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The solubility of hydrogen in rhodium, ruthenium, iridium and nickel.

The temperature variation of the solubility of hydrogen in rhodium, ruthenium, iridium, and nickel in equilibrium with H2 gas at 1 atm pressure has been measured by a technique involving saturating the solvent metal with hydrogen, quenching, and analyzing in resultant solid solutions. The solubilities determined are small (atom fraction of H is in the range from 0.0005 to 0.00001, and the results are consistent with the simple quasi-regular model for dilute interstitial solid solutions. The relative partial enthalpy and excess entropy of the dissolved hydrogen atoms have been calculated from the solubility data and compared with well-known correlations between these quantities.

Mclellan, R. B.↗

The Microbial Community and Functional Potential in the Midland Basin Reveal a Community Dominated by Both Thiosulfate and Sulfate-Reducing Microorganisms

The Permian Basin is the highest producing oil and gas reservoir in the United States. Hydrocarbon resources in this region are often accessed by unconventional extraction methods, including horizontal drilling and hydraulic fracturing. Despite the importance of the Permian Basin, there is no publicly available microbiological data from this region. We completed an analysis of Permian produced water samples to understand the dynamics present in hydraulically fractured wells in this region. We analyzed produced water samples taken from 10 wells in the Permian region of the Midland Basin using geochemical measurements, 16S rRNA gene sequencing, and metagenomic sequencing. Compared to other regions, we found that Permian Basin produced water was characterized by higher sulfate and lower total dissolved solids (TDS) concentrations, with a median of 1,110 mg/L and 107,000 mg/L. Additionally, geochemical measurements revealed the presence of frac hits, or interwell communication events where an established well is affected by the pumping of fracturing fluid into a new well. The occurrence of frac hits was supported by correlations between the microbiome and the geochemical parameters. Our 16S rRNA gene sequencing identified a produced water microbiome characterized by anaerobic, halophilic, and sulfur reducing taxa. Interestingly, sulfate and thiosulfate reducing taxa including Halanaerobium, Orenia, Marinobacter, and Desulfohalobium were the most prevalent microbiota in most wells. We further investigated the metabolic potential of microorganisms in the Permian Basin with metagenomic sequencing. We recovered 15 metagenome assembled genomes (MAGs) from seven different samples representing 6 unique well sites. These MAGs corroborated the high presence of sulfate and thiosulfate reducing genes across all wells, especially from key taxa including Halanaerobium and Orenia. The observed microbiome composition and metabolic capabilities in conjunction with the high sulfate concentrations demonstrate a high potential for hydrogen sulfide production in the Permian Basin. Additionally, evidence of frac hits suggests the possibility for the exchange of microbial cells and/or genetic information between wells. This exchange would increase the likelihood of hydrogen sulfide production and has implications for the oil and gas industry.

16S RNA↗

Thermal responses of dissolved organic matter under global change

The diversity of intrinsic traits of different organic matter molecules makes it challenging to predict how they, and therefore the global carbon cycle, will respond to climate change. Here we develop an indicator of compositional-level environmental response for dissolved organic matter to quantify the aggregated response of individual molecules that positively and negatively associate with warming. We apply the indicator to assess the thermal response of sediment dissolved organic matter in 480 aquatic microcosms along nutrient gradients on three Eurasian mountainsides. Organic molecules consistently respond to temperature change within and across contrasting climate zones. At a compositional level, dissolved organic matter in warmer sites has a stronger thermal response and shows functional reorganization towards molecules with lower thermodynamic favorability for microbial decomposition. The thermal response is more sensitive to warming at higher nutrients, with increased sensitivity of up to 22% for each additional 1 mg L -1 of nitrogen loading. The utility of the thermal response indicator is further confirmed by laboratory experiments and reveals its positive links to greenhouse gas emissions.

54 ENVIRONMENTAL SCIENCES↗

Investigation of enhanced CO 2 storage in deep saline aquifers by WAG and brine extraction in the Minnelusa sandstone, Wyoming

Geological CO 2 sequestration in deep saline aquifers has been extendedly investigated to reach the goal of carbon neutral as large amount of CO 2 can be reduced in a short time. Here, this study investigates the feasibility of water-alternating-gas (WAG) injection and brine extraction on enhancing CO 2 storage in a target deep saline aquifer, Minnelusa Sandstone in the Powder River Basin (PRB) of Wyoming. An integrated numerical model is developed to account for four scenarios: (1) CO 2 continuous injection (CI) through one injection well, (2) WAG injection through one injection well, (3) CO 2 CI through one injection well and brine extraction through one producer, (4) WAG injection through one injection well and brine extraction through one producer. Simulation results suggest that WAG injection and brine extraction corporately make it possible to enhance CO 2 injectivity while securing CO 2 storage safety. For instance, WAG injection considerably reduces structural trapping contribution while enhances dissolved and residual trapping contributions. As for brine extraction, it can decrease the maximum averaged reservoir pressure by 37% and 22% for CI and WAG injection, respectively. Besides, sensitive analyses of the operational parameters for the fourth scenarios are performed. Results reveal that, when the amount of total CO 2 injection has been predetermined, CO 2 injection time and rate within each period of WAG should be small whereas it is preferable to have large water injection time and rate. This is to secure desirable dissolved and residual trapping contributions (store CO 2 with safety). Sensitive degree results confirm that CO 2 injection rate, water injection time, and CO 2 injection time of WAG injection exhibit significant effects on CO 2 storage whereas the impacts of producer bottom-hole pressure (BHP), water injection rate, and CO 2 -water injection time are relatively weaker. This study not only sheds light on achieving double-win goal: enhance CO 2 injectivity and store CO 2 with safety, but also can be a critical reference for other CO 2 storage in deep saline aquifers.

58 GEOSCIENCES↗

Quantifying Drivers of Methane Hydrobiogeochemistry in a Tidal River Floodplain System

The influence of coastal ecosystems on global greenhouse gas (GHG) budgets and their response to increasing inundation and salinization remains poorly constrained. In this study, we have integrated an uncertainty quantification (UQ) and ensemble machine learning (ML) framework to identify and rank the most influential processes, properties, and conditions controlling methane behavior in a freshwater floodplain responding to recently restored seawater inundation. Our unique multivariate, multiyear, and multi-site dataset comprises tidal creek and floodplain porewater observations encompassing water level, salinity, pH, temperature, dissolved oxygen (DO), dissolved organic carbon (DOC), total dissolved nitrogen (TDN), partial pressure of carbon dioxide (pCO 2 ), nitrous oxide (pN 2 O), methane (pCH 4 ), and the stable isotopic composition of methane (δ 13 CH 4 ). Additionally, we incorporated topographical data, soil porosity, hydraulic conductivity, and water retention parameters for UQ analysis using a previously developed 3D variably saturated flow and transport floodplain model for a physical mechanistic understanding of factors influencing groundwater levels and salinity and, therefore, CH 4 . Principal component analysis revealed that groundwater level and salinity are the most significant predictors of overall biogeochemical variability. The ensemble ML models and UQ analyses identified DO, water level, salinity, and temperature as the most influential factors for porewater methane levels and indicated that approximately 80% of the total variability in hourly water levels and around 60% of the total variability in hourly salinity can be explained by permeability, creek water level, and two van Genuchten water retention function parameters: the air-entry suction parameter α and the pore size distribution parameter m. These findings provide insights on the physicochemical factors in methane behavior in coastal ecosystems and their representation in local- to global-scale Earth system models.

54 ENVIRONMENTAL SCIENCES↗

Carbon Isotope Biogeochemistry of Methane from Anoxic Sediments

The isotopic composition of naturally occurring methane was used to constrain the tropospheric budget of that radiatively active gas. Numerous studies have shown that the isotopic composition is not constant, even for a specific source, and may vary temporally and spatially. The objective was to develop a process-level model that reproduced the seasonal variations in the C-13/C-12 composition of methane observed at the coastal site, Cape Lookout Bight, NC. Details of the mass balance are provided. Experiments and models designed to determine what factors incluence C-13/C-12 ratio of dissolved CO2 are reported. All the factors described were combined in a model that faithfully reproduces the seasonal C-13/C-12 variations observed at Cape Lookout. The model is described.

Blair, Neal E.↗

Incorporation of Solar Noble Gases from a Nebula-Derived Atmosphere During Magma Ocean Cooling

The presence of solar noble gases in the deep interior of the Earth is inferred from the Ne isotopic compositions of MORB (Mid-ocean Ridge Basalts) and OIB (Oceanic Island Basalt); Ar data may also consistent with a solar component in the deep mantle. Models of the transport and distribution of noble gases in the earth's mantle allow for the presence of solar Ar/Ne and Xe/Ne ratios and permit the calculation of lower mantle noble gas concentrations. These mantle data and models also indicate that the Earth suffered early (0.7 to 2 x 10(exp 8) yr) and large (greater than 99 percent) losses of noble gases from the interior, a result previously concluded for atmospheric Xe. We have pursued the suggestion that solar noble gases were incorporated in the forming Earth from a massive, nebula-derived atmosphere which promoted large-scale melting, so that gases from this atmosphere dissolved in the magma ocean and were mixed downward. Models of a primitive atmosphere captured from the solar nebula and supported by accretion luminosity indicate that pressures at the Earth's surface were adequate (and largely more than the required 100 Atm) to dissolve sufficient gases. We have calculated the coupled evolution of the magma ocean and the overlying atmosphere under conditions corresponding to the cessation (or severe attenuation) of the sustaining accretion luminosity, prior to the complete removal of the solar nebula. Such a condition was likely to obtain, for instance, when most of the unaccumulated mass resided in large bodies which were only sporadically accreted. The luminosity supporting the atmosphere is then that provided by the cooling Earth, consideration of which sets a lower limit to the time required to solidify the mantle and terminate the incorporation of atmospheric gases within it. In our initial calculations, we have fixed the nebula temperature at To = 300K, a value likely to be appropriate for nebular temperatures at lAU in the early planet-building epoch. We treated the background (nebula) pressure as an adjustable, time-dependent parameter. Additional information is contained within the original extended abstract.

Woolum, D. S.↗

Cryptic cycling by electroactive bacterioplankton in Trout Bog Lake

The potential for extracellular electron transfer (EET) is a prevailing genomic feature of humic lake bacterioplankton. However, there has been little evidence for the substantial ecological contribution predicted by genetics. We hypothesized that anoxygenic phototrophic electrotrophs and accompanying heterotrophic electrogens cycle dissolved organic matter (DOM) between oxidized and reduced states. We predicted that such bacterioplankton would exhibit diel-scale oscillations due to the light dependency of photosynthesis. Using Trout Bog Lake in Wisconsin, USA, as our model ecosystem, we profiled the water column with depth-discrete metagenomic, physiochemical, and electrochemical analyses. We observed variation in oxidation reduction potential (ORP) in response to sunlight, initiating at depths populated by anoxygenic phototrophs with EET genes. We developed an automated buoy to measure electric current flow between many pairs of electrodes simultaneously, observing correlation in electron consumption to sunlight. Our results, combined with published metatranscriptomic analysis, indicate the occurrence of electron cycling between phototrophic oxidation (electrotrophic metabolism) by Chlorobium and anaerobic respiration (electrogenic metabolism) by Geothrix, involving DOM. We also repeatedly observed gradual seasonal increases in hypolimnion ORP throughout summer. These diel and seasonal patterns imply that electroactive DOM mediates the ecology of electroactive bacteria in lakes, controlling humic lake methane emissions.IMPORTANCEWe investigated the physical, chemical, and redox characteristics of a bog lake and electrodes hung therein to test the hypothesis that dissolved organic matter is being cycled between oxidized and reduced states by electroactive bacterioplankton powered by phototrophy. To do so, we performed field-based analyses on multiple timescales using both established and novel instrumentation. We paired these analyses with recently developed bioinformatics pipelines for metagenomics data to investigate genes that enable electroactive metabolism and accompanying metabolisms. Our results are consistent with our hypothesis and yet upend some of our other expectations. Our findings have implications for understanding greenhouse gas emissions from lakes, including electroactivity as an integral part of lake metabolism throughout more of the anoxic parts of lakes and for a longer portion of the summer than expected. Our results also give a sense of what electroactivity occurs at given depths and provide a strong basis for future studies.

carbon emissions↗

Bedrock weathering rates, reactive nitrogen influxes and effluxes, and nitrous oxide emissions rates from the Pumphouse Hillslope, East River Watershed, Colorado

Atmospheric nitrous oxide contributes directly to global warming, yet models of the nitrogen cycle do not account for bedrock, the largest pool of terrestrial nitrogen, as a source of nitrous oxide. Although it is known that release rates of nitrogen from bedrock are large, there is an incomplete understanding of the connection between bedrock-hosted nitrogen and atmospheric nitrous oxide. Here, we quantify nitrogen fluxes and mass balances at a hillslope underlain by marine shale. We found that at this site bedrock weathering contributes 78% of the subsurface reactive nitrogen, while atmospheric sources (commonly regarded as the sole sources of reactive nitrogen in pristine environments) account for only the remaining 22%. About 56% of the total subsurface reactive nitrogen denitrifies, including 14% emitted as nitrous oxide. The remaining reactive nitrogen discharges in porewaters to a floodplain where additional denitrification likely occurs. We also found that the release of bedrock nitrogen occurs primarily within the zone of the seasonally fluctuating water table and suggest that the accumulation of nitrate in the vadoes zone, often attributed to fertilization and soil leaching, may also include contributions from weathered nitrogen-rich bedrock. Our hillslope study suggests that under oxygenated and moisture-rich conditions, weathering of deep, nitrogen-rich bedrock makes an important contribution to the nitrogen cycle. The data files are in Excel, which can be accessed using Microsoft Office, and consist of many data sets from the Pumphouse Hillslope PLM (Pumphouse Lower Montane) 1, 2, 3, and 4. They include soil to rock (0-10 meters) solid phase minerals and elements compositions; time- and depth-resolved pore-water chemistry and pore-gas compositions; time- and depth-resolved water table depths and water fluxes; subsurface weathering rates; nitrogen influxes and effluxes and mass balance. The attached paper is in a Word document, which can be accessed using Microsoft Office, and in pdf format.

54 ENVIRONMENTAL SCIENCES↗

The free radical chemistry of cloud droplets and its impact upon the composition of rain

Calculations are presented that simulate the free radical chemistries of the gas phase and aqueous phase within a warm cloud during midday. It is demonstrated that in the presence of midday solar fluxes, the heterogeneous scavenging of OH and HO2 from the gas phase by cloud droplets can represent a major source of free radicals to cloud water, provided the accommodation or sticking coefficient for these species impinging upon water droplets is not less than 0.0001. The aqueous-phase of HO2 radicals are found to be converted to H2O2 by aqueous-phase chemical reactions at a rate that suggests that this mechanism could produce a significant fraction of the H2O2 found in cloud droplets. The rapid oxidation of sulfur species dissolved in cloudwater by this free-radical-produced H2O2 as well as by aqueous-phase OH radicals could conceivably have a significant impact upon the chemical composition of rain.

Chameides, W. L.↗

Self-Sealing Mafic Sills for Carbon and Hydrogen Storage

Tabular igneous intrusions (sills) are common features in sedimentary basins and have the potential to be useful seals for fluids (e.g., CO 2 or H 2 ) in geological storage scenarios, and may be important as the need for geologic carbon sequestration and alternative fuel storage increases. This is advantageous in regions without ready access to large-volume reservoirs in depleted hydrocarbon plays and saline aquifers, like the northeastern United States. Moreover, geological H 2 storage requires more demanding conditions than typically associated with oil and gas. An enhanced seal will have the properties of a traditional seal - competent, low permeability, and laterally extensive - with the addition of being able to self-seal pre-existing and induced fractures. Self-sealing will occur along fluid pathways like fractures where CO 2 , water, and minerals like plagioclase, olivine, and pyroxene react together. Dolerite sills from the Gettysburg Basin, Pennsylvania, have remarkably low permeability and homogeneous compositions that include minerals that will readily react with CO 2 dissolved in water. Here, we characterize the physical properties and chemical gradients within several mafic sills cored in five boreholes. In addition, preliminary CO 2 -reaction experiments on dolerite samples demonstrated rapid carbonate mineralization.

58 GEOSCIENCES↗

Biogeochemistry of the Antrim Shale Natural Gas Reservoir

The Antrim Shale, located in the Michigan Basin, United States (U.S.), is a major U.S. shale play having produced over 2.5 Trillion Cubic Feet (Tcf) of unconventional shale natural gas as of 2010. The shallow nature of this formation sets it apart from other, more characterized unconventional shale gas plays. The depth of gas production of the Antrim ranges from approximately 150 to 600 m and it is typically vertically drilled, contrary to deeper, horizontally drilled shales. A thorough understanding of the biogeochemistry and microbiology of this complex system will be advantageous for improving well performance, produced water management, and potential biocidal treatment as microbial community composition can vary substantially even among closely spaced wells. In this study, we analyzed produced water collected from nine different wells in the Antrim Shale by investigating the geochemical and microbial community composition of the produced water to gain greater insight into the overall biogeochemistry of this unique shale system. The majority of the wells from this study had high total dissolved solids (TDS) primarily composed of chloride and sodium, averaging 86,804 mg/L with a maximum 116,223 mg/L; however, three of the wells sampled along the northern margin of the basin exhibited significantly lower TDS ranging from 4932 to 6496 mg/L. Overall, our microbial community analysis revealed relatively low abundance within our samples and high variability of the microbial community among the sampled wells. The majority of bacterial sequences were identified within Proteobacteria, Firmicutes, and Actinobacteria phyla and metagenomic sequencing revealed the low presence of Methanobacteriaceae within each sample. We also investigated potential microbial community drivers and found that TDS, sodium, chloride, iodide, bromide, ammonium, potassium, and strontium were significantly correlated with the observed microbial community. The varying geochemical conditions between wells demonstrate different subsurface environmental niches, potentially driving the heterogeneous microbial communities we observed from well to well. This analysis suggests an important relationship between both well location and geochemistry and the observed microbial community that can persist in the reservoir. Continued studies of the Antrim Shale will improve our understanding of the complex interdependencies of this ecosystem.

03 NATURAL GAS↗

Field Validation of a Pilot-Scale Black Liquor Membrane for Water Removal

Pulp and paper processing is considered one of the most energy-intensive industries in the manufacturing sector. Concentrating black liquor is a particularly energy-intensive process in this industry, used to recover pulping chemicals and generate high-pressure steam from dissolved wood solids. About 7% of pulp and paper energy usage, or nearly 164 trillion British thermal units (Btu) per year, is used to remove water from black liquor in U.S. kraft mills. The U.S. Department of Energy’s Industrial Efficiency and Decarbonization Office is interested in this black liquor membrane technology because it offers the potential for a more energy-efficient and less carbon-intensive kraft pulping process. The membrane is intended to pretreat black liquor to reduce natural gas usage in evaporators that remove water from black liquor. This technology has the potential to be replicated across 99 kraft pulp mills in 24 states. This membrane technology is considered precommercial, and the demonstration was a small-scale side-stream field validation. To make an assessment on performance with a higher level of certainty, additional studies at larger scales are recommended.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

Thompson, David W.↗

Representing methane emissions from wet tropical forest soils using microbial functional groups constrained by soil diffusivity

Tropical ecosystems contribute significantly to global emissions of methane (CH 4 ), and landscape topography influences the rate of CH 4 emissions from wet tropical forest soils. However, extreme events such as drought can alter normal topographic patterns of emissions. Here we explain the dynamics of CH 4 emissions during normal and drought conditions across a catena in the Luquillo Experimental Forest, Puerto Rico. Valley soils served as the major source of CH 4 emissions in a normal precipitation year (2016), but drought recovery in 2015 resulted in dramatic pulses in CH 4 emissions from all topographic positions. Geochemical parameters including (i) dissolved organic carbon (C), acetate, and soil pH and (ii) hydrological parameters like soil moisture and oxygen (O 2 ) concentrations varied across the catena. During the drought, soil moisture decreased in the slope and ridge, and O 2 concentrations increased in the valley. We simulated the dynamics of CH 4 emissions with the Microbial Model for Methane Dynamics-Dual Arrhenius and Michaelis–Menten (M3D-DAMM), which couples a microbial functional group CH 4 model with a diffusivity module for solute and gas transport within soil microsites. Contrasting patterns of soil moisture, O 2 , acetate, and associated changes in soil pH with topography regulated simulated CH 4 emissions, but emissions were also altered by rate-limited diffusion in soil microsites. Changes in simulated available substrate for CH 4 production (acetate, CO 2 , and H 2 ) and oxidation (O 2 and CH 4 ) increased the predicted biomass of methanotrophs during the drought event and methanogens during drought recovery, which in turn affected net emissions of CH 4 . A variance-based sensitivity analysis suggested that parameters related to aceticlastic methanogenesis and methanotrophy were most critical to simulate net CH 4 emissions. This study enhanced the predictive capability for CH 4 emissions associated with complex topography and drought in wet tropical forest soils.

54 ENVIRONMENTAL SCIENCES↗

Sequential Abiotic-Biotic Processes Drive Organic Carbon Transformation in Peat Bogs

Peatlands, which store one-third of the terrestrial carbon (C), are subject to large disturbances under a changing climate. It is crucial to understand how microbial and physiochemical factors affect the vulnerability of these large C stores to predict climate induced greenhouse gas fluxes. Here, we used a combination of mass spectrometry and spectroscopy techniques, to understand sequential biotic and abiotic degradation pathways of Sphagnum fallax leachate in an anaerobic incubation experiment, in the presence and absence of microorganisms. Removal of microorganisms was carried out by passing aqueous samples through 0.2 µm filters. In this work, our results revealed that Sphagnum fallax leachate degradation by abiotic reactions is a significant contributor to CO 2 production. Further, abiotic factors, such as low pH, are responsible for partial dissolved organic carbon (DOC) degradation that produces bioavailable compounds that shift microbial metabolic pathways and stimulate respiration in peat bogs. Acid-catalyzed hydrolysis of Sphagnum-produced glycosides can provide the microbial communities with glucose and stimulate microbial respiration of DOC to CO 2 . These results, while unique to peatlands, demonstrate the importance and underscore the complexity of sequential abiotic and biotic processes on C cycling in peat bogs. It is therefore crucial to incorporate abiotic degradation and sequential below-ground biotic and abiotic interactions into climate models for a better prediction of the influence of climate change on DOC stability in peatlands. These findings might not be representative of other ecosystems with different environmental conditions including mineral-rich peatlands and plant matter in surface peat horizons that comprise discrete microbial populations, and DOC composition.

54 ENVIRONMENTAL SCIENCES↗

Final report on assessment of molten salt corrosion testing of unirradiated and ion irradiated advanced manufactured high entropy alloys

Generation IV reactors and future fusion reactor designs have led to more demanding materials performance requirements due to their increased operating temperatures, corrosive coolants, and increased radiation doses compared to the current light-water reactor fleet. Among the innovative nuclear technologies under development, molten salt reactors stand out for their potential to offer superior fuel utilization, intrinsic safety characteristics, and economic viability. Of the proposed Generation IV designs, the gas fast reactor operates at 450 to 850°C and the molten salt reactor operates at 565 to 850°C, with the molten salt reactor design needing molten salt corrosion resistant materials [1, 2]. These increased temperatures and more extreme corrosion environments necessitate higher material performance, such as creep strength, radiation-tolerant microstructures, corrosion resistance, and high-temperature tensile properties. Hastelloy-N, a nickel-based alloy with additions of molybdenum and chromium, has been successfully employed to contain molten fluoride salt at temperatures up to 705°C. However, Hastelloy-N becomes embrittled upon neutron irradiation, primarily due to the accumulation of helium produced by (n,a) transmutation reactions. Furthermore, the corrosive nature of molten fluoride and chloride salts presents a formidable challenge, as these salts can react with and dissolve alloying elements such as Cr, Mo, and Fe, leading to selective leaching, loss of protective oxide layers, and accelerated degradation. High entropy alloys (HEAs) and refractory high entropy alloys (RHEAs) have emerged as a prominent area of interest, due to their ability to achieve tailored chemical compositions for specific applications. Unlike conventional alloys, HEAs are characterized by having multiple principal elements in equimolar or near equimolar ratios, leading to an unconventional alloying strategy [3]. This alloying strategy is believed to promote unique properties, such as single-phase stabilization of chemically compatible elements, lattice distortion effects due to atomic radius differences, and proposed sluggish diffusion effects. For extreme-environment applications, RHEAs have garnered much research interest because of the possibility of creating relatively ductile materials that can operate in extremely high-temperature environments, beyond the operating temperatures where other Ni-based superalloys begin to lose strength [4-6]. Idaho National Laboratory (INL) initiated a joint international effort with the Czech Republic to explore the feasibility of manufacturing HEAs for high-temperature nuclear applications using advanced manufacturing. This effort was funded at INL by the United States Department of Energy's Office of Nuclear Energy under the Advanced Reactor Technologies and Advanced Materials and Manufacturing Technologies (AMMT) Program. The HEAs were specifically designed for the corrosive and irradiation environments experienced in gas-cooled fast reactors, molten salt reactors, and fusion power. These alloys have been manufactured by multiple processes to determine the impact of manufacturing processes on the performance of the alloys in corrosive and irradiation environments. Preliminary molten salt corrosion testing showed that equimolar MoNbTiV and MoNbTi alloys exhibit exceptional performance, with arc-melted variants demonstrating only minimal degradation after 1000 hours of exposure to molten chloride salt at 700°C. Conversely, Nb2TiVZr2 showed significant molten salt corrosion susceptibility and microstructural instability during high-temperature molten salt exposures, and was, therefore deemed unfit for molten salt reactor applications. The MoNbTiV, MoNbTi, and Nb2TiVZr2 alloys were further evaluated through ion irradiation experiments conducted at the Michigan Ion Beam Laboratory at the University of Michigan. The microstructural stability and the evolution of irradiation-induced defects were characterized to assess the irradiation resistance of each of these alloys.

36 - MATERIALS SCIENCE↗

Molecular Simulation of Lithium Carbonate Reactive Vapor–Liquid Equilibria Using a Deep Potential Model

We developed a first-principles machine learning model for the reactive vapor–liquid phase behavior of molten Li 2 CO 3 . The model was trained on ab initio electronic density functional theory data using the Deep Potential (DP) methodology, and its accuracy was evaluated by comparing model predictions of density and viscosity to experimental measurements. Direct coexistence simulations with the DP model over time scales of tens of nanoseconds were used to observe equilibrium dissociation of Li 2 CO 3 into CO 2 residing primarily in the vapor phase and Li 2 O which remains dissolved in the liquid. The simulations covered a range of temperatures, overall system sizes, and vapor-to-liquid volume ratios. Results were analyzed in terms of the observed chemical composition of the liquid and vapor phases, product structure, and CO 2 partial pressures. In addition, we calculated equilibrium constants for the dissociation reaction by assuming ideal-solution behavior for the liquid. As expected on the basis of thermodynamic arguments and prior experiments for this system, the observed partial pressure of CO 2 in the gas phase depends on both the temperature and the ratio of vapor to liquid volumes, while the calculated equilibrium constants only depend on temperature. DP model predictions for the equilibrium constant of the reaction are generally consistent with the available experimental measurements. Furthermore, the present study establishes the validity of the DP methodology for the description of reactive, multiphase equilibria from first principles, with possible applications to many other systems of scientific and technological interest even in the absence of relevant experimental measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗