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151 records · Page 9

Oxygen Production from Lunar Regolith using Ionic Liquids

The objective of this work and future follow-on work is to develop a safe, efficient, and recyclable method for oxygen and/or metals extraction from lunar regolith, in support of establishing a manned lunar outpost. The approach is to solubilize the oxides that comprise lunar regolith in media consisting of ionic liquids (ILs) and/or their mixtures at temperatures at or below 300 C. Once in solution, electrolysis can either be performed in-situ to generate oxygen at the anode and hydrogen and/or metals (silicon, iron, aluminum, titanium, etc.) at the cathode. Alternatively, the water that is generated during the solubilization process can be distilled out and condensed into a separate IL and then electrolysized to produce hydrogen and oxygen. In the case of lunar regolith, this method could theoretically produce 44g oxygen per 100g of regolith. The oxygen can be used for human life support and/or as an oxidizer for rocket fuels, and the metals can be used as raw materials for construction and/or device fabrication. Moreover, the hydrogen produced can be used to re-generate the acidic medium, which can then be used to process additional regolith, thereby making the materials recyclable and limiting upmass requirements. An important advantage of IL acid systems is that they are much "greener" and safer than conventional materials used for regolith processing such as sulfuric or hydrochloric acids. They have very low vapor pressures, which means that they contain virtually no toxic and/or flammable volatile content, they are relatively non-corrosive, and they can exhibit good stability in harsh environments (extreme temperatures, hard vacuum, etc.). Furthermore, regolith processing can be achieved at lower temperatures than other processes such as molten oxide electrolysis or hydrogen reduction, thereby reducing initial power requirements. Six ILs have been synthesized and tested for their capability to dissolve lunar simulant, and for electrochemical and thermal stability. The results showed that ILs can be very efficient electrolytes; in particular IL/phosphoric-acid mixtures appear extremely promising for solubilizing lunar simulant. Results from preliminary experiments for distillation of water produced from the oxygen within the metal oxides of the simulant and the hydrogen from the acid indicates that over 75% of the oxygen from the simulant can be harvested as water at a temperature of 150 C. A method for collection of oxygen from electrolysis of the water derived from solubilizing simulant was developed by using a liquid nitrogen trap to liquefy and collect the oxygen. Although precise quantification of the liquid oxygen trapped is difficult to obtain, the amount of hydrogen and oxygen collected from electrolysis of water in this system was greater than 98%. This set-up also included a portable mass spectrometer for the identification of gases released from electrolysis cells. Regeneration of ILs through re-protonation was also demonstrated. Four sequential re-generations of an IL following solubilization of simulant showed no significant differences in amounts of simulant dissolved. Follow-on work for this project should include more studies of IL/phosphoric acid systems. Also, much more work is necessary for defining methods for electrolysis and purification of metals from regolith solubilized in ILs, and for developing a system to use the produced hydrogen to regenerate the spent IL. Finally, design and development of flight breadboard and prototype hardware is required.

Paley, Mark Steven↗

Autogenous acid production using a regulated bio-oxidation method for economical recovery of REEs and critical metals from coal-based resources

Acid is a necessary component for the successful leaching of minerals containing REEs (rare earth elements) and other sources. Pyrite (FeS2), which is present in REE containing minerals, can be used to produce acid. Pyrite is utilized as a source to create ferric sulfate and sulfuric acid in the presence of A. Ferroxidans. Such microorganism-based bio-oxidation necessitates the establishment of optimal conditions for continual acid production. For efficient acid generation, additional optimization was done by varying residence time, solid percentage, and airflow rate. A step-by-step analysis and associated details are offered in this work, which used pyrite to create acid for leaching. For the bio-oxidation of pyrite with varying purity, an automated bioreactor was used. Scanning electron microscopy with energy-dispersive X-ray spectroscopy was used to examine the morphology and elemental content of bioleaching sediments. Eh and pH measurements were continuously done to ensure healthy operation of the bioreactors. The analysis suggested that, the Eh value in the range of ∼ 640–680 mV, pH range of ∼ 1.3–1.5 and residence time of 4–6 days with 6% solid feed are favorable conditions of operation.

99 GENERAL AND MISCELLANEOUS↗

Are Marine Low Cloud Droplet Concentrations Buffered by Entrained Aitken‐Mode Aerosol (Final Technical Report)

During the summertime, the high-latitude oceans come to life with green phytoplankton, which gain their energy from sunlight and are food for sea creatures small and large. When the phytoplankton are eaten or die, sulfur-rich gases are released under the ocean surface and mix into the air. Observations suggest that, over the Southern Ocean, frequent storms lift this air high into the atmosphere while raining out particulates like salt. As a result, the sulfur-rich air then spawns high concentrations of small ‘Aitken-mode’ aerosol particles. We hypothesize that these particles work their way down into the marine boundary layer, where they can replenish the supply of cloud-condensation nuclei scavenged by frequent precipitation. Further, this process maintains high concentrations of liquid cloud droplets in austral summer, promoting more sunlight to be reflected to space. We call this ‘Aitken buffering’. The primary objective of this project has been to document and test what role Aitken-mode aerosols play in clouds over the Southern Ocean and elsewhere. This effort has included three main components: 1) developing a computer model that realistically simulates the aerosol processes and the small-scale turbulent air motions that move aerosols around and create the clouds, 2) using that model to interpret and extend these observations for process understanding, by allowing different factors that contribute to the aerosol budget, such as surface wind speed, precipitation, surface gas exchange, etc. to be separated, and 3) studying Aitken-mode aerosol and its variability with a focus over the Southern Ocean and Antarctica, using data from Atmospheric Radiation Measurement (ARM) sites and other available observations. Initial computer studies in more idealized conditions found that elevated concentrations of Aitken-mode aerosols above the clouds could help prevent the breakup of those clouds by acting as cloud-condensation nuclei after they were entrained into the cloudy boundary layer. Simulations of a day during the ACE-ENA field campaign showed that Aitken-mode aerosols could also prevent cloud breakup under more realistic conditions. A new method that extracts information about Aitken-mode aerosols from measurements of aerosols onto which cloud droplets can form finds that Aitken-mode aerosols do vary seasonally over the Southern Ocean, with a peak in summertime, as described above. Other work during this project has focused on understanding how patterns of water vapor, clouds and precipitation are coupled within low-lying clouds over the oceans, and also on how cloud droplets cluster within clouds and how the distribution of cloud droplet sizes change as dry air is mixed into clouds, with the latter studies also using observations from ACE-ENA.

54 ENVIRONMENTAL SCIENCES↗

Terminal Proterozoic reorganization of biogeochemical cycles

The Proterozoic aeon (2,500-540 million years ago) saw episodic increases in atmospheric oxygen content, the evolution of multicellular life and, at its close, an enormous radiation of animal diversity. These profound biological and environmental changes must have been linked, but the underlying mechanisms have been obscure. Here we show that hydrocarbons extracted from Proterozoic sediments in several locations worldwide are derived mainly from bacteria or other heterotrophs rather than from photosynthetic organisms. Biodegradation of algal products in sedimenting matter was therefore unusually complete, indicating that organic material was extensively reworked as it sank slowly through the water column. We propose that a significant proportion of this reworking will have been mediated by sulphate-reducing bacteria, forming sulphide. The production of sulphide and consumption of oxygen near the ocean surface will have inhibited transport of O2 to the deep ocean. We find that preservation of algal-lipid skeletons improves at the beginning of the Cambrian, reflecting the increase in transport by rapidly sinking faecal pellets. We suggest that this rapid removal of organic matter will have increased oxygenation of surface waters, leading to a descent of the O2-sulphide interface to the sea floor and to marked changes in the marine environment, ultimately contributing to the Cambrian radiation.

Non-NASA Center↗

Total metals & anion concentration data; Slate River floodplain, Crested Butte, CO; May 2020-September 2020

This data package includes processed and undiluted measurements for metal and anion concentrations from pore water (groundwater) samples from the Slate River floodplain of Crested Butte, CO, a focus field site for the SLAC Floodplain Hydro-Biogeochemistry SFA. The data was generated as part of the work targeting the overarching research question for the SLAC SFA: How do ubiquitous subsurface interfaces mediate molecular-scale biogeochemical processes and groundwater quality in floodplains and watersheds? Samples were collected between May and September of 2020. These measurements were all recorded at the Arizona Laboratory for Emerging Contaminants (ALEC) at the University of Arizona located in Tucson, AZ. Groundwater samples were extracted from a network of installed rhizon (Rhizosphere Research Products, part no. 19.60.21F, 0.6 micrometer mesh size) and piezometer wells within the river floodplain. All water samples were shaded from sun exposure during extraction from the subsurface and preserved at 4C until measured at ALEC.Analysis by ICP-MS:Measurements for total metals were made on the Agilent 7700x ICP-MS (for total metals) – Agilent Technologies, Santa Clara, CA.The analytical QA/QC protocol was adapted from US EPA Method 200.8 for analysis by ICP-MS. Calibration standards were prepared from multi-element stock solution (Sigma-Aldrich Multielement standard solution for ICP, St. Louis, MO) using matrix matched to sample solutions (either 2% HCl or HNO3 from AriStar Plus,grade acids from VWR Scientific). Calibration curves include at least 7 points with correlation coefficients > 0.995. The QC protocol includes a continuing calibration blank (CCB), a continuing calibration verification (CCV) solution and at least one quality control sample (QCS) to be analyzed just after calibration and again after every 12 samples and at the completion of the run. The QCS solutions are from an independent source, such as NIST SRM 1643e - Trace Elements in Water, or QCS solutions from High Purity Standards (Charleston, SC). Acceptable QC responses must be between 90 and 110% of the certified value. An internal standard (Rh) is added via on-line addition into the sample line using a mixing tee.Analysis by Ion Chromatography (Anions):The protocol follows Method 4110 in Standard Methods for Examination of Water and Wastewater.The instrument used is the Thermo Scientific Dionex ICS-6000 using AS+AG22 column set for anion analysis with isocratic method using sodium carbonate eluent. Detection is by chemical suppression of eluent conductivity. Quality control solutions and mixed analyte standards purchased from Inorganic Ventures, Christiansburg, VA.All files are in csv format.

54 ENVIRONMENTAL SCIENCES↗

Laboratory Investigation of the Effect of Venusian Weathering on Mineral Spectra

Introduction: The recent selection of two missions to Venus has renewed the importance of deter-mining weathering reactions between minerals and the Venusian atmosphere, and the spectral signatures of minerals before, during, and after these reactions. The rate at which weathering reactions progress also constrain show long unstable minerals will be present on the surface (e.g., [1]), and enables the use of mineralogy as a constraint on surface age(e.g., [2-3]).In order to gain an understanding of how mineral compositions and spectra change with weathering, we have begun conducting experiments in a 1 atm experimental setup at Wesleyan University. This setup exposes minerals to the temperature and most abundant gases of the Venus atmosphere (CO2, SO2, N2).We conducted initial experiments using biotite, calcite, and montmorillonite in order to test our methodology with minerals that may be relevant to recording the history of water on Venus. Methods: Experiments were conducted in Thermo Fisher Scientific Lindberg/Blue M Mini-Mite horizontal tube furnaces at Wesleyan University. Experiments used natural mineral chips and powders, and were conducted at 1 atmosphere and 460 °C under pre-mixed gases provided by Air Gas(Table 1). The furnaces are set up in a flow through configuration so that solid samples are exposed to a fixed gas composition, and quartz glass process tubes were used in all experiments (1/4” diameter for experiment V4, ½” diameter for all others). These conditions were maintained for the du-rations listed in Table 1, at which point the furnace was turned off with gas flowing until the sample was cool enough to extract under N2and be placed in a desiccator for storage. Run products were carbon coated and examined using a Hitachi SU5000 Field Emission Gun Scanning Electron Microscope (SEM) equipped with an EDAX Octane Pro EDS detector located at Wesley-an University. Visible-Near Infrared Spectroscopy (VNIR) analysis was performed on powdered samples under a nitrogen atmosphere using an ASD Fieldspec Proover the 350-2500 nm range. Powdered mineral samples were milled to a particle size of < 45μm and were spiked with an internal standard (Al2O3, corundum) to obtain quantitative mineralogy. Samples were analyzed using a Panalytical X’Pert pro X-ray Diffractometer (XRD), with an X’Celerator high speed detector and Co Kα radiation, with data collected at a step size of 0.02 ̊/minute step counting rate from 2 to 80 degrees 2θ at 45 mA/40kV in the X-ray Diffraction Laboratory located at NASA Johnson Space Center. Materials Data Inc (MDI) software suite, JadeTMv9 was used for Rietveld refinement to determine phase abundances and mineral identification by comparing XRD patterns to International Center for Diffraction Data (ICDD) database patterns. Table 1: Experimental matrix. Experiment Name Duration (Days)Gas Com-position (trace gas)MineralsV487SO2/N2(1.4%)Montmorillonite, biotiteV519SO2/N2(1.4%)CalciteV619CO2/SO2/N2(1.4% SO2, 2.1% N2)Montmorillonite, biotiteV828SO2/N2(1.4%)Biotite, calcite Results: Calcite. In both experiments, calcite was exposed to the SO2/N2gas mixture, and in both experimental run products, XRD analysis detected anhydrite, which is consistent with EDS measurements conducted in the SEM. The XRD analyses show greater amounts of anhydrite present after 28 days than 19, suggesting the calcite reaction progressed further given longer duration. Grain surface morphology as seen in the SEM also shows secondary mineral growth (Fig. 1). VNIR spectra show no change, as expected since anhydrite lacks spectral features in this wavelength range. Montmorillonite. Montmorillonite was exposed to two different gas mixtures, the SO2/N2mix and CO2/SO2/N2mix over different durations (87 and 19 days, respectively). VNIR analyses of both run products show a reduction in the 1441and1910 nm water features as well as a shift of the 1411 and 2011 nm features to shorter wavelengths that may indicate re-structuring in the crystal lattice and the production of amorphous phases [4]. XRD results are consistent with this, showing a shift of the 001 peak from 15Åto 10Åin both run products. The amount of X-ray amorphous material in the montmorillonite run products was greater than that present in the unreacted clay, being the greatest in the 87 day V4 experiment. No other secondary phases were detected in the run products, however sulfur was present in EDS analyses of powder samples.

A R Santos↗

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.

Non-NASA Center↗