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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.

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All sourcesNASA NTRSDOE OSTI
NASA NTRS1979

Altered rock spectra in the visible and near infrared

The author has identified the following significant results. Visible and near-infrared (0.35 to 2.5 micron m) bidirectional reflection spectra recorded for a suite of well-characterized hydrothermally altered rock samples typically display well defined bands caused by both electronic and vibrational processes in the individual mineral constituents. Electronic transitions in the iron-bearing constituent minerals produce diagnostic minima near 0.43, 0.65, 0.85, and 0.93 micron m. Vibrational transitions in clay and water-bearing mineral constituents produce characteristic single or multiple features over limited spectral ranges near 1.4, 1.75, 1.9, 2.2, and 2.35 micron m. The most abundant feature-producing minerals present in these rocks are hematite, goethite, and alunite. Others frequently present are jarosite, kaolinite, potassium micas, pyrophyllite, montmorillonite, diaspore, and gypsum. The spectral region near 2.2 micron m is particularly important for detecting altered rocks by remote sensing.

Hunt, G. R.↗
NASA NTRS1982

Mars weathering analogs - Secondary mineralization in Antarctic basalts

Alkalic basalt samples from Ross Island, Antarctica, are evaluated as terrestrial analogs to weathered surface materials on Mars. Secondary alteration in the rocks is limited to pneumatolytic oxidation of igneous minerals and glass, rare groundmass clay and zeolite mineralization, and hydrothermal minerals coating fractures and vesicle surfaces. Hydrothermal mineral assemblages consist mainly of K-feldspar, zeolites (phillipsite and chabazite), calcite, and anhydrite. Low alteration rates are attributed to cold and dry environmental factors common to both Antarctica and Mars. It is noted that mechanical weathering (aeolian abrasion) of Martian equivalents to present Antarctic basalts would yield minor hydrothermal minerals and local surface fines composed of primary igneous minerals and glass but would produce few hydrous products, such as palagonite, clay or micas. It is thought that leaching of hydrothermal vein minerals by migrating fluids and redeposition in duricrust deposits may represent an alternate process for incorporating secondary minerals of volcanic origin into Martian surface fines.

Berkley, J. L.↗
NASA NTRS2010

Inferring Properties of Ancient Cyanobacteria from Biogeochemical Activity and Genomes of Siderophilic Cyanobacteria

Interrelationships between life and the planetary system could have simultaneously left landmarks in genomes of microbes and physicochemical signatures in the lithosphere. Verifying the links between genomic features in living organisms and the mineralized signatures generated by these organisms will help to reveal traces of life on Earth and beyond. Among contemporary environments, iron-depositing hot springs (IDHS) may represent one of the most appropriate natural models [1] for insights into ancient life since organisms may have originated on Earth and probably Mars in association with hydrothermal activity [2,3]. IDHS also seem to be appropriate models for studying certain biogeochemical processes that could have taken place in the late Archean and,-or early Paleoproterozoic eras [4, 5]. It has been suggested that inorganic polyphosphate (PPi), in chains of tens to hundreds of phosphate residues linked by high-energy bonds, is environmentally ubiquitous and abundant [6]. Cyanobacteria (CB) react to increased heavy metal concentrations and UV by enhanced generation of PPi bodies (PPB) [7], which are believed to be signatures of life [8]. However, the role of PPi in oxygenic prokaryotes for the suppression of oxidative stress induced by high Fe is poorly studied. Here we present preliminary results of a new mechanism of Fe mineralization in oxygenic prokaryotes, the effect of Fe on the generation of PPi bodies in CB, as well as preliminary analysis of the diversity and phylogeny of proteins involved in the prevention of oxidative stress in phototrophs inhabiting IDHS.

McKay, David S.↗
NASA NTRS2015

Germanium Enrichments in Sedimentary Rocks in Gale Crater, Mars: Constraining the Timing of Alteration and Character of the Protolith

Rocks enriched in Ge have been discovered in Gale Crater, Mars, by the Alpha-particle X-ray spectrometer (APXS) on the Mars Science Lab (MSL) rover, Curiosity. The Ge concentrations in Gale Crater (commonly >50 ppm) are remarkably high in comparison to Earth, where Ge ranges from 0.5-4.0 ppm in igneous rocks and 0.2-3.3 ppm in siliciclastic sediment. Primary meteoritic input is not likely the source of high Ge because Ge/Ni in chondrites (approx.0.003) and irons (<0.04) is lower than in Gale rocks (0.08-0.2). Earth studies show Ge is a useful geochemical tracer because it is coherent with Si during magmatic processes and Ge/Si varies less than 20% in basalts. Ge and Si fractionate during soil/regolith weathering, with Ge preferentially sequestered in clays. Ge is also concentrated in Cu- and Zn-rich hydrothermal sulfide deposits and Fe- and Mnrich oxide deposits. Other fluid-mobile elements (K, Zn, Cl, Br, S) are also enriched at Gale and further constrain aqueous alteration processes. Here, we interpret the sediment alteration history and present a possible model for Ge enrichments at Gale involving fluid alteration of the protolith.

Berger, J. A.↗
NASA NTRS2004

Microbial Paleontology, Mineralogy and Geochemistry of Modern and Ancient Thermal Spring Deposits and Their Recognition on the Early Earth and Mars"

The vision of this project was to improve our understanding of the processes by which microbiological information is captured and preserved in rapidly mineralizing sedimentary environments. Specifically, the research focused on the ways in which microbial mats and biofilms influence the sedimentology, geochemistry and paleontology of modem hydrothermal spring deposits in Yellowstone national Park and their ancient analogs. Toward that goal, we sought to understand how the preservation of fossil biosignatures is affected by 1) taphonomy- the natural degradation processes that affect an organism from the time of its death, until its discovery as a fossil and 2) diagenesis- longer-term, post-depositional processes, including cementation and matrix recrystallization, which collectively affect the mineral matrix that contains fossil biosignature information. Early objectives of this project included the development of observational frameworks (facies models) and methods (highly-integrated, interdisciplinary approaches) that could be used to explore for hydrothermal deposits in ancient terranes on Earth, and eventually on Mars.

Farmer, Jack D.↗
NASA NTRS2004

Evidence for exclusively inorganic formation of magnetite in Martian meteorite ALH84001

Magnetite crystals produced by terrestrial magnetotactic bacterium MV-1 are elongated on a [111] crystallographic axis, in a so-called truncated hexa-Octahedral shape. This morphology has been proposed to constitute a biomarker (i.e., formed only in biogenic processes). A subpopulation of magnetite crystals associated with carbonate globules in Martian meteorite ALH84001 is reported to have this morphology, and the observation has been taken as evidence for biological activity on Mars. In this study, we present evidence for the exclusively inorganic origin of [111]-elongated magnetite crystals in ALH84001. We report three-dimensional(3-D) morphologies for approx.1000 magnetite crystals extracted from: (1) thermal decomposition products of Fe-rich carbonate produced by inorganic hydrothermal precipitation in laboratory experiments; (2) carbonate globules in Martian meteoriteeALH84001; and (3) cells of magnetotactic bacterial strain MV-1. The 3-D morphologies were derived by fitting 3-D shape models to two-dimensional bright-field transmission-electron microscope (TEAM) images obtained at a series of viewing angles. The view down the {110} axes closest to the [111] elongation axis of magnetite crystals ([111]x{110) not equal to 0) provides a 2-D projection that uniquely discriminates among the three [111]-elongated magnetite morphologies found in these samples: [111]-elongated truncated hexaoctahedron ([111]-THO), [111]-elongated cubo-octahedron ([111]-ECO), and [111]-elongated simple octahedron ([111]-ESO). All [111] -elongated morphologies are present in the three types of sample, but in different proportions. In the ALH84001 Martian meteorite and in our inorganic laboratory products, the most common [111]-elongated magnetite crystal morphology is [111]-ECO. In contrast, the most common morphology for magnetotactic bacterial strain MV-1 is [111]-THO. These results show that: (1) the morphology of [111]-elongated magnetite crystals associated with the carbonate globules in Martian meteorite ALH84001 is replicated by an inorganic process; and (2) the most common crystal morphology for biogenic (MV-1) magnetite is distinctly different from that in both ALH84001 and our inorganic laboratory products. Therefore, [111]-elongated magnetite crystals in ALH84001 do not constitute, as previously claimed, a robust biosignature and, in fact, an exclusively inorganic origin for the magnetite is fully consistent with our results. Furthermore, the inorganic synthesis method, i.e., the thermal decomposition of hydrothermally precipitated Fe-rich carbonate, is a process analogue for formation of the magnetite on Mars. Namely, precipitation of carbonate globules from carbonate-rich hydrothermal solutions followed at some later time by a thermal pulse, perhaps in association with meteoritic impact or volcanic processes on the Martian surface.

Golden, D. C.↗
DOE OSTI2024

Hydrothermal conditioning of oleaginous yeast cells to enable recovery of lipids as potential drop-in fuel precursors

Abstract Background Lipids produced using oleaginous yeast cells are an emerging feedstock to manufacture commercially valuable oleochemicals ranging from pharmaceuticals to lipid-derived biofuels. Production of biofuels using oleaginous yeast is a multistep procedure that requires yeast cultivation and harvesting, lipid recovery, and conversion of the lipids to biofuels. The quantitative recovery of the total intracellular lipid from the yeast cells is a critical step during the development of a bioprocess. Their rigid cell walls often make them resistant to lysis. The existing methods include mechanical, chemical, biological and thermochemical lysis of yeast cell walls followed by solvent extraction. In this study, an aqueous thermal pretreatment was explored as a method for lysing the cell wall of the oleaginous yeast Rhodotorula toruloides for lipid recovery. Results Hydrothermal pretreatment for 60 min at 121 °C with a dry cell weight of 7% (w/v) in the yeast slurry led to a recovery of 84.6 ± 3.2% (w/w) of the total lipids when extracted with organic solvents. The conventional sonication and acid-assisted thermal cell lysis led to a lipid recovery yield of 99.8 ± 0.03% (w/w) and 109.5 ± 1.9% (w/w), respectively. The fatty acid profiles of the hydrothermally pretreated cells and freeze-dried control were similar, suggesting that the thermal lysis of the cells did not degrade the lipids. Conclusion This work demonstrates that hydrothermal pretreatment of yeast cell slurry at 121 °C for 60 min is a robust and sustainable method for cell conditioning to extract intracellular microbial lipids for biofuel production and provides a baseline for further scale-up and process integration. Graphical abstract

09 BIOMASS FUELS↗
DOE OSTI2021

Opportunities and challenges for flow-through hydrothermal pretreatment in advanced biorefineries

Hydrothermal pretreatment (HTP) using only water offers great potential to reduce the overall cost of the bioconversion process. However, traditional HTP performed in a batch has limitations in removing lignin and often needs to be performed under severe conditions to achieve reasonable pretreatment effects. Additionally, lignin left in the pretreated residue at these conditions is also highly condensed, thus possessing an even more adverse impact on the hydrolysis process, which requires high enzyme loadings. To address these technical challenges, HTP performed in a flow-through configuration was developed to simultaneously achieve near-complete hemicellulose recovery, high lignin removal and high sugar release. Despite facing challenges such as potentially large water usage, flow-through HTP still represents one of the most cost-effective and eco-friendly pretreatment methods. This review mainly covers the latest cutting-edge innovations of flow-through HTP along with structural and compositional changes of cellulose, hemicellulose, and lignin before and after pretreatment.

09 BIOMASS FUELS↗
NASA NTRS2010

History of Nebular Processing Traced by Silicate Stardust in IDPS

Chondritic porous interplanetary dust particles (CP-IDPs) may be the best preserved remnants of primordial solar system materials, in part because they were not affected by parent body hydrothermal alteration. Their primitive characteristics include fine grained, unequilibrated, anhydrous mineralogy, enrichment in volatile elements, and abundant molecular cloud material and silicate stardust. However, while the majority of CP-IDP materials likely derived from the Solar System, their formation processes and provenance are poorly constrained. Stardust abundances provide a relative measure of the extent of processing that the Solar System starting materials has undergone in primitive materials. For example, among primitive meteorites silicate stardust abundances vary by over two orders of magnitude (less than 10-200 ppm). This range of abundances is ascribed to varying extents of aqueous processing in the meteorite parent bodies. The higher average silicate stardust abundances among CP-IDPs (greater than 375 ppm) are thus attributable to the lack of aqueous processing of these materials. Yet, silicate stardust abundances in IDPs also vary considerably. While the silicate stardust abundance in IDPs having anomalous N isotopic compositions was reported to be 375 ppm, the abundance in IDPs lacking N anomalies is less than 10 ppm. Furthermore, these values are significantly eclipsed among some IDPs with abundances ranging from 2,000 ppm to 10,000 ppm. Given that CP-IDPs have not been significantly affected by parent body processes, the difference in silicate stardust abundances among these IDPs must reflect varying extents of nebular processing. Here we present recent results of a systematic coordinated mineralogical/isotopic study of large cluster IDPs aimed at (1) characterizing the mineralogy of presolar silicates and (2) delineating the mineralogical and petrographic characteristics of IDPs with differing silicate stardust abundances. One of the goals of this study is to better understand the earliest stages of evolution of the Solar System starting materials.

Messenger, Scott R.↗
DOE OSTI2018

Effect of Hydrothermal Aging on Injection Molded Short Jute Fiber Reinforced Poly(Lactic Acid) (PLA) Composites

This work focused on the durability of short jute fiber reinforced poly(lactic acid) (PLA) composites in distilled water at different temperatures (23, 37.8 and 60 °C). Morphological, thermal and mechanical properties (tensile, flexural, and impact) of jute/PLA composites were investigated before and after aging. Different from traditional synthetic fiber reinforced polymer composites, the stability of jute/PLA composites in water was significantly influenced by hydrothermal temperature. The mechanical properties of the composites and molecular weight of PLA matrix declined quickly at 60 °C, however, this process was quite slower at temperatures of 23 and 37.8 °C. Impact properties of the composites were hardly decreased, but the tensile and flexural properties suffered a drop though to various degrees with three degradation stages at 23 and 37.8 °C. The poor interface of composites and the degradation of PLA matrix were the main damage mechanism induced by hydrothermal aging. Furthermore, considering the hydrolysis of PLA matrix, the cleavage of PLA molecular chain in different aging time was quantitatively investigated for the first time to illustrate hydrolysis degree of PLA matrix at different aging time.

36 MATERIALS SCIENCE↗
NASA NTRS1990

Evaluation of the airborne visible-infrared imaging spectrometer for mapping subtle lithological variation

The Airborne Visible/Infrared Imaging Spectrometer (AVIRIS), flown aboard the NASA ER-2 aircraft in 1987 and 1989, used four linear arrays and four individual spectrometers to collect data simultaneously from the 224 bands in a scanned 614 pixel-wide swath perpendicular to the aircraft direction. The research had two goals. One was to evaluate the AVIRIS data. The other was to look at the subtle lithological variation at the two test sites to develop a better understanding of the regional geology and surficial processes. The geometric characteristics of the data, adequacy of the spatial resolution, and adequacy of the spectral sampling interval are evaluated. Geologic differences at the test sites were mapped. They included lithological variation caused by primary sedimentary layering, facies variation, and weathering; and subtle mineralogical differences caused by hydrothermal alterations of igneous and sedimentary rocks. The investigation used laboratory, field, and aircraft spectral measurements; known properties of geological materials; digital image processing and spectrum processing techniques; and field geologic data to evaluate the selected characteristics of the AVIRIS data.

Kruse, Fred A.↗
DOE OSTI2018

Final Report for the Project Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils

The Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils project developed processes to extract value from the organics within aqueous streams derived from biomass direct liquefaction processes. The focus of the project was twofold. First, we characterized a diverse set of aqueous streams from numerous processes and feedstocks. The characterization effort served to inform this project toward development around the most prevalent compounds to maximize versatility and impact. We analyzed diverse streams from hydrothermal liquefaction of lignocellulosic, algal, and waste feedstocks; catalytic fast-pyrolysis aqueous phases; fast-pyrolysis aqueous phases; and aqueous phases produced by hydroprocessing of fast-pyrolysis bio-oil. Second, thermochemical catalytic processes were developed to convert aqueous-phase organics into useful products. These processes focused mostly on organic acids and specifically acetic acid, which was found to be ubiquitous from the characterization effort. A La x Zr y O z catalyst was discovered and developed for the ketonization of acids to ketones in the condensed aqueous phase. A dual-bed steam reforming process was developed to convert acids and other organics to hydrogen for bio-oil hydroprocessing. The dual-bed reforming process consisted of a ketonization step followed by a steam reforming step with Co as the active metal. The dual-bed process significantly reduced the rate of coke deposition versus direct steam reforming of the organic acids and beneficially produced CH 4 below the equilibrium value. Finally, we demonstrated direct conversion of aqueous-phase organics to olefins over a Zn x Zr y O z catalyst. Each thermochemical catalytic process was demonstrated with process-derived aqueous mixtures. Model compounds were used to benchmark performance and optimize conditions, but emphasis was placed on utilizing “real” aqueous streams whenever possible. A liquid-liquid extraction process using methyl tert-butyl ether as the solvent was developed to segregate dissolved inorganic species and sugars from desirable light oxygenates such as acids and alcohols. Furthermore, a carbon treatment to remove color bodies was employed after it was found the presumably heavy organic chromophore species deactivated catalysts. These economic separation processes allowed for the successful demonstration of stable catalytic processing in the condensed-phase ketonization, dual-bed reforming, and direct olefin production processes for tens to hundreds of hours, which were limited only by the quantity of feed available. Techno-economic analysis of these processes demonstrated the impact possible when capturing “waste” organics as valuable products. The condensed-phase ketonization process for converting aqueous stream acids to ketones followed by reduction and dehydration to olefins sold as a co-product resulted in the reduction of the minimum fuel selling price by about 13% compared to the anaerobic-digestion, aqueous-phase treatment base case (3.74 to 4.29/GGE). The dual-bed reforming process was commensurate in price to the anaerobic digestion base case (4.24 versus 4.29/GGE). However, the need for external natural gas to produce hydrogen for bio-oil hydroprocessing was eliminated, thereby lowering the carbon impact of the process.

09 BIOMASS FUELS↗
DOE OSTI2025

Develop an efficient and cost-effective novel anaerobic digestion system producing high purity of methane from diverse waste biomass

This project focuses on developing an advanced, intensified anaerobic digestion system aimed at transforming the treatment and conversion of organic wastes into valuable products, specifically renewable natural gas. The motivation for this research stems from the limitations of conventional anaerobic digestion technologies, which often face challenges such as long retention times, high operational costs, and incomplete organic material degradation. The new technology called Intensified Versatile Anaerobic Digestion (IVAD), is developed to address these challenges by incorporating innovative reactors and processes that enhance the overall efficiency and output of anaerobic digestion. The significance of this project lies in its potential to revolutionize waste management practices and waste biomass utilization. The IVAD system integrates a hyperthermophilic anaerobic acidification reactor, a hydrothermal treatment (HTT) unit, and both thermophilic and mesophilic methanogenic reactors. This combination enables a higher rate of organic breakdown and energy recovery, resulting in faster processing times, reduced reactor sizes, and lower operational costs compared to traditional systems. Key data include an increase in methane productivity to 1.18 m 3 /m 3 /day, a significant improvement compared to the baseline technology’s 0.64 m 3 /m 3 /day. Additionally, the IVAD system achieves a 45% reduction in levelized cost of energy (LCOE), down to $\$$10.04/MMBTU, and an energy return on investment (EROI) of 3.19, representing an 87% increase over baseline levels. Technical and economic analyses highlight that the IVAD system significantly reduces hydraulic retention time (HRT) and solid retention time (SRT). The HRT for the HTT reactor can be reduced from 1 hour to 0.5 hours, while decoupling SRT from HRT in the anaerobic acidification reactor (AAR) allows for further reductions. These design optimizations lead to smaller reactor volumes, cutting down equipment and construction costs. Despite these advancements, energy consumption remains comparable to conventional methods due to a novel heat recovery strategy, enhancing overall process productivity. The system also achieves in-situ CO 2 removal and ammonia stripping features, resulting in biogas with a methane purity level of 75%, and produces high-quality nitrogen fertilizer as an additional by-product. Public benefits of the IVAD system are substantial, contributing to sustainable waste management and renewable energy production. By providing a scalable solution that can be adopted by dairy farms and similar agricultural operations, the IVAD system helps reduce waste, produce renewable natural gas (RNG) suitable for transportation fuel, and generate fertilizer, supporting a circular economy. This project plays a role in achieving broader environmental objectives by mitigating greenhouse gas emissions and promoting energy independence. Additionally, it offers a pathway for farmers to lower operational costs while adopting practices that are both environmentally sustainable and economically advantageous.

03 NATURAL GAS↗
NASA NTRS2001

Potential Mars Exploration Rover Landing Sites West and South of Apollinaris Patera

Apollinaris provides an exceptional site for astrobiological, geological, and climatalogical purposes. Fluvial (including ground water sapping) and associated processes were likely pervasive from the late Noachian, through the Hesperian, and into the Amazonian. Long-lived and large scale hydrothermal systems were certainly present throughout much if not all of this period. Thermal springs likely persisted for long periods. Water from the highlands via Ma'adim Valles and other smaller valley networks deposited highland-derived material in the area. In short, Apollinaris provides an excellent variety of rock types and ages and may preserve evidence of biologic or pre-biologic processes in associated thermal spring deposits.

Gulick, Virginia C.↗
DOE OSTI2026

Data for Optimization of Pre-Commercial Enzymes Dosage for a Potential Lignocellulosic Biorefinery

Lignocellulolytic enzymes remain one of the primary cost constraints in second-generation (2G) ethanol biorefineries. Achieving efficient hydrolysis of structural carbohydrates with minimal enzyme dosage, maintaining slurry fermentability for industrially relevant ethanol titers, and maximizing ethanol yield per ton of biomass are among the major challenges in 2G processes. In this study, we optimized the dosages of pre-commercial cellulase (NS22257) and hemicellulase (NS22244) on pilot-scale, hydrothermally pretreated lignocellulosic substrates. Enzyme dosages were evaluated at three levels: 20 mg of cellulase with 7.25 mg of hemicellulase (ED-1), 40 mg with 14.5 mg (ED-2), and 60 mg with 21.75 mg (ED-3). As expected, the highest sugar yields were obtained with ED-3; however, for sweet sorghum, oilcane, and miscanthus, sugar yields from ED-2 and ED-3 were not significantly different (p < 0.05). For example, sweet sorghum produced 123.78 ± 1.54 g L−1 and 125.76 ± 0.46 g L−1 of total sugars (glucose and xylose) with ED-2 and ED-3, respectively. Although energycane exhibited a statistically significant difference between ED-2 and ED-3, the incremental gain with ED-3 was modest, increasing sugar release by only 9.02 g L−1 relative to ED-2. Importantly, ED-1 resulted in sugar yields of 88.88 ± 3.64 to 106.86 ± 1.21 g L−1, sufficient to achieve ethanol titers ≥40 g L−1, the threshold required for industrial relevance. A semi-integrated bioprocess validated this outcome, producing 42.09 ± 2.38 g L−1 ethanol and an estimated yield of 213.38 L of ethanol per dry ton of pretreated biomass, requiring only 20.83 L of cellulase and 6.25 L of hemicellulase per ton. Remarkably, these enzyme dosages were approximately tenfold lower than those reported in prior studies.

Energycane↗
NASA NTRS2023

An evolutionary system of mineralogy, Part VI: Earth’s earliest Hadean crust (> 4370 Ma)

Part VI of the evolutionary system of mineralogy catalogs 262 kinds of minerals, formed by 18 different processes, that we suggest represent the earliest solid phases in Earth’s crust. All of these minerals likely formed during the first tens of millions of years following the global-scale disruption of the Moon-forming impact prior to ~4.4 Ga, though no samples of terrestrial minerals older than ~4.37 Ga are known to have survived on Earth today. Our catalog of the earliest Hadean species includes 80 primary phases associated with ultramafic and mafic igneous rocks, as well as more than 80 minerals deposited from immiscible S-rich fluids and late-stage Si-rich residual melts. Earth’s earliest crustal minerals also included more than 200 secondary phases of these primary minerals that were generated by thermal metamorphism, aqueous alteration, impacts, and other processes. In particular, secondary mineralization related to pervasive near-surface aqueous fluids may have included serpentinization of mafic and ultramafic rocks, hot springs and submarine volcanic vent mineralization, hydrothermal sulfide deposits, zeolite and associated mineral formation in basaltic cavities, marine authigenesis, and hydration of subaerial lithologies. Additional Hadean minerals may have formed by thermal metamorphism of lava xenoliths, sublimation at volcanic fumaroles, impact processes, and volcanic lightning. These minerals would have occurred along with more than 180 additional phases found in the variety of meteorites that continuously fell to Earth’s surface during the early Hadean Eon.

Philosophy of mineralogy↗
DOE OSTI2023

Modeling aqueous association constants and mineral solubilities at subcritical and supercritical temperatures

The need for sustainable power generation has increased interest in the use of hydrothermal fluids for industrial applications. New high-enthalpy geothermal systems and biowaste-to-fuel processes are two relevant examples that employ supercritical fluids which require an in-depth understanding of complex chemical reactions occurring near the supercritical temperature of water (374 °C). As these processes operate in thermodynamic regimes that are not currently covered by a standard molar Gibbs energy of formation model, only empirical fits for single reaction systems are available which limit the use of multi-component phase equilibria calculations that are standard practice for less extreme environments. Here, in this paper, we advance a standard molar Gibbs energy of formation model able to operate in these otherwise inaccessible thermodynamic states to include species needed for key mineral solubility systems and ion association reactions. This work extends a model based on molecular statistical thermodynamics (MST) into four new systems (Na 3 PO 4 -H 2 O, LiOH-H 2 O, KOH-H 2 O, and BaSO 4 -H 2 O) by extending the model to cover 10 new species. For each of these systems, model predictions were consistently within the experimental uncertainties for the new systems covered. A breakdown of MST contributions to the model revealed that electrostatic and hard sphere contributions were key to reproducing density dependencies of standard molar Gibbs energy of formation values around the critical point of water.

42 ENGINEERING↗