coagulant additives must play an important role in controlling sorption. High resolution powder XRD reveals the presence of only a few crystalline minerals mostly derived from source waters or additives. Fe was detected by XRF in all samples, whereas Mn was present in significant levels in samples with potassium permanganate as additive. The chemical speciation of these elements was characterized by performing spectral decompositions of XAS spectra. The spectral features of Fe are consistent with iron(III) oxides/hydroxides and structural iron in clays. On the other hand, Mn is predominantly present under its reduced form, Mn(II).

54 ENVIRONMENTAL SCIENCES↗

Near-Infrared Spectroscopy and Spectral Mapping of Jupiter and the Galilean Satellites: Results from Galileo's Initial Orbit

The Near Infrared Mapping Spectrometer performed spectral studies of Jupiter and the Galilean satellites during the June 1996 perijove pass of the Galileo spacecraft. Spectra fora5-micrometer hotspot on Jupiter are consistent with the absence of a significant watercloud above 8 bars and with a depletion of water compared to that predicted for solar composition, corroborating results from the Galileo probe. Great Red Spot (GRS) spectral images show that parts of this feature extend upward to 240 millibars, although considerable altitude-dependent structure is found within it. A ring of dense clouds surrounds the GRS and is lower than it by 3 to 7 kilometers. Spectra of Callisto and Ganymede reveal a feature at 4.25 micrometers, attributed to the presence of hydrated minerals or possibly carbon dioxide on their surfaces. Spectra of Europa's high latitudes imply that fine-grained water frost overlies larger grains. Several active volcanic regions were found on lo, with temperatures of 420 to 620 kelvin and projected areas of 5 to 70 square kilometers.

Carlson, R.↗

Use of thermal inertia determined by HCMM to predict nocturnal cold prone areas in Florida

Surface temperatures derived from HCMM data were compared with to those obtained by GOES satellite and the apparent thermal inertia (ATI) calculated. For two dates, the HCMM temperatures appear to be about 5 C lower than the GOES temperatures. The ATI for excessively-drained to well-drained mineral soils was greater than for drained organic soils possibly because of long periods of low rainfall during late 1980 and early 1981. Organic soils cropped to sugar cane showed lower ATI after a severe killing freeze. With dead leaves, there was less transpiration and more solar radiation probably reached the dark soil surface. This would explain the larger diurnal temperature amplitude observed.

Allen, L. H., Jr.↗

Effect of multiple calcination cycles on CO 2 capture efficiency during carbonation of MgO in a mineral looping process

Magnesium oxide (MgO) is considered as a potential sorbent for direct air capture of carbon dioxide in a looping process. Previous research on mineral looping for carbon capture from flue gas using MgO has shown deactivation of the sorbent with repeated cycles but repeated cycling for carbonation at ambient conditions has not been yet investigated. Here, we tested three cycles of carbonation for MgO nano-scale powders with different starting surface area. We find that carbonation efficiency is higher at higher surface area. No decrease in carbonation efficiency was observed with cycling, instead we find that carbonation efficiency and surface area are stable or even increasing with cycling. Based on our experimental data, we hypothesize that the carbonation in presence of relative humidity leads to first hydration of MgO, leading to formation of brucite (Mg(OH) 2 ). This formation of Mg(OH) 2 is a volume-increasing reaction, which leads to fracturing of MgO particles and results in an increase in surface area. We observed formation of amorphous and crystalline hydrated carbonates. The crystalline phase observed was nesquehonite (MgCO 3 ⋅ 3H 2 O). Our results show that MgO does not show any deactivation with repeated cycling for carbon capture at ambient conditions and in the presence of humidity. These findings therefore indicate that MgO is a suitable candidate as sorbent material for direct air capture of carbon dioxide.

Ambient weathering↗

Three-Dimensional Imaging and Quantification of Gas Storativity in Nanoporous Media via X-rays Computed Tomography

This study provides the engineering science underpinnings for improved characterization and quantification of the interplay of gases with kerogen and minerals in shale. Natural nanoporous media such as shale (i.e., mudstone) often present with low permeability and dual porosity, making them difficult to characterize given the complex structural and chemical features across multiple scales. These structures give nanoporous solids a large surface area for gas to sorb. In oil and gas applications, full understanding of these media and their sorption characteristics are critical for evaluating gas reserves, flow, and storage for enhanced recovery and CO 2 sequestration potential. Other applications include CO 2 capture from industrial plants, hydrogen storage on sorbent surfaces, and heterogeneous catalysis in ammonia synthesis. Therefore, high-resolution experimental procedures are demanded to better understand the gas–solid behavior. In this study, CT imaging was applied on the sub-millimeter scale to shale samples (Eagle Ford and Wolfcamp) to improve quantitative agreement between CT-derived and pulse decay (mass balance) derived results. Improved CT imaging formulations are presented that better match mass balance results, highlighting the significance of gas sorption in complex nanoporous media. The proposed CT routine implemented on the Eagle Ford sample demonstrated a 17% error reduction (22% to 5%) when compared to the conventional CT procedure. These observations are consistent in the Wolfcamp sample, emphasizing the reliability of this technique for broader implementation of digital adsorption studies in nanoporous geomaterials.

42 ENGINEERING↗

Ranger's Legacy

With its Landsat satellites, development of sensors, and advancement of processing techniques, NASA provided the initial technology base for another Earth-benefit application of image processing, Earth resources survey by means of remote sensing. Since each object has its own unique "signature," it is possible to distinguish among surface features and to generate computer-processed imagery identifying specific features of importance to resource managers. This capability, commercialized by Perceptive Scientific Instruments, Inc., offers practical application in such areas as agricultural crop forecasting, rangeland and forest management, land use planning, mineral and petroleum exploration, map making, water quality evaluation and disaster assessment. Major users of the technology have been federal, state, and local governments, but it is making its way into commercial operations, for example, resource exploration companies looking for oil, gas and mineral sources, and timber production firms seeking more efficient treeland management. Supporting both government and private users is a small industry composed of companies producing the processing hardware software. As is the case in the medical application, many of these companies are direct offspring of NASA's work.

Source record↗

The surface of Syrtis Major - Composition of the volcanic substrate and mixing with altered dust and soil

The study characterizes Syrtis Major, an old, low relief volcanic plateau near the equatorial regions of Mars, on the basis of ISM data in order to characterize the spectral properties of the surface, to identify the major mafic mineralogy of the volcanic materials, and to derive estimates of the chemistry of these minerals. The value and spatial distribution of four primary spectral variables (albedo, continuum slope, wavelength of the ferric-ferrous band minimum, and area of the ferric-ferrous absorption) are mapped and coregistered to Viking digital photomosaics. It is shown that although there is a high degree of overall spectral variability on the plateau, the key indicators of mafic mineralogy are relatively homogeneous.

Mustard, John F.↗

Hydrogen Plasma Reduction

Hydrogen plasma increases efficiency by strategically using energy to break bonds within the regolith to liberate oxygen instead of heating the entire bed of regolith. The energy used by the plasma system would be imparted into the H2 gas, forming highly energetic ions, electrons, and neutrals that would interact with the regolith surface. The energized atomic and ionic H2 provide the energy needed to make reduction of SiO2 (Silicon Dioxide) and other regolith mineral oxides favorable. What’s more, the high-energy plasma interaction occurs in a small, localized volume, and thus requires relatively little energy. The lunar regolith is well-suited for the process as the fine particles naturally available provide a high surface area for the plasma to interact with. The process would require a system to collect the regolith composed of metal oxides (MxOy) and load it into a reactor. An H2 plasma would pass over the surface (potentially at a low pressure, reducing complexity of the system as it would not require large increases in pressure from the lunar vacuum), then the gases from the plasma reaction would be collected and processed, and the spent regolith would be carried away. The gross reaction temperature would be near ambient (due to the localized nature of the plasma), eliminating the necessity of a regolith heating mechanism or handling of molten regolith. Also, the H2 used in the plasma could be subsequently recovered from the water produced by the plasma reaction. Thus, this approach would not require significant amounts of added commodities.

Elspeth Petersen↗

A Combined XRD/XRF Instrument for Lunar Resource Assessment

Robotic surface missions to the Moon should be capable of measuring mineral as well as chemical abundances in regolith samples. Although much is already known about the lunar regolith, our data are far from comprehensive. Most of the regolith samples returned to Earth for analysis had lost the upper surface, or it was intermixed with deeper regolith. This upper surface is the part of the regolith most recently exposed to the solar wind; as such it will be important to resource assessment. In addition, it may be far easier to mine and process the uppermost few centimeters of regolith over a broad area than to engage in deep excavation of a smaller area. The most direct means of analyzing the regolith surface will be by studies in situ. In addition, the analysis of the impact-origin regolith surfaces, the Fe-rich glasses of mare pyroclastic deposits, are of resource interest, but are inadequately known; none of the extensive surface-exposed pyroclastic deposits of the Moon have been systematically sampled, although we know something about such deposits from the Apollo 17 site. Because of the potential importance of pyroclastic deposits, methods to quantify glass as well as mineral abundances will be important to resource evaluation. Combined x ray diffraction (XRD) and x ray fluorescence (XRF) analysis will address many resource characterization problems on the Moon. XRF methods are valuable for obtaining full major-element abundances with high precision. Such data, collected in parallel with quantitative mineralogy, permit unambiguous determination of both mineral and chemical abundances where concentrations are high enough to be of resource grade. Collection of both XRD and XRF data from a single sample provides simultaneous chemical and mineralogic information. These data can be used to correlate quantitative chemistry and mineralogy as a set of simultaneous linear equations, the solution of which can lead to full characterization of the sample. The use of Rietveld methods for XRD data analysis can provide a powerful tool for quantitative mineralogy and for obtaining crystallographic data on complex minerals.

Vaniman, D. T.↗