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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
DOE OSTI2022

Iron precipitation under controlled oxygen flow: Mineralogical implications for BIF precursors in the Archean ocean

Banded iron formation (BIF) deposition in the Archean ocean is thought to have been initiated by the oxidation of dissolved iron into ferric primary precursor phases that descended through the water column and were deposited on the seafloor. Effective interpretation of the trace element and isotopic composition of BIFs in the geologic record requires an understanding of the identity and longevity of those precursor phases. Temporal and spatial variation in oxidant concentration and ocean chemistry may have driven precursor mineralogy. Furthermore, precursor phases may undergo transitions during descent and burial. This experimental study follows the evolution of iron mineralogy, speciation, and redox state during the precipitation of iron under variable oxygen fluxes and in fluids containing different iron-complexing anions (chloride, sulfate, and phosphate). Additionally, suspensions collected after incomplete oxidation were anoxically aged to simulate changes to precursor mineralogy during descent below the seawater redoxcline. Results from X-ray diffraction, sequential dissolution, colorimetric determination of Fe redox state, and Fe K-edge X-ray absorption fine structure spectroscopy showed that under all experimental conditions, intermediate precipitates collected before complete iron uptake contained mineralized ferrous iron. Purely ferric mineral assemblages were not observed until iron was removed from solution. In low-oxygen experiments, intermediate precipitates contained phases with stoichiometric Fe 2+ , including magnetite, vivianite, and green rust (GR). Chloride green rust (GR1) had more ferric iron than sulfate green rust (GR2) and more readily transitioned to magnetite via disproportionation. GR2 was stable over a broader range of iron uptake; magnetite appeared mainly as an additional oxidation product in sulfate solution. In high oxygen experiments, mineralized ferrous iron occurred in amorphous phases or as a non-stoichiometric component in ferric oxides; final ferric assemblages were less crystalline than in low-oxygen equivalents. Low concentrations of phosphate increased the total iron oxidation rate, but also increased the ferrous content of intermediate precipitates. The incorporation of phosphate stabilized GR2 and facilitated GR2 precipitation over a larger range of iron uptake. In higher concentrations of phosphate, vivianite and poorly crystalline ferric hydroxides formed in place of GR. Here, these findings suggest that over a range of possible ocean chemistries, mixed-valence phases may have been short lived but relevant precursors to BIF. Additionally, anionic chemistry and oxidant concentration are shown to influence the crystallinity and chemical resistivity of final ferric assemblages, affecting their reactivity during later anoxic burial.

58 GEOSCIENCES↗
DOE OSTI2022

Synergies between H, He and radiation damage in dual and triple ion irradiation of candidate fusion blanket materials

Three ferritic/martensitic alloys were studied to understand the synergistic effect between single ion beam (Fe 2+ ), dual ion beam (Fe 2+ +He 2+ and Fe 2+ +H + ), and triple ion beam (Fe 2+ +He 2+ +H + ) irradiations on cavity evolution. A commercial alloy, F82H, a castable nanostructured alloy, CNA3, and a high purity model alloy, Fe8Cr2W, were irradiated at 400°C to 600°C to a damage level of 50 dpa at a damage rate of 1 × 10 –3 dpa/s with He and H injection rates of 10 and 40 appm/dpa, respectively. Post-irradiation characterization via bright field transmission electron microscopy and high-angle annular dark-field scanning transmission electron microscopy was performed on all irradiated conditions to characterize the cavity size distribution and determine the effects of H/He injection on cavity microstructure. In all three alloys, hydrogen co-injection with helium resulted in an increased cavity number density and maximum cavity size, producing an increase in swelling over that from helium injection alone. Swelling in F82H appears to peak between 450°C and 500°C. At 600°C, swelling was minimal and cavities of high density and small size were confined to grain boundaries and dislocations while at 400°C, swelling is also low with a nearly homogeneous, high density, distribution of very small cavities throughout. Swelling was least in the commercial alloy F82H due to the high sink strength. The CNA3 alloy underwent dissolution of precipitates that lowered the sink strength and resulted in higher swelling than F82H, but less than the model alloy. Electron energy loss spectroscopy (EELS) elemental mapping revealed hydrogen forming a halo-like structure about the periphery of the cavities and helium residing within the cavities themselves. Finally, this observation suggests that hydrogen reduces the surface energy of helium-filled cavities which results in both increased cavity number density and cavity size in triple beam irradiation over dual beam irradiation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Investigation of Nanoparticle Degradation in Hydrogen Fuel Cell Systems through Automated Electron Microscopy

Proton exchange membrane fuel cells (PEMFC) are promising devices for the deployment of hydrogen-powered heavy-duty vehicles, providing a higher efficiency for similar driving range and fueling time than the existing ones. However, PEMFCs still encounter durability challenges mainly due to catalyst degradation in the cathode. Mitigating these performance losses requires a better understanding of the degradation mechanisms under heavy-duty accelerated stress tests (ASTs) [1]. Scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) are key tools for the analysis of Pt and PtCo nanoparticle size, spatial distribution and composition [2]. Electron tomography is also used to determine the rate and type of degradation of catalyst nanoparticles as a function of their position on the carbon support. In this work, automated data acquisition software, paired with a custom Python code, have been used to study the effect of different accelerated stress tests (ASTs) on nanoparticle coarsening [2]. Figure 1 shows high-angle annular dark-field (HAADF)-STEM images and EDS maps comparing the cathodes of membrane electrode assemblies (MEAs) following an electrocatalyst AST performed under H2/N2 with that of the heavy-duty AST performed under H2/air. We will discuss how AST conditions affect considerably the spatial distribution of the nanoparticles across the electrode between the membrane and microporous layer. Although the median particle size increased more in the MEA aged under the heavy-duty AST, as determined using a high-throughput image analysis, the quantitative EDS measurements demonstrate that the electrocatalyst AST resulted in more Pt and Co dissolution from the cathode, which is another important indicator of electrocatalyst degradation. We will further present the impact of the relative humidity (% RH) on the degradation mechanisms demonstrated using the same approach. Electron tomography has been used to distinguish the Pt nanoparticles residing on the carbon support surface (exterior) from those within the pore structure (interior) in order to determine the relative stability of interior and exterior nanoparticles. As shown in Figure 2, we will compare the Pt catalyst particle size at the beginning of test (BOT) and end of test (EOT), and discuss the importance of automating the electron tomography workflow, i.e. acquisition, reconstruction, and visualization, to increase sampling and determine the standard deviation of these measurement. The outlook for utilizing low-dose cryo-tomography for limiting damage to the catalyst, support, and especially proton-conducting ionomer will also be discussed [3].

Amichi, Lynda↗
DOE OSTI2019

Initiation and Development of Wetlands in Southern Florida Karst Landscape Associated With Accumulation of Organic Matter and Vegetation Evolution

Biological processes can exert important controls on geomorphic evolution in karst landscapes, because carbonate mineral dissolution is augmented and spatially focused by the production of CO 2 and biogenic acids from organic matter (OM) decomposition. In Big Cypress National Preserve (BICY) in southwest Florida (USA), depressional wetlands embedded in a mosaic of pine uplands exhibit regular patterning. To understand the impact of OM decomposition as well as different OM sources on carbonate dissolution and landscape patterning, we measured bulk OM property and biomarker proxies (fatty acids and lignin phenols) in different zones (center vs. edge) of the depressional wetlands. We also constructed age profiles of sediment accretion and pattern genesis using 210Pb activities and compound- specific radiocarbon analysis (CSRA) of long-chain fatty acids. Bulk OM and biomarker data indicate rapid OM accumulation in wetland centers resulting from high primary production and near permanent inundation, in contrast to negligible OM accumulation at wetland edges. Age discontinuities suggest episodic periods of near complete OM loss due to decomposition and/or fire. Based on CSRA, landscape patterning likely initiated in the mid-to-late Holocene, with wetlands at slight higher elevation initiated earlier than wetlands at lower elevation. Bulk stable isotope and lignin phenol biomarkers indicate wetland vegetation was initially dominated by herbaceous species and shifted to woody dominated vegetation as landscape hydrology adjusted to changing precipitation. The rate of weathering is likely impacted by hydrological conditions, vegetation dynamics and environmental perturbations like precipitation and fires, suggesting that this karst landscape is a manifestation of complex ecosystem feedbacks.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1998

Ground Based Program for the Physical Analysis of Macromolecular Crystal Growth

During the past year we have focused on application of in situ Atomic Force Microscopy (AFM) for studies of the growth mechanisms and kinetics of crystallization for different macromolecular systems. Mechanisms of macrostep formation and their decay, which are important in understanding of defect formation, were studied on the surfaces of thaumatin, catalase, canavalin and lysozyme crystals. Experiments revealed that step bunching on crystalline surfaces occurred either due to two- or three-dimensional nucleation on the terraces of vicinal slopes or as a result of uneven step generation by complex dislocation sources. No step bunching arising from interaction of individual steps in the course of the experiment was observed. The molecular structure of the growth steps for thaumatin and lipase crystals were deduced. It was further shown that growth step advance occurs by incorporation of single protein molecules. In singular directions growth steps move by one-dimensional nucleation on step edges followed by lateral growth. One-dimensional nuclei have different sizes, less then a single unit cell, varying for different directions of step movement. There is no roughness due to thermal fluctuations, and each protein molecule which incorporated into the step remained. Growth kinetics for catalase crystals was investigated over wide supersaturation ranges. Strong directional kinetic anisotropy in the tangential step growth rates in different directions was seen. The influence of impurities on growth kinetics and cessation of macromolecular crystals was studied. Thus, for catalase, in addition to pronounced impurity effects on the kinetics of crystallization, we were also able to directly observe adsorption of some impurities. At low supersaturation we repeatedly observed filaments which formed from impurity molecules sedimenting on the surfaces. Similar filaments were observed on the surfaces of thaumatin, canavalin and STMV crystals as well, but the frequency was low compared with catalase crystallization. Cessation of growth of xylanase and lysozyme crystals was also observed and appeared to be a consequence of the formation of dense impurity adsorption layers. Attachment: "An in situ AFM investigation of catalase crystallization", "Atomic force microscopy studies of living cells: visualization of motility, division, aggregation, transformation, and apoptosis", AFM studies on mechanisms of nucleation and growth of macromolecular crystals", and "In situ atomic force microscopy studies of surface morphology, growth kinetics, defect structure and dissolution in macromolecular crystallization".

Malkin, Alexander J.↗
NASA NTRS2020

Cycling phosphorus on the Archean Earth: Part II. Phosphorus limitation on primary production in Archean ecosystems

Several lines of evidence point to low rates of net primary production (NPP) in Archean oceans. However, whether Archean NPP was limited by electron donors or nutrients, particularly phosphorus (P), and how these factors might have changed over a billion years of recorded Archean history, remains contentious. One major challenge is to understand quantitatively the biogeochemical cycling of P on the early Earth. In Part I of this series (Hao et al., 2020), we estimated the weathering flux of P to the oceans as a function of temporally increasing continental emergence and elevation through Archean time. In Part II, we conduct thermodynamic and kinetic simulations to understand key processes of P cycling within the Archean ocean, including seafloor weathering, recycling of organic P, the solubility and precipitation of secondary phosphate minerals, and the burial diagenesis of P precipitates. Our calculations suggest low solubilities of apatite minerals in Archean seawater, primarily due to nearly neutral pH and high levels of Ca. This low solubility, in turn, implies a negligible contribution of apatite dissolution to P bioavailability in Archean seawater. We also simulate the solubility limits of common secondary P-bearing minerals, showing that vivianite would have been the least soluble P mineral in ferruginous Archean seawater (0.1–0.3 µM), even at moderate supersaturation states (Ω = 100 or 1000). If vivianite precipitation was kinetically favorable by microbial activities and mineral adsorption, the sinking flux of P as vivianite in Archean seawater could have reached the modern sinking flux, implying that vivianite precipitation was a potentially major sink for P in Archean oceans. During burial diagenesis, however, vivianite in porewater would have become less stable than Ca-phosphates of lower solubility. At elevated temperatures (>100 °C) associated with burial diagenesis and low-grade metamorphism, vivianite is predicted to react irreversibly with calcite to form apatite. Optimistic assumptions about the recycling efficiency of P on the Archean Earth lead us to estimate that by the end of the eon the total flux of P (continental weathering + recycling) could have supported NPP at levels up to 7% of the modern. The total flux of P would have been much lower on the early and middle Archean Earth, whereas fluxes of electron donors could have been higher, suggesting very low productivity and P-limitation of marine ecosystems during much of the eon. Comparing our estimates of NPP as limited by P supply with the estimate by Ward et al. (2019), in which NPP was limited by electron donors and metabolic efficiency, there could have been a transition between P-limited productivity in the early to middle Archean to electron donor-limitation closer to the eon’s end (assuming no oxygenic photosynthesis). Once oxygenic photosynthesis reached ecological significance, probably near the end of the Archean, our estimated flux of P would allow rapid oxidation of atmosphere.

Vivianite↗
DOE OSTI2024

The role of annealing and grain boundary controls on the mechanical properties of limestones and marbles

Chemical and mechanical processes are coupled in many geological and geochemical environments. Reactive processes anneal defects and restructure grain boundaries, modifying their elastic properties, levels of internal friction, wave propagation rates and fracture behaviors. The nature of these changes is, however, contingent on the initial state of the rock. Here, in this study, impulse excitation was used to measure changes in mechanical properties as a function of dry and steam heating time at 300 °C for three carbonate rocks: Carrara marble, Carthage marble (Burlington Limestone), and Texas Cream limestone (Edwards limestone), with initial porosities of about 1 %, 3 %, and 27 %, respectively. Frequency-dependent phenomena along with mineral recrystallization were observed. This was coupled with small-angle X-ray and neutron scattering analysis to determine the relationship between changes in bulk mechanical and microstructural properties. An observed decrease in both the Young's and shear moduli in the experimental limestones as a function of heating time reflects and quantifies a reduction in the stiffness of the rock due to annealing. The internal friction of the samples first increases then decreases with reaction time, reflecting defect annealing, but this was balanced against grain boundary dissolution apparently driven by condensation of steam in the confined grain-boundary environment. This suggests an increase in the boiling point under confinement leading to dissolution, increased porosity and widening of the grain boundaries. In addition, comparison of small-angle X-ray and neutron scattering results suggests that it is inappropriate to assume that pores are empty for quantitative analysis of typical small-angle scattering samples.

58 GEOSCIENCES↗
DOE OSTI2019

Unveiling the Role of Al 2 O 3 in Preventing Surface Reconstruction During High-Voltage Cycling of Lithium-Ion Batteries

Recent achievements in high-energy batteries have been made by using Ni-rich NMC cathodes (LiNi x Mn y Co 1–x–y O 2 with x > 0.5) in conjunction with higher cell voltages. However, these gains have come at a cost of fast capacity fade and poor rate performace. In our previous study, we showed that Al 2 O 3 ALD coatings on LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) and LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) cathodes prevented surface phase transitions, reduced impedance, and extended cycle life in high voltage cells. In this work, neutron diffraction (ND), X-ray photoelectron spectroscopy (XPS), and electron energy loss spectroscopy (EELS) are used to fully investigate the mechanism by which ALD surface coatings mitigate NMC811 cathode degredation. Refinement of ND patterns indicated no changes in the bulk crystal structure of cycled cathodes with or without the Al 2 O 3 coating. Rather, the improved performance of ALD-coated cathodes is clearly due to surface stabilization. EELS established that all three transition metal oxidation states were reduced at the surface of the uncoated cathode after cycling, whereas the coated cathode showed no changes in surface oxidation states relative to the bulk. The surface coatings also prevented transition metal dissolution and crossover. XPS analysis of the anode harvested from cycled cells with uncoated cathodes showed significant amounts of Mn deposited within the SEI. In contrast, no Mn could be detected on the anodes cycled with coated cathodes. These results affirm that ALD coatings can effectively reduce the reactivity of the NMC surface and prevent detrimental side reactions that shorten battery cycle life.

25 ENERGY STORAGE↗
DOE OSTI2022

SEI formation mechanisms and Li + dissolution in lithium metal anodes: Impact of the electrolyte composition and the electrolyte-to-anode ratio

The lithium metal battery is one of today's most promising high-energy-density storage devices. Its full-scale implementation depends on solving operational and safety issues intrinsic to the Li metal high reactivity leading to uncontrolled electrolyte decomposition and uneven Li deposition. In this work, we study the spontaneous formation of the solid electrolyte interphase (SEI) upon contact of Li metal with the electrolyte and describe the heterogeneous SEI morphological features. Multiple electrolyte formulations based on lithium bis(fluorosulfonyl)imide (LiFSI), dimethoxyethane (DME), dimethyl carbonate (DMC), 1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) and bis(2,2,2-trifluoroethyl) ether (BTFE) are used. Findings include the description of the SEI evolution from dispersed LiO, LiS, LiN, and LiF clusters to a continuous and compact inorganic phase in which the LiO and LiF content depend on the presence of fluorine diluents. Further, the role of the DME ether solvent helping the growth of a “wet-SEI” is compared to that of the highly unstable carbonate DMC, which decomposes into complex radical oligomers that might contribute to further electrolyte decomposition. The impact of the electrolyte-to-anode ratio on LiFSI decomposition is highlighted. Finally, we suggest the existence of a critical LiFSI concentration and electrolyte-to-anode ratio that could potentially balance the rate of electrolyte depletion and lithium consumption.

25 ENERGY STORAGE↗
DOE OSTI2023

Polysulfide regulation by defect-modulated Ta 3 N 5- x electrocatalyst toward superior room-temperature sodium-sulfur batteries

Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metal-sulfur batteries. Motivated by a theoretical prediction, herein, we strategically propose nitrogen-vacancy tantalum nitride (Ta 3 N 5-x ) impregnated inside the interconnected nanopores of nitrogen-decorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in room-temperature sodium-sulfur batteries. Through a pore-constriction mechanism, the nitrogen vacancies are controllably constructed during the nucleation of Ta 3 N 5-x . Further, the defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level, not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials, but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion. Moreover, the interconnected continuous Ta 3 N 5-x -in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior. Due to these attributes, the as-developed Ta 3 N 5-x -based electrode achieves superior rate capability of 730 mAh g -1 at 3.35 A g -1 , long-term cycling stability over 2000 cycles, and high areal capacity over 6 mAh cm -2 under high sulfur loading of 6.2mgcm -2 . This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries, but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.

25 ENERGY STORAGE↗
DOE OSTI2023

Mixing Study for the Modification of H-Canyon Tank 31 and 32 Recirculation Lines Via M-Star®

As a part of the Accelerated Basin De-Inventory (ABD) program Tanks 31 or 32 will be re-purposed to support increasing the number of annual Material Test Reactor (MTR) and High Flux Isotope Reactor (HFIR) dissolutions. The proposed plan will allow Tanks 31 or 32 to be used as the dissolver cold chemical solution makeup tank and storage tank. The dissolver cold chemicals are 50% nitric acid, process water, mercuric nitrate, and gadolinium nitrate. Tanks 31 and 32 are 9 ft. (outer diameter) x 36 ft, horizontal, and can hold approximately 56,000 liters (15,000 gallons) each. One full volume of Tanks 31 or 32 can support 4 HFIR 6.4D equivalent batches. Both tanks are equipped with liquid level instrumentation. Tank 31 is equipped with 1 pump used for transfer and recirculation while Tank 32 is equipped with two pumps, one for transfer and the other for recirculation. Each of the pumps is equipped with sample taps. The tanks do not have specific gravity instrumentation, an agitator, or a sampler. Piping modifications will also be performed to supply the tank with cold chemicals. The current dissolver chemical composition is 5.0 -8.5M HNO3 and ~0.2 g Gd/L. The recirculating pump connected to Tank 31 is rated for a flowrate 175 gpm while the pump connected to Tank 32 is rated for a flowrate 50 gpm.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Grain boundary widening controls siderite (FeCO3) replacement of limestone (CaCO3)

Abstract The microstructure of minerals and rocks can significantly alter reaction rates. This study focuses on identifying transport paths in low porosity rocks based on the hypothesis that grain boundary widening accelerates reactions in which one mineral is replaced by another (replacement reaction). We conducted a time series of replacement experiments of three limestones (CaCO 3 ) of different microstructures and solid impurity contents using FeCl 2 . Reacted solids were analyzed using chemical imaging, small angle X-ray and neutron scattering and Raman spectroscopy. In high porosity limestones replacement is reaction controlled and complete replacement was observed within 2 days. In low porosity limestones that contain 1–2% dolomite impurities and are dominated by grain boundaries, a reaction rim was observed whose width did not change with reaction time. Siderite (FeCO 3 ) nucleation was observed in all parts of the rock cores indicating the percolation of the solution throughout the complete core. Dolomite impurities were identified to act as nucleation sites leading to growth of crystals that exert force on the CaCO 3 grains. Widening of grain boundaries beyond what is expected based on dissolution and thermal grain expansion was observed in the low porosity marble containing dolomite impurities. This leads to a self-perpetuating cycle of grain boundary widening and reaction acceleration instead of reaction front propagation.

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

Biological response of eelgrass epifauna, Taylor's Sea hare ( Phyllaplysia taylori ) and eelgrass isopod ( Idotea resecata ), to elevated ocean alkalinity

Abstract. Marine carbon dioxide removal (mCDR) approaches are under development to mitigate the effects of climate change by sequestering carbon in stable reservoirs, with the potential co-benefit of local reductions in coastal acidification impacts. One such method is ocean alkalinity enhancement (OAE). A specific OAE method is the generation of aqueous alkalinity via electrochemistry to enhance the alkalinity of the receiving water by the extraction of acid from seawater, thereby avoiding the issues of solid dissolution kinetics and the release of impurities into the ocean from alkaline minerals. While electrochemical acid extraction is a promising method for increasing the carbon dioxide sequestration potential of the ocean, the biological effects of increasing seawater alkalinity and pH within an OAE project site are relatively unknown. This study aims to address this knowledge gap by testing the effects of increased pH and alkalinity, delivered in the form of aqueous NaOH, on two eelgrass epifauna in the US Pacific Northwest, Taylor's sea hare (Phyllaplysia taylori) and eelgrass isopod (Idotea resecata), chosen for their ecological importance as salmon prey and for their role in eelgrass ecosystems. Four-day experiments were conducted in closed bottles to allow measurements of the evolution of carbonate species throughout the experiment, with water refreshed twice daily to maintain elevated pH, across pHNBS (NBS standard scale) treatments ranging from 7.8 to 9.3. Sea hares experienced mortality in all pH treatments, ranging from 37 % mortality at pHNBS 7.8 to 100 % mortality at pHNBS 9.3. Isopods experienced lower mortality rates in all treatment groups, ranging from 13 % at pHNBS 7.8 to 21 % at pHNBS 9.3, which did not significantly increase with higher pH treatments. These experiments represent an extreme of constant exposure to elevated pH and alkalinity, which should be considered in the context of both the natural variation and the dilution of alkalinity experienced by marine communities across an OAE project site. Different invertebrate species will likely have different responses to increased pH and alkalinity, depending on their physiological vulnerabilities. Investigation of the potential vulnerabilities of local marine species will help inform the decision-making process regarding mCDR planning and permitting.

marine carbon dioxide removal↗
DOE OSTI2023

Chemical composition, coordination, and stability of Ca–organic associations in the presence of dissolving calcite

Environmental biotic and abiotic factors and soil physical, mineralogical, and chemical properties control the chemical composition of soil organic matter (SOM). Particularly, soil mineralogy and the presence of multivalent cations affect SOM labile fraction composition, stability, and environmental persistence. The persistence of SOM in aridic or limestone deposit derived soils, i.e., calcareous soils, has been partially attributed to SOM stabilization through adsorption or inclusion into the calcite mineral structure. Recently, however, it was shown that Ca(aq) released during calcite dissolution formed aqueous Ca–organic associations with OM components, which were unbound to mineral surface sites. This study investigates the structure, composition, and coordination of these associations by characterizing lyophilized Ca–organic containing solutions with spectromicroscopy [Scanning Transmission X-ray Microscopy (STXM)] and with a nanoimaging chemical probe [Infrared scattering-Scanning Nearfield Optical Microscopy (IR s-SNOM)]. Chemical stability of Ca–organic associations is furthermore determined with pyrolysis mass spectrometry analysis. The results demonstrate that Ca–organic associations are formed in the presence of dissolving calcite and OM components relevant to soil chemistry, i.e., lignin and amino acids. This study further reveals a spatial homogeneity of solution-derived (bi) carbonate in Ca–organic associations indicating for the first time that an inorganic anion, such as (bi)carbonate, may be part of these associations. Most likely, Ca ions are bound to both the (bi)carbonate and the organic components. These Ca (bi)carbonate–organic associations seem to have greater chemical stability than the pristine organic mixtures and, possibly, a higher environmental stability and reduced mineralization rate.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1992

Environmental fatigue of an Al-Li-Cu alloy. Part 2: Microscopic hydrogen cracking processes

Based on a fractographic analysis of fatigue crack propagation (FCP) in Al-Li-Cu alloy 2090 stressed in a variety of inert and embrittling environments, microscopic crack paths are identified and correlated with intrinsic da/dN-delta K kinetics. FCP rates in 2090 are accelerated by hydrogen producing environments (pure water vapor, moist air, and aqueous NaCl), as defined in Part 1. For these cases, subgrain boundary fatigue cracking (SGC) dominates for delta K values where the crack tip process zone, a significant fraction of the cyclic plastic zone, is sufficiently large to envelop 5 micron subgrains in the unrecrystallized microstructure. SGC may be due to strong hydrogen trapping at T1 precipitates concentrated at sub-boundaries. At low delta K, the plastic zone diameter is smaller than the subgrain size and FCP progresses along (100) planes due to either local lattice decohesion or aluminum-lithium hydride cracking. For inert environments (vacuum, helium, and oxygen), or at high delta K where the hydrogen effect on da/dN is small, FCP is along (111) slip planes; this mode does not transition with increasing delta K and plastic zone size. The SGC and (100) crystallographic cracking modes, and the governing influence of the crack tip process zone volume (delta K), support hydrogen embrittlement rather than a surface film rupture and anodic dissolution mechanism for environmental FCP. Multi-sloped log da/dN-log delta K behavior is produced by changes in process zone hydrogen-microstructure interactions, and not by purely micromechanical-microstructure interactions, in contradiction to microstructural distance-based fatigue models.

Robert S Piascik↗
DOE OSTI2019

Enhanced Corrosion of Magnesium as a Treatment for Legacy SNF - 19369

The ability of high concentrations of MgCl{sub 2} to induce activity-controlled dissolution of magnesium has been investigated in the context of providing a means of stabilising reactive metal fuel wastes, as oxide/hydroxide corrosion products, to enhance the resilience of the waste form following disposal. Kinetic parameters were measured using a novel immersion testing method that utilise the gravimetric measurement of evolving hydrogen produced by the oxidation of the metal. This method demonstrates extremely high precision relative to a traditional volumetric approach and appears to be relatively robust in its accuracy despite its sensitivity to changing temperature. An effective activation energy of 10.2 kJmoL{sup -1} was measured for the reaction using the Arrhenius equation over a temperature range of 30-70 deg. C. This implies that the reaction remains controlled by the diffusion of reactants to the metal surface and fails to corroborate the effect previously observed by Casey and Bergeron. This may be explained by differences in initial conditions, or it could be that the system transitions into the previously observed state as it reaches equilibrium, a possibility that was not accounted for in this study as the experiments focussed on measuring the initial rate of reaction. Repeat testing and further study is warranted given that enhanced corrosion could offer a means to produce a self-immobilising waste form with minimal intrusion, offering both improved safety tolerances and cost savings for the decommissioning and waste disposal efforts ongoing at the Sellafield site. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Factors affecting the reactivity of slag at early and late ages

This study investigates the difference between the reactivity of slag in NaOH solution (w/s = 100) and in cement paste (w/b = 0.4). The reactivity of slag is much higher in NaOH solution than in cement paste. When the NaOH solution is saturated with portlandite, the rate of reaction of slag decreases to approach that in cement paste. This suggests that the slower reaction of slag in cement paste might be due to the presence of calcium ions released by the clinker phases. At 28 days, relative humidity measurements indicate that water is only present in pores less than 6 nm. Above 6 nm, hydration cannot take place due to the lack of water. From a thermodynamic point of view, the small size of water filled pores may slow down the slag reaction due to the high concentration of species in solution required for hydrate growth to balance the increase of the surface energy.

36 MATERIALS SCIENCE↗
NASA NTRS2013

Towards Probablistic Assessment of Hypobaric Decompression Sickness Treatment

INTRODUCTION: Pressure, oxygen (O2), and time are the pillars to effective treatment of decompression sickness (DCS). The NASA DCS Treatment Model links a decrease in computed bubble volume to the resolution of a symptom. The decrease in volume is realized in two stages: a) during the Boyle's Law compression and b) during subsequent dissolution of the gas phase by the O2 window. METHODS: The cumulative distribution of 154 symptoms that resolved during repressurization was described with a log-logistic density function of pressure difference (deltaP as psid) associated with symptom resolution and two other explanatory variables. The 154 symptoms originated from 119 cases of DCS during 969 exposures in 47 different altitude tests. RESULTS: The probability of symptom resolution [P(symptom resolution)] = 1 / (1+exp(- (ln(deltaP) - 1.682 + 1.089×AMB - 0.00395×SYMPTOM TIME) / 0.633)), where AMB is 1 when the subject ambulated as part of the altitude exposure or else 0 and SYMPTOM TIME is the elapsed time in min from start of the altitude exposure to recognition of a DCS symptom. The P(symptom resolution) was estimated from computed deltaP from the Tissue Bubble Dynamics Model based on the "effective" Boyle's Law change: P2 - P1 (deltaP, psid) = P1×V1/V2 - P1, where V1 is the computed volume of a spherical bubble in a unit volume of tissue at low pressure P1 and V2 is computed volume after a change to a higher pressure P2. V2 continues to decrease through time at P2, at a faster rate if 100% ground level O2 was breathed. The computed deltaP is the effective treatment pressure at any point in time as if the entire deltaP was just from Boyle's Law compression. DISCUSSION: Given the low probability of DCS during extravehicular activity and the prompt treatment of a symptom with options through the model it is likely that the symptom and gas phase will resolve with minimum resources and minimal impact on astronaut health, safety, and productivity.

Conkin, J.↗