Search NASA⌕ Search

SEARCH · Search NASA

Results for “Mineral dissolution”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Organo-mineral interactions in active layer and permafrost soils along aging Arctic landscapes

Rising temperatures are accelerating permafrost thaw, exposing large soil organic carbon (SOC) stocks to microbial decomposition with implications for global climate. Understanding how permafrost carbon is stored and protected through associations with minerals is critical for predicting its vulnerability to decomposition upon thaw. However, how landscape age, substrate chemistry, and soil depth influence mineral associations remain relatively unexplored. We investigated organo-mineral associations in active layer and permafrost soils across a landscape age and geochemical gradient on Alaska’s North Slope, spanning three glaciated (~11,500–125,000 years) and one unglaciated site. Using selective dissolution extractions, X-ray diffraction, and Mössbauer spectroscopy, we characterized minerals and their relationship with SOC. The three recently deglaciated sites had low soil pH that decreased with age and greater abundances of pyrophosphate- and oxalate-extractable Al and Fe, whereas the oldest unglaciated site exhibited near-neutral pH, greater pyrophosphate-extractable Ca, and distinct mineralogy. Across sites, SOC was positively associated with Al and Fe mineral phases, with stronger relationships in acidic soils. Pyrophosphate-extractable Ca also showed strong relationships with SOC at the acidic sites (up to ~10x greater), suggesting that Ca-mediated protection may operate beyond traditionally recognized high-pH soils. Permafrost soils showed depth-related changes in pH, SOC, and Fe mineralogy, suggesting chemically active, heterogeneous layers may shape mineral dynamics and associated carbon. Our results highlight how landscape age, parent material, and depth create distinct geochemical environments that govern mineral-organic associations. As thaw exposes soil to new conditions, these mineral-mediated protection mechanisms may be altered, potentially affecting the permafrost carbon-climate feedback.

Synthetic Biology↗
DOE OSTI2023

Mechanism and kinetic study of rare earth extraction from allanite by direct acid leaching

Direct acid leaching was conducted to recover rare earth elements (REEs) from an allanite ore assaying 9,861.4 ppm of REEs. The effects of operational variables such as acid type, sulfuric acid (H 2 SO 4 ) concentration, temperature, solid/liquid (S/L) ratio, and particle size on the total REE (TREE) recovery were systematically examined. The REE mineralogy and the involved leaching mechanisms were investigated by microscopic characterization and residue re-leaching tests. It was found that approximately 80% of REEs was extracted using 1 M H 2 SO 4 at 75 °C for 2 h. Increasing temperature significantly improved the REE extraction, while changing acid type, H 2 SO 4 concentration, and particle size did not. The TREE recovery also gradually decreased at higher S/L ratios. The low fraction of Si leached (<4.0%) suggested that the extraction did not significantly alter the crystal structure of the dominant mineral. The leaching kinetics of REEs were fast within the first 10 min, followed by a much slower stage (i.e., 10-120 min). The kinetic modeling results showed that each stage may be controlled by both chemical reaction and diffusion (i.e., mix control). The activation energies for REE leaching using 1 M H 2 SO 4 in the 0-10 min and 10-120 min were determined to be 20.3 and 10.8 kJ/mol, respectively. Finally, the residue re-leaching results suggested that the fast leaching kinetics at the beginning may be explained by the preferential decomposition of metamict allanite rather than the formation of silica gel, while the following slower leaching stage was due to the dissolution of difficult-to-leach REE-bearing minerals such as well-crystallized allanite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Reactive CO 2 capture and mineralization of magnesium hydroxide to produce hydromagnesite with inherent solvent regeneration

Valorization of multiple low value streams including CO 2 emissions and magnesium-hydroxide bearing mine tailings to produce magnesium carbonate through reactive CO 2 capture and mineralization provides a less explored opportunity to manage several gigatons of CO 2 emissions. To resolve the feasibility of converting magnesium hydroxide to magnesium carbonate through reactive CO 2 capture and mineralization, CO 2 capture solvents such as sodium glycinate are harnessed to capture CO 2 and react directly with Mg(OH) 2 to produce hydromagnesite (Mg 5 [(CO 3 )4(OH) 2 ]·4H 2 O). This approach eliminates the energy-intensive step of producing high purity CO 2 associated with regenerating the solvent, and redissolving CO 2 to produce magnesium carbonate. Interestingly, while temperatures below 50 °C facilitate CO 2 capture, the mineralization kinetics are slow. However, at higher temperatures, accelerated carbon mineralization is favored by the faster kinetics of Mg(OH) 2 dissolution and precipitation of magnesium carbonate. Reacting Mg(OH) 2 at 90 °C with 15 wt% solids in the presence of 2.5 M sodium glycinate after 3 hours under well-stirred conditions results in an extent of carbon mineralization of 75.5%. The theoretical maximum extent of carbon mineralization when hydromagnesite is formed is 80%. Pre-loading CO 2 on the solvent is also an effective approach to ensure that sufficient CO2 is available for reactive CO 2 capture and mineralization, particularly when dilute CO 2 and N 2 mixtures are used. Higher extents of carbon mineralization are associated with an increase in the particle size and a reduction in the cumulative pore volume. These insights unlock the feasibility of harnessing reactive CO 2 capture and mineralization as a pathway to convert magnesium-hydroxide bearing resources into industrially relevant magnesium carbonate products.

Reactive CO2↗
NASA NTRS1999

Origin and Reactivity of the Martian Soil: A 2003 Micromission

The role of water in the development of the martian surface remains a fundamental scientific question. Did Mars have one or more "warm and wet" climatic episodes where liquid water was stable at the surface? If so, the mineral phases present in the soils should be consistent with a history of aqueous weathering. More generally, the formation of hydrated mineral phases on Mars is a strong indicator of past habitable surface environments. The primary purpose of this investigation is to help resolve the question of whether such aqueous indicators are present on Mars by probing the upper meter for diagnostic mineral species. According to Burns [1993], the formation of the ferric oxides responsible for the visible color of Mars are the result of dissolution of Fe (+2) phases from basalts followed by aqueous oxidation and precipitation of Fe" mineral assemblages. These precipitates likely included iron oxyhydroxides such as goethite (a-FeOOH) and lepidocrocite (g-FeOOH), but convincing evidence for these phases at the surface is still absent. The stability of these minerals is enhanced beneath the surface, and thus we propose a subsurface search for hydroxylated iron species as a test for a large-scale chemical weathering process based on interactions with liquid water. It is also possible that the ferric minerals on Mars are not aqueous alteration products of the rocks. A chemical study of the Pathfinder landing site concluded that the soils are not directly derived from the surrounding rocks and are enhanced in Mg and Fe. The additional source of these elements might be from other regions of Mars and transported by winds, or alternatively, from exogenic sources. Gibson [1970] proposed that the spectral reflectivity of Mars is consistent with oxidized meteoritic material. Yen and Murray [1998] further extend Gibson's idea and show, in the laboratory, that metallic iron can be readily oxidized to maghemite and hematite under present-day martian surface conditions (in the absence of liquid water). A test for a meteoritic component of the soil can be conducted, as described below, by searching for the presence of Ni at the martian surface. The average abundance of nickel in an Fe-Ni meteorite is about 7% and, if present at measurable levels in the soil, would be indicative of an exogenic contribution. In addition, it may be possible to directly search for mineral phases common in meteorites. An understanding of the formation and evolution of the martian soil would not be complete without addressing the unusual reactivity discovered by the Viking Landers The presence of an inorganic oxidant, possibly one produced as a results of photochemical processes, is the most widely accepted explanation of the Viking results. Are these chemical species simply adsorbed on soil grains, or have they reacted with the metal oxide substrates and altered the mineral structures? Could a completely different (non-photochemical) process be responsible for the soil reactivity? The various ideas for the nature of this putative oxidant could be constrained by a measurement of the change in reactivity with depth. Different compositions will have different lifetimes and mobilities and thus will have different vertical profiles. Because the oxidizing compounds are believed to actively destroy organic molecules, determination of the reactivity gradient also has significant implications for the search for life on Mars. A DS2-based microprobe system can be instrumented for a 2003 micromission to investigate the origin and reactivity of the martian soil. These measurements would provide invaluable information regarding the climate history and exobiological potential of the planet. The NMR, X ray and chemiresistor measurement approach described embodies a highly synergistic and general set of soil interrogation methods for elements, compounds, and crystal structures and can also be applied to other geologic questions of interest. For example, if the capability for precise targeting of the probes is available, then in-situ investigations of suspected evaporite and hydrothermal deposits would be possible with the same set of instruments. Additional information is contained in the original.

Yen, Albert S.↗
NASA NTRS2022

Effect of Ni2+, Zn2+, and Co2+ on green rust transformation to magnetite

In this study, we investigated Ni2+, Zn2+, and Co2+ mineralogical incorporation and its effect on green rust transformation to magnetite. Mineral transformation experiments were conducted by heating green rust suspensions at 85 °C in the presence of Ni2+, Zn2+, or Co2+ under strict anoxic conditions. Transmission electron microscopy and powder X-ray diffraction showed the conversion of hexagonal green rust platelets to fine grained cubic magnetite crystals. The addition of Ni2+, Zn2+, and Co2+ resulted in faster rates of mineral transformation. The conversion of green rust to magnetite was concurrent to significant increases in metal uptake, demonstrating a strong affinity for metal sorption/ co-precipitation by magnetite. Dissolution ratio curves showed that Ni2+, Zn2+, and Co2+ cations were incorporated into the mineral structure during magnetite crystal growth. The results indicate that the transformation of green rust to magnetite is accelerated by metal impurities, and that magnetite is a highly effective scavenger of trace metals during mineral transformation. The implications for using diagenetic magnetite from green rust precursors as paleoproxies of Precambrian ocean chemistry are discussed.

Hydrosulfate green rust↗
DOE OSTI2025

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↗
DOE OSTI2025

The CO2 mineralization potential of New Mexico basalts and associated critical element behavior and mobility.

This presentation reports on laboratory experiments assessing the carbon dioxide (CO₂) mineralization potential of New Mexico basalts, including trachybasalt and basalt lithologies. Using simulated groundwater and controlled conditions, the study evaluates the kinetics of CO₂ sequestration, mineral saturation indices, and secondary mineral formation. It also investigates the mobility of critical and trace elements such as Ni, Zn, Cu, and Li during basalt dissolution. Results indicate that New Mexico basalts can effectively sequester CO₂ through carbonate formation, with grain size and mineral composition influencing reaction rates and elemental behavior. These findings support the viability of geologic carbon storage in mafic volcanic terrains and inform strategies for critical element recovery.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Testing Destruction of Clay Minerals By Silica-Poor Brines in Gale Crater, Mars Using Laboratory and Field Experiments

The Mars Science Laboratory (MSL) Curiosity rover landed in Gale crater to investigate the cause for mineralogical changes seen from orbit, including the clay-sulfate mineral transition observed on its central mound, Aeolis Mons. The lower strata show spectral signatures of clay minerals, hematite, and hydrated Mg sulfates, and the upper strata are dominated by hydrated Mg sulfate signatures. This significant transition has been observed in other locations on Mars, and therefore processes related to the clay mineral-sulfate transition are likely important broadly across Mars. The bulk mineralogy of ~3.7 Ga sedimentary rocks in Gale crater is a product of variations in sediment sources and depositional processes, with overprinting by episodes of early and late diagenetic alteration. Sedimentary analyses of the smectite clay minerals observed in the Glen Torridon (GT) region of Mount Sharp suggest formation in a lacustrine aqueous environment. Examination of the Vera Rubin ridge (VRR) strata indicate that it was formed at the same time as GT and later altered by extensive diagenesis. Recent work suggests that the observed mineral transition from smectites and talc-serpentinites in GT to iron oxides and oxyhydroxides and VRR may have resulted from extensive diagenetic alteration by density driven, silica-poor brines sourced from the overlying sulfur-bearing unit on Mount Sharp. This process of alteration by silica-poor brines is observed in limited locations on Earth. We are therefore working to demonstrate the impacts of silica poor brines on clay mineral alteration in laboratory column and terrestrial analog burial experiments. Column experiments allow the investigation of dissolution and precipitation under conditions that represent a closer analog to natural environments, while burial experiments allow examination of weathering reactions of a known starting material after a specific period of time in a natural field environment. Both methods are valuable for interpreting the water-rock interactions between clay minerals and brines. In preparation for these longer-term column and burial experiments, we are performing preliminary batch dissolution experiments on materials relevant to Glen Torridon: nontronite and serpentinite. We are using magnesium sulfate brine solutions relevant to those proposed on Mars. The results of this study can provide constraints on the characteristics of the diagenetic fluids that formed the altered minerals in Gale crater. They can also provide insights into the role of brine density-driven diagenesis in past aqueous environments on Mars, which have been proposed to be widespread.

J E Valdueza↗
DOE OSTI2024

Structure and Dynamics of Aqueous Electrolytes at Quartz (001) and (101) Surfaces

Here, understanding and describing reactivity at mineral-water interfaces such as ion adsorption, the kinetics of dissolution, or surface charge development depends on our ability to improve the accuracy of electrical double layer (EDL) models. While molecular dynamics (MD) simulations are routinely used to investigate the structure and energetics of adsorbed ions comprising the EDL, less attention is paid to their self-diffusion dynamics, which can uniquely inform on coupling to interfacial reactions. Here we use MD to investigate both the organization and diffusion dynamics of water and electrolyte ions (NaCl, KCl, CaCl 2 ) at hydroxylated quartz (001) and (101) surfaces, a comparison which allowed us to assess surface structural effects of corrugation and silanol density. We found that inner- versus outer-sphere complex formation depends on cation size and charge but not necessarily hydration energies. Participation of surface silanols in the hydration spheres of Na + and K + generally indicated their preference for inner-sphere complexation, but this depends strongly on the orientation of the surface considered through its influence over the organization and dynamics of adsorbed water layers. In particular, surface orientation substantially affects the diffusive behavior of the near-surface water. Na + was found to decrease the mobility of water in the first layer, consistent with an increasing frequency of hydrolysis implied by faster quartz dissolution rates observed in experiments via the well known salt effect. Our results are also in good agreement with the observed dissolution rate of quartz vs. surface adsorption strength measure by Dove and Nix. This study sets the stage for a forthcoming paper examining how the dynamics at quartz/electrolyte interfaces are influenced by externally applied electric fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Selective sulfidation of metal compounds

There is urgent, unprecedented demand for critical by-product and co-product metallic elements for the infrastructure (magnets, batteries, catalysts and electronics) needed to power society with renewable electricity1,2,3. However, the extraction of d-block and f-block metals from mineral and recycled streams is thermodynamically difficult, typically requiring complete dissolution of the materials, followed by liquid–liquid separation using metal-ion complexing or chelating behaviour4,5. The similar electronic structure of these metals results in poor separation factors, necessitating immense energy, water and chemicals consumption6,7,8. Here a metal-processing approach based on selective anion exchange is proposed. Several simple process levers (gas partial pressure, gas flowrate and carbon addition) are demonstrated to selectively sulfidize a target metal from a mixed metal-oxide feed. The physical and chemical differences between the sulfide and oxide compounds (for example, density, magnetic susceptibility and surface chemistry) can then be exploited for vastly improved separation compared with liquid–liquid methods9. The process conditions of sulfidation are provided for 56 elements and demonstrated for 15 of them. An assessment of the environmental and economic impacts suggests a path towards 60–90% reductions in greenhouse gas emissions while offering substantial capital cost savings compared with liquid–liquid hydrometallurgy.

36 MATERIALS SCIENCE↗
DOE OSTI2022

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↗
DOE OSTI2025

Bipartisan Infrastructure Law (BIL) – Illinois Rare Earth Novel Extraction and Supply (IRENES) - Report on Technology Down Select No. 1 - Acid Baking vs. Heap Leaching

An essential step for recovering rare earth and critical minerals from coal mine waste is one that achieves adequate dissolution of the target elements into a pregnant leachate solution. The simplest technical approach was thought to be heap-leaching that could proceed using mild acid dosing or naturally generated acid from biological activity. For this reason, the University of Kentucky at Lexington (UKY) undertook two efforts to evaluate feasibility, including a laboratory column leaching evaluation and a pilot heap-leaching demonstration. Later, the UK evaluated a pyrometallurgical approach using roasting combined with acid baking and tank leaching at elevated temperatures to improve extraction efficiencies. This report surveys the previously reported leaching yields and calculates the gross value of rare earth oxides as a basket in the pregnant leachate solution.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1979

Isotopic anomalies of noble gases in meteorites and their origins. IV - C3 /Ornans/ carbonaceous chondrites

The C3O chondrites Kainsaz, Lance, and Ornans were studied by an acid dissolution technique to characterize the noble gas components in 3 mineral fractions: HF, HCl-solubles, chromite and carbon, and 'phase Q', a trace mineral containing Ar, Kr, Xe. For all fractions, gas contents decline in the order Kainsaz, Lance, Ornans; this trend parallels volatile contents but not heterogeneity of olivine composition or degree of metamorphism, and reflects progressively higher condensation temperature from the solar nebula. The Ar/Xe ratios and compositions of the three mineral fractions are discussed, and it is concluded that in all primitive chondrites the amount and the chemical separability of CCFXe parallel the abundance of primordial noble gases and other volatiles, such as C, N, Tl, Bi, and In. The close correlation of CCFXe with properties of local origin, such as volatile content and petrologic type, is more consistent with a local than with an extrasolar origin of the component.

Alaerts, L.↗
DOE OSTI2019

Accuracy of Thermodynamic Databases for Hydroxyapatite Dissolution Constant

We report that discrepancies have been noted in the solubility constant values of calcium phosphate minerals between various databases employed in widely-used aqueous speciation calculation software programs. This can cause serious errors in the calculated speciation of waters using these software programs. The aim of the present communication was to bring to light these discrepancies. Experimental determinations of the hydroxyapatite solubility product vary by as much as ten orders of magnitude as a result of experimental challenges related to the presence of impurities in the hydroxyapatite used, incongruent dissolution and the contamination of solutions with dissolved carbon dioxide. Finally, it is suggested that the value used in the database Thermo.dat is consistent with experimental data devoid of common experimental problems, while other common databases use values that lead to a vastly overestimated solubility of hydroxyapatite.

58 GEOSCIENCES↗
DOE OSTI2022

Nanoscale Mg-Depleted Layers Slow Carbonation of Forsterite (Mg 2 SiO 4 ) When Water Is Limited

Passivation of silicate surfaces by accumulated reaction products is an obstacle to efficient CO 2 mineralization. In this study, we investigate a unique passivation effect during the carbonation of the basalt mineral forsterite (Mg 2 SiO 4 ) in humid supercritical CO 2 (50 °C, 90 bar). Using in situ high-pressure infrared spectroscopy, we demonstrate that dissolution of forsterite into a thin water film slows significantly after reaction for ˜24 h, even under far-from-equilibrium conditions. Further, 29 Si magic angle spinning nuclear magnetic resonance spectroscopy detects a highly polymerized amorphous silica at this stage. On the basis of transmission electron microscopy and energy dispersive X-ray spectroscopy, we show that the silica is present as a Mg-depleted layer that is just 2–3 nm thick on the reacted forsterite particles. The decrease in the level of forsterite dissolution in the presence of an extraordinarily thin Mg-depleted layer can be strongly linked to properties of the thin fluid film at the surface, highlighting the importance of water during mineral carbonation. This study furthers our understanding of silicate mineral carbonation under select low-water, humidified fluid conditions relevant to basaltic geologic reservoirs, recovery of critical elements by carbonation of mafic ores, and sequestration of atmospheric CO 2 by enhanced rock weathering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Effect of Nucleation Heterogeneity on Mineral Precipitation in Confined Environments

Abstract The formation of new mineral phases in confined environments, especially in porous media, is crucial for various geological processes like mineralization and diagenesis. The nucleation and precipitation of minerals are initiated at the microscale through fluid‐rock interaction, where dissolution of primary phases leads to supersaturated conditions and nucleation and growth of secondary ones. Previous research has focused primarily on either precipitation or nucleation, without fully exploring their combined impact. Our study introduces a computational framework that integrates classical nucleation theory with the micro‐continuum method. We validated our model by comparing with experiments, and discovered that different surface nucleation rate changes the mode of precipitation from a preferential to uniform precipitate textures. Furthermore, our study uncovered that the conventional deterministic precipitation method tends to underestimate the permeability of the porous matrix. In contrast, the new framework significantly improves model accuracy by incorporating preferential precipitation and heterogeneous nucleation.

58 GEOSCIENCES↗
DOE OSTI2022

Investigating Abiotic and Biotic Mechanisms of Pyrite Reduction

Pyrite (FeS 2 ) has a very low solubility and therefore has historically been considered a sink for iron (Fe) and sulfur (S) and unavailable to biology in the absence of oxygen and oxidative weathering. Anaerobic methanogens were recently shown to reduce FeS 2 and assimilate Fe and S reduction products to meet nutrient demands. However, the mechanism of FeS 2 mineral reduction and the forms of Fe and S assimilated by methanogens remained unclear. Thermodynamic calculations described herein indicate that H 2 at aqueous concentrations as low as 10 –10 M favors the reduction of FeS 2 , with sulfide (HS – ) and pyrrhotite (Fe 1–x S) as products; abiotic laboratory experiments confirmed the reduction of FeS 2 with dissolved H 2 concentrations greater than 1.98 × 10 –4 M H 2 . Growth studies of Methanosarcina barkeri provided with FeS 2 as the sole source of Fe and S resulted in H 2 production but at concentrations too low to drive abiotic FeS 2 reduction, based on abiotic laboratory experimental data. A strain of M. barkeri with deletions in all [NiFe]-hydrogenases maintained the ability to reduce FeS 2 during growth, providing further evidence that extracellular electron transport (EET) to FeS 2 does not involve H 2 or [NiFe]-hydrogenases. Physical contact between cells and FeS 2 was required for mineral reduction but was not required to obtain Fe and S from dissolution products. The addition of a synthetic electron shuttle, anthraquinone-2,6-disulfonate, allowed for biological reduction of FeS 2 when physical contact between cells and FeS 2 was prohibited, indicating that exogenous electron shuttles can mediate FeS 2 reduction. Here, transcriptomics experiments revealed upregulation of several cytoplasmic oxidoreductases during growth of M. barkeri on FeS 2 , which may indicate involvement in provisioning low potential electrons for EET to FeS 2 . Collectively, the data presented herein indicate that reduction of insoluble FeS 2 by M. barkeri occurred via electron transfer from the cell surface to the mineral surface resulting in the generation of soluble HS – and mineral-associated Fe 1–x S. Solubilized Fe(II), but not HS – , from mineral-associated Fe 1–x S reacts with aqueous HS – yielding aqueous iron sulfur clusters (FeS aq ) that likely serve as the Fe and S source for methanogen growth and activity. FeS aq nucleation and subsequent precipitation on the surface of cells may result in accelerated EET to FeS 2 , resulting in positive feedback between cell activity and FeS 2 reduction.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

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↗