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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Characterization of Arsenic and Selenium in Coal Fly Ash to Improve Evaluations for Disposal and Reuse Potential (Final Technical Report)

Coal fly ash is a high volume waste material that is discarded in landfills and surface water impoundments across the U.S. and is also widely recycled for a variety of applications. The leaching of potential of contaminants of concern, such as arsenic (As) and selenium (Se), is often the driver of risk assessments for coal ash disposal and reuse. The extent of leachable As and Se depends on several factors related to environmental conditions and fly ash characteristics. Previous studies employed various methods to delineate the concentration, chemical form, and distribution of As and Se in fly ash materials. However, few studies have attempted to directly correlate these properties to mobilization parameters relevant to disposal and reuse. Instead, the coal residuals industries often rely upon standardized leaching protocols that can be laborious or involve hazardous chemicals. The goals of the project were to: 1) Develop and evaluate a characterization protocol that can be used to screen fly ash samples for leachability of As and Se; 2) Characterize As, Se, and associated constituents of fly ash particles at multiple length scales (nanometer to micrometer) to determine if elemental associations differ as a function of the resolution of characterization; and 3) Establish a predictive model for the chemical composition of coal ash produced annually at major U.S. coal fired power facilities on 50-year national coal supply records. For the first objective, we performed leaching experiments with 52 fly ash samples collected from 15 different U.S. power plants and representing coal feedstocks from the three major domestic coal regions. For this work, we assessed the mobilization potential of As and Se in fly ash based on standardized leaching protocols and performed multivariate and lasso regression analyses to explore correlations of leachable As and Se contents with characteristics such as major element contents, loss on ignition (LOI) and pH. The results of regression models indicated that major elements (Fe, Ca, Al) for a wide range of fly ashes can serve as predictor variables for the leaching potential of As, but not for Se. LOI and pH were not important predictive variables in the models. Both regression approaches resulted in relatively strong fits for leachable As (correlation coefficient R 2 = 0.78 for both models) compared to models for leachable Se (R 2 = 0.49). Overall, these results suggest that correlation models combined with on-site elemental analysis with portable analyzers may enable a screening method for leachable As in coal ash. For the second objective, we utilized nanoscale 2-D imaging (30-50 nm spot size) with the Hard X-ray Nanoprobe (HXN) in combination with microprobe X-ray capabilities (~5 µm resolution) to determine As and Se elemental associations in fly ash particles. Speciation of As and Se was also measured at the nano- to microscale with X-ray absorption spectroscopy. The enhanced resolution of HXN showed As and Se that were diffusely located around or comingled with Ca- and Fe-rich particles. The results also showed nanoparticles of Se attached to the surface of fly ash grains. Overall, a comparison of As and Se species across scales highlights the heterogeneity and complexity of chemical associations for these trace elements of concern in coal fly ash. For the final objective, we developed a predictive model for major element composition of coal ash in reserve at disposal sites of major U.S. coal fired power plants. This model was constructed from coal purchase records of 705 power stations from 1973-2022 and was trained on coal ash composition data showing that coal ash elemental composition is strongly associated with the source of feedstock coal. The model showed regional shifts in the major element contents of ash produced by power plants in the last 50 years, particularly for calcium and iron (expressed as %CaO and %Fe 2 O 3 ), as coal-fired power stations changed their source of coal over this time frame. Our approach enables an estimation of coal ash chemical composition that is stored in waste impoundments at individual power stations. Such information can help delineate the regional market potential for material applications that would utilize coal ash harvested from disposal sites across the U.S.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2026

Assembly and Repair of the Photosystem II Reaction Center

This project investigated the biochemical and biophysical mechanisms governing assembly and repair of Photosystem II (PSII), the membrane protein complex responsible for solar-driven water oxidation in oxygenic photosynthesis. The work focused on three integrated areas: (1) protein–protein interactions that facilitate PSII assembly in cyanobacterial biogenesis centers, (2) the chemical mechanism of photo-assembly of the Mn 4 CaO 5 oxygen-evolving complex (OEC), and (3) mechanisms that target PSII reaction centers for degradation and repair in photosynthetic organisms. Using electron paramagnetic resonance spectroscopy, protein biochemistry, molecular genetics, quantitative mass spectrometry, and computational modeling, the project demonstrated that proton release events limit early steps of OEC assembly and that chloride and calcium ions facilitate Mn oxidation and intermediate stabilization. Complementary studies identified chaperone recruitment mechanisms in cyanobacterial PSII biogenesis centers and translation and protease factors involved in PSII turnover in Chlamydomonas. Together, these results establish proton management and coordinated protein quality control as central design principles in PSII assembly and repair and provide mechanistic insight relevant to biological and artificial photosynthetic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Integrated Anaerobic Membrane Bioreactor (AnMBR) – electro assisted fermentation platform for total resource recovery from diverse wastewaters

The overall objective of the project was to demonstrate a successful wastewater resource recovery platform comprising an Anaerobic Membrane Bioreactor (AnMBR) to achieve >50% Carbon sequestration efficiency as Volatile Fatty Acids (VFAs) or as methane gas from agricultural (animal feeding operations) wastewater along with the generation of final water exceeding Biological Nutrient Removal (BNR) standards for indirect potable reuse by coupling with constructed wetlands has been successfully accomplished. The AnMBR achieved stable performance over 350 days, removing 80–90% of COD and BOD₅ and recovering methane (0.17±0.07 L CH4/g COD at 66.5±0.03% v/v) at 3-5 LMH flux and 5-9 days HRT with 3-5% w/v total solids. Phosphorus recovery via CaO addition in an 80-L coagulation-flocculation-sedimentation unit ranged from 40.6% to 99.7%, yielding products with 11.4–13.6% P content and citric acid solubility of 32–38.6% P, comparable to rock phosphate mineral. Ammonium adsorption achieved ~94.5% recovery with exchange capacity of 10 – 16 g NH4-N/kg clinoptilolite. The CW polishing step met Kansas discharge standards for BOD5 and TN (<30 and <10 mg /L,) and approached the TP standard (~2.5 – 4 mg P/L). These findings have either already resulted in two peer reviewed publications, two patent applications, and one publication in conference proceedings.

42 ENGINEERING↗
DOE OSTI2022

Enhancing CO 2 Mineralization Rate and Extent of Iron and Steel Slag via Grinding

Roughly 10% of the CO 2 emissions from iron and steel making are attributable to the direct release of CO 2 from the thermal decomposition of carbonates to produce flux, mainly CaO, used for impurity removal. Notably, these direct emissions remain even if carbon-based steelmaking is replaced by hydrogen-based steelmaking. After removing impurities from the molten metal, this flux becomes the solid waste product called ‘slag’, a primarily Ca-silicate material. The transformation of slag back into carbonates is thermodynamically spontaneous with negative ΔG in the ambient environment, meaning that ~10% of the CO 2 emissions from iron and steel making could be negated if equipment and methods were developed to support CO 2 mineralization. However, the rate of CO 2 mineralization using slag is slowed by several environmental, geometric, and processing factors. We leverage an experimentally verified model of CO 2 mineralization to determine how to efficiently accelerate the process. Increasing the crystallinity of slag, increasing the relative humidity, and reducing the grain size of slag particles provide the greatest increase in CO 2 mineralization rate at the lowest energy penalty. Increasing the concentration of CO 2 and the temperature provide only modest increases in the CO 2 mineralization rate while incurring a substantial energy penalty. For steelmaking slags, CO 2 mineralization represents low-hanging fruit as the current reuse pathways are low value. For ironmaking slag, replacing the production of amorphous slag for the cement industry with the production of crystalline slag for CO 2 mineralization becomes financially preferable when a carbon price/tax exceeds 67.40 USD/t-CO 2 .

42 ENGINEERING↗
DOE OSTI2023

Magnesium production by molten salt electrolysis with liquid tin cathode and multiple effect distillation

Low-cost clean primary production of magnesium metal is important for its use in many applications, from light-weight structural components to energy technologies. This work describes new experiments and cost and emissions analysis for a magnesium metal production process. The process combines molten salt electrolysis of MgO using MgF₂-CaF₂ electrolyte and a reactive liquid tin cathode, with gravity-driven multiple effect thermal system (G-METS) distillation to separate out the magnesium product, and re-use of the tin. Electrolysis experiments with carbon anodes showed current yield above 90%, while a yttria-stabilized zirconia solid oxide membrane (SOM) anode experiment showed 84% current yield. G-METS distillation is an important component of the envisioned process. It can potentially lower costs and energy use considerably compared with conventional magnesium distillation. Techno-economic analysis including detailed mass and energy balances shows that this electrolyte composition could lower costs by utilizing CaO, which is the primary impurity in MgO, as the Hall-Héroult process uses the sodium impurity in alumina. Analysis options include: raw material types (magnesite rock vs. brine or seawater), drying and calcining using electricity vs. natural gas, and carbon vs. SOM anode type. Using SOM inert anodes results in a cost premium around 10%–15%, mostly due to higher electrical energy usage resulting from membrane resistance, and reduces GHG emissions by approximately 1 kg CO₂/kg Mg product. Capital and operating cost estimates, and cradle to gate greenhouse gas (GHG) emissions analysis under several raw material and process technology scenarios, show comparable costs and emissions to those of aluminum production.

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

Ocean liming effect on a North Atlantic microbial community: changes in composition and rates

The ongoing rise in atmospheric CO 2 levels and the consequent global warming make it increasingly difficult to maintain the global temperature within the 1.5 - 2°C target set by the Paris Agreement. Therefore, strategies to remove carbon dioxide from the atmosphere are being developed, with ocean alkalinity enhancement (OAE) gaining most attention. Within OAE, ocean liming- the addition of quicklime (CaO) or hydrated lime (Ca(OH) 2 )- can not only remove CO 2 from the atmosphere but potentially counteract the effects of ocean acidification. Although quite attractive, these technologies have yet to be tested regarding ecological safety and efficacy. Here we report the impacts of ocean liming on the abundance, composition and extracellular enzymatic activity (EEA) rates of a North Atlantic planktonic community. The results demonstrate that OAE led to a decreased phytoplankton development, mainly diatoms. The bacterial response to OAE was community-specific, with a consistent increase in the relative abundance of the order Oceanospirillales. OAE also led to increased EEA rates, especially within the bacterial community. These findings suggest that while initial effects on phytoplankton may be limited, the specific impacts on bacterial groups suggest that OAE could influence the remineralization of organic matter. If our results apply to other communities, OAE might initially affect marine microbial dynamics, but further studies are needed to determine if these effects are long-term.

16S↗
DOE OSTI2021

Evaluating and Enhancing Iron Removal via Filterable Iron Precipitates Formation during Coal-Waste Bioleaching

Iron removal via jarosite precipitate formation is a commonly used technique in various hydrometallurgical processes. Excess iron removal often becomes essential to an overall metal recovery circuit. This is particularly important to processes involving iron-bearing minerals. A technique, which involved the use of pyrite to generate acid for leaching, for iron removal is critical to enabling the process. Iron removal using CaO or similar reagents is expensive and often results in lost product. In the present study, various compounds that facilitate jarosite formation, namely Na2SO4, NH4OH, KCl, and KOH, were utilized and their effect in precipitation was observed. Visual Minteq assisted simulations were run in order to evaluate favorable conditions for iron removal. Morphology and elemental composition of precipitates were analyzed using scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy, and the phase purity was identified using X-ray diffraction analysis.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2020

Structural Modifications of Single-Crystal Aragonite CaCO 3 Beginning at ~15 GPa: In Situ Vibrational Spectroscopy and X-Ray Diffraction Evidence

The structural chemistry of carbonates under mantle conditions facilitates our understanding of carbon recycling pathways in the earth’s interior. It also has impacts on the dynamics of mantle–slab interactions. Aragonite is a common calcium carbonate mineral in pelagic marine sediments. The structural chemistry of single-crystal aragonite during successive compression and the behavior of a structural H+ have been investigated by micro-vibrational spectroscopy and synchrotron X-ray diffraction techniques in diamond anvil cells. We describe a reduction of the b-axial compressibility beginning at ~15 GPa, and the related discontinuities in the first-order derivatives of the vibrational modes. The structural modifications of aragonite are manifested by mutations occurring in the pressure relations of the wavenumbers of the O-C-O bending modes, and of the bandwidth and band intensities of the measured internal and external modes. These anomalies are indicative of changes occurring in the force constant of the C-O bonds, and possibly a second-order phase transition. Besides, the [CaO 9 ] polyhedra begin to deform, possibly with some Ca-O bonds becoming elongated and the others shortening. An increase in the co-ordination number for the Ca 2+ sites could be expected under higher pressures. Additionally, the weakening of the OH modes may imply H + -loss from the aragonite lattice above 11.5 GPa.

58 GEOSCIENCES↗
NASA NTRS1972

Exploration of alloy surface and slurry modification to improve oxidation life of fused silicide coated niobium alloys

Edge and surface modifications of niobium alloys were investigated prior to coating with Si-20Cr-20Fe and slurry composition modification for performance in a 1370 C ambient pressure slow cycle test. The best coating obtained was Si-20Cr-20Mn with an average life of 63 cycles, compared to 40 for Si-20Cr-20Fe on FS-85 (100 percent improvement in weight parity life). Edge beading extended the lives of Si-20Cr-20Fe-coated Cb-752 and FS-85 to 57 and 41 cycles respectively (50 and 20 percent improvements in weight parity life respectively). W, Al2O3 and ZrO2(CaO) surface modifications altered coating crack frequency and microstructure and increased life somewhat.

Levine, S. R.↗
NASA NTRS1971

Hibonite, Ca2/Al, Ti/24O38, from the Leoville and Allende chondritic meteorites.

Hibonite was discovered in light-colored, Ca-Al-Ti-rich and Si-Fe-poor, achondritic inclusions of the Leoville and Allende HL-group chondrites. Two varieties of hibonite occur: one emits a bright red-orange luminescence under electron bombardment and has high amounts of Al2O3 (87.7; 87.9) and low amounts of MgO (0.65; 0.8) and TiO2 (0.68; 0.8). The other emits a bright blue luminescence and is low in Al2O3 (78.7; 79.2) and high in MgO (3.3; 3.7) and TiO2 (6.5; 7.9) (in wt. %). The oxide CaO is about the same in both varieties. It is suggested that the change in the color of the visible luminescence results from changes in composition. The origin of hibonite which occurs in complex mineral assemblages together with anorthite, gelhenite, wollastonite, aluminous diopside, andradite, Ca-pyroxene, perovskite, spinel, taenite, chromite, and pentlandite, and in close proximity to nodules containing calcite, whewellite, forsterite and many of the aforementioned phases, is discussed. The proposition that hibonite and associated phases originated by contact metamorphism and metasomatism of calcite-dolomite bearing assemblages cannot, at this time, be completely ruled out.

Keil, K.↗
NASA NTRS1973

Thermophysical properties of plasma sprayed coatings

Thermophysical properties of plasma sprayed materials were determined for the following plasma sprayed materials: CaO - stabilized ZrO2, Y2O3 - stabilized ZerO2, Al2O3, HfO2 Mo, nichrome, NiAl, Mo-ZrO2, and MoAl2O3 mixtures. In all cases the thermal conductivity of the as-sprayed materials was found to be considerably lower than that of the bulk material. The flash-laser thermal diffusivity technique was used both for diffusivity determination of single-layer materials and to determine the thermal contact resistance at the interface of two-layer specimens.

Wilkes, K. E.↗
NASA NTRS1972

Niobian rutile in an Apollo 14 KREEP fragment.

Niobian rutile was found in a KREEP lithic fragment of basaltic texture. The niobian rutile contains 85.3% TiO2, 7.1% Nb2O5, 2.65% Cr2O3, 0.70% ZrO2, 0.61% SiO2, 0.82% Al2O3 0.61% FeO, 0.52% CaO, 0.22% V2O3 in addition to minor amounts of MnO, MgO, and CeO2. Rare-earth elements were not detected, in contrast with lunar niobian rutile of Marvin (1971). Coexisting minerals in the KREEP fragment are major amounts of plagioclase and orthopyroxene, and minor amounts of olivine, ilmenite, augite, barian K-feldspar, whitlockite, troilite, Ni-Fe, zirkelite, and chromite.

Hlava, P. F.↗
NASA NTRS1972

The Oro Grande, New Mexico, chondrite and its lithic inclusion.

The Oro Grande, New Mexico, U.S.A., chondrite was found in 1971. Electron microprobe analyses and microscopic examination show the following mineralogy: olivine (Fa 19.3 mole %), orthopyroxene (Fs 16.2 mole %), diopside, feldspar (An 13.6 mole %), chlorapatite, whitlockite, kamacite, taenite, troilite, chromite, and an iron-bearing terrestrial weathering product. A bulk chemical analysis of the meteorite shows the following results (weight %): Fe 0.84, Ni 1.46, Co 0.07, FeS 3.62, SiO2 34.18, TiO2 0.14, Al2O3 1.83, Cr2O3 0.55, Fe2O3 21.25, FeO 9.13, MnO 0.31, MgO 21.52, CaO 1.72, Na2O 0.70, K2O 0.08, P2O5 0.25, H2O(+) 2.14, H2O(-) 0.40, C 0.22, sum 100.41. On the basis of composition and texture the Oro Grande meteorite is classified as an H5 chondrite.

Fodor, R. V.↗
NASA NTRS1973

Major and trace elements in igneous rocks from Apollo 15.

The concentrations of major and trace elements have been determined in igneous rocks from Apollo 15. All materials analyzed have typical depletions of Eu except for minerals separated from sample 15085. Four samples have concentrations of trace elements that are similar to those of KREEP. The samples of mare basalt from Apollo 15 have higher concentrations of FeO, MgO, Mn, and Cr and lower concentrations of CaO, Na2O, K2O, and rare-earth elements (REE) as compared to the samples of mare basalt from Apollos 11, 12, and 14. The samples can be divided into two groups on the basis of their normative compositions. One group is quartz normative and has low concentrations of FeO while the other is olivine normative and has high concentrations of FeO. The trace element data indicate that the samples of olivine normative basalt could be from different portions of a single lava flow.

Helmke, P. A.↗
NASA NTRS1973

Electron Microprobe Analyses of Lithic Fragments and Their Minerals from Luna 20 Fines

The bulk analyses (determined with the broad beam electron microprobe technique) of lithic fragments are given in weight percentages and are arranged according to the rock classification. Within each rock group the analyses are arranged in order of increasing FeO content. Thin section and lithic fragment numbers are given at the top of each column of analysis and correspond to the numbers recorded on photo mosaics on file in the Institute of Meteoritics. CIPW molecular norms are given for each analysis. Electron microprobe mineral analyses (given in oxide weight percentages), structural formulae and molecular end member values are presented for plagioclase, olivine, pyroxene and K-feldspar. The minerals are selected mostly from lithic fragments that were also analyzed for bulk composition. Within each mineral group the analyses are presented according to the section number and lithic fragment number. Within each lithic fragment the mineral analyses are arranged as follows: Plagioclase in order of increasing CaO; olivine and pyroexene in order of increasing FeO; and K-feldspar in order of increasing K2O. The mineral grains are identified at the top of each column of analysis by grain number and lithic fragment number.

Conrad, G. H.↗
NASA NTRS1972

Synthesis of calcium superoxide

Efforts to prepare Ca(O2) sub 2 from reactions of calcium compounds with 100% O3 and with O(D-1) atoms generated by photolysis of O3 at 2537 A are described. Samples of Ca(OH) sub 2, CaO, CaO2, Ca metal, and mixtures containing suspected impurities to promote reaction have been treated with excess O3 under static and flow conditions in the presence and absence of UV irradiation. Studies with KO2 suggest that the superoxide anion is stable to radiation at 2537 A but reacts with oxygen atoms generated by the photolysis of O3 to form KO3. Calcium superoxide is expected to behave in an analogous.

Rewick, R. T.↗
NASA NTRS1973

Analysis of the ultrafine fraction of the Apollo 14 regolith

Analyses were obtained on more than 2400 randomly selected particles from the sub-37 micron (ultrafine) fraction of ten Apollo 14 regolith samples. The analyses were conducted with an energy dispersive electron microprobe system. The semiquantitative data were used to group the particles into ten categories. The pyroxene/plagioclase and olivine/plagioclase ratios are inconsistent with those ratios in the Apollo 14 breccias and rocks. The data suggest that fragmented basalts similar to Apollo 12 olivine basalts may have made significant contributions to the ultrafine fraction of the Fra Mauro regolith. Among a number of unusual particles encountered are brown, birefringent lath-shaped grains with 60 wt % SiO2 and 34 wt % FeO(FeSi2O5) and a glass with 20 to 25 wt % CaO, 0 to 8 wt % MgO, 40 to 45 wt % Al2O3 and approximately 30 wt % SiO2.

Finkelman, R. B.↗