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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Systematic characterization of selenium speciation in coal fly ash

Millions of tons of coal fly ashes (CFAs) are produced annually during coal combustion in the U.S., which are commonly beneficially used in the concrete industry or disposed of in ash ponds. CFAs contain trace amounts of a range of toxic heavy metals including selenium (Se). Because the toxicity of Se is dependent on its speciation, investigating Se speciation in CFAs as affected by coal source and combustion conditions can help understand the related environmental and human health impacts during disposal or beneficial reuse. In this study, a set of representative CFA samples were characterized for Se speciation using synchrotron X-ray absorption spectroscopy (XAS) and micro-X-ray fluorescence spectromicroscopy (μ-XRF/XAS). Se-containing particles were highly heterogeneous, and individual particles might contain multiple oxidation states including Se(0), Se(IV), and Se(VI). Principal component analysis was performed for sample characteristics including Al 2 O 3 , SiO 2 , CaO, FeO, loss on ignition, average particle size, Se concentration, and Se oxidation state. Selective catalytic reduction (SCR), which is used to limit nitrogen oxide (NO x ) emissions during coal combustion, was found to be associated with the presence of reduced Se oxidation states, with up to 90% Se(0) observed in samples with SCR. Alongside SCR, FeO content may also influence Se speciation.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Magnetic structure and multiferroicity of Sc-substituted hexagonal YbFeO 3

The hexagonal rare-earth ferrite RFeO 3 family represents a unique class of multiferroics exhibiting weak ferromagnetism, and a strong coupling between magnetism and structural trimerization is predicted. However, the hexagonal structure for RFeO 3 remains metastable in conventional conditions. We have succeeded in stabilizing the hexagonal structure of polycrystalline YbFeO 3 by partial Sc substitution of Yb. Using bulk magnetometry and neutron diffraction, we find that Yb 0.42 Sc 0.58 FeO 3 orders into a canted antiferromagnetic state with the Néel temperature T N ~ 165K, below which the Fe 3+ moments form the triangular configuration in the ab plane and their in-plane projections are parallel to the [100] axis, consistent with magnetic space group P6 3 c'm'. It is determined that the spin canting is aligned along the c axis, giving rise to the weak ferromagnetism. Furthermore, the Fe 3+ moments reorient toward a new direction below reorientation temperature T R ~ 40K, satisfying magnetic subgroup P6 3 , while the Yb 3+ moments order independently and ferrimagnetically along the c axis at the characteristic temperature T Yb ~ 15K. Interestingly, reproducible modulation of electric polarization induced by magnetic field at low temperature is achieved, suggesting that the delicate structural distortion associated with two-up/one-down buckling of the Yb/Sc planes and tilting of the FeO 5 bipyramids may mediate the coupling between ferroelectric and magnetic orders under magnetic field. Furthermore, the present work represents substantial progress to search for high-temperature multiferroics in hexagonal ferrites and related materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Spin-flop coupling at L⁢a 0.5 ⁢S⁢r 0.5 ⁢Fe⁢O 3 /L⁢a 0.7⁢ S⁢r 0.3 ⁢Mn⁢O 3 interfaces

Antiferromagnetic (AFM) spintronics offer several benefits compared to their ferromagnetic (FM) counterparts, such as high storage capacity and faster processing speed, however, difficulties in manipulating and detecting the AFM moments impede their implementation. Spin-flop coupling, the interfacial perpendicular coupling between FM and AFM moments, can be utilized to control the orientation of AFM moments with the application of moderate magnetic fields on the scale of tenths of a Tesla. Here, in this work, epitaxial bilayers of AFM La 0.5 Sr 0.5 FeO 3 (LSFO)/FM La 0.7 Sr 0.3 MnO 3 (LSMO) with fixed LSMO thickness (~85 u.c.) and LSFO thicknesses varying from 10 to 50 u.c. were investigated to determine the effect of Sr doping and La 1-x Sr x FeO 3 magnetocrystalline anisotropy on the strength of spin-flop coupling. X-ray magnetic linear dichroism demonstrated that the spin-flop coupling strength decreased with increasing LSFO layer thickness, persisting at a thickness of 50 u.c. (~20 nm). Furthermore, photoemission electron microscopy revealed a domain-by-domain correlation between the FM and AFM domains consistent with the perpendicular orientation dictated by spin-flop coupling. These results demonstrate that LSFO/LSMO bilayers have the potential to serve as a model materials system for AFM spin transport measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Structure–property relations of sodium iron phosphate nuclear waste glasses: Effects of iron redox ratio and glass composition

Iron phosphate glasses, known for their exceptional chemical durability and potential applicability in nuclear waste management, have gained significant attention over the years. The structures of these glasses are complicated by the coexistence of Fe 3+ and Fe 2+ , which plays a crucial role in determining their structures and properties. Here, this work uses molecular dynamics simulations to study the structural changes in Na 2 O–Fe 2 O 3 –P 2 O 5 glasses with varying glass composition and Fe 2+ /Fe 3+ redox ratio. It was found that the redox ratio and modifier contents significantly affected the short-range and medium-range orders in the glasses. Significant changes in the local environments around P 5+ and Fe 3+ were observed, as reflected by the bond distances and coordination numbers. Na + cations are found to preferentially associate with Fe 3+ (rather than Fe 2+ ), whereas Fe 2+ has stronger association with P 5+ than Na + , confirming the structural role of Fe 2+ as a glass modifier. The disruptions in P–O–P linkages upon increasing FeO suggest that FeO causes glass depolymerization. These glasses achieved higher connectivity with increasing Fe 3+ / (Fe 3+ + Fe 2+ ) ratios, conerting phosphorous Q 2 to Q 3 units and iron Q 5 units to Q 4 units. The decrease of nonbridging oxygen fractions with increasing Fe 3+ / (Fe 3+ + Fe 2+ ) ratios, through creating P–O–Fe linkages, is the main reason of enhanced network connectivity. Quantitative structure–property relationship analyses with different structural descriptors were used to correlate with measured properties. The analyses provided valuable insights into structure–property relationships, emphasizing the importance of choosing relevant energy parameters and defining glass network connectivity, particularly in F net descriptors. It was found the Fe–O–P linkage density exhibits strong correlations to measured dissolution rates, supporting the importance of these linkages in improving the chemical durability in iron phosphate glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1972

Mineralogy, petrology and chemistry of lunar rock 12039.

Rock 12039 belongs to the olivine-depleted group of magmatic rocks characterized by normative and modal SiO2, absence or very low abundance of olivine, and high FeO/(FeO + MgO), Ti/Cr, and CaO/MgO ratios. Clinopyroxenes in this rock show a complex, essentially continuous, compositional zonation from augite cores through ferroaugite to ferrohedenbergite with an abrupt discontinuity at the pyroxferroite contact and, thus, are different from pyroxene in most other Apollo 12 rocks. Two grains contain thin subcalcic pigeonite zones. Texture, presence of very fine (less than 1 micron) exsolution lamallae, and pyroxene zoning indicate a relatively rapid cooling history and pronounced in situ chemical fractionation.

Bunch, T. E.↗
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 NTRS1977

Interpretations of optical observations of Mercury and the moon

Optical, thermal and radar remote-sensing measurements indicate that Mercury is covered with a relatively thick layer of soil similar in texture and thickness to lunar regolith. Photometric limb profiles measured by Mariner 10 imply that the small-scale slopes on Mercury are about half those on the moon, probably because of differing gravity. The differential photometric functions of Mercury and the moon have a latitudinal dependence which can be completely accounted for by shadowing in craters. The lack of polar darkening on Mercury in spite of the presence of a magnetic field implies that the dominant soil-darkening process on Mercury, and by extension, on the moon is not dependent on the solar wind, but probably is deposition of material evaporated by meteorite impacts. Recent measurements of Mercury's spectral reflectivity in the IR and vacuum UV are both consistent with the surface rocks of Mercury being lower in FeO than those of the moon. Based on laboratory experiments the average FeO content on the surface of Mercury is estimated to be between 3 and 6%.

Hapke, B.↗
NASA NTRS1977

Effects of thermal metamorphism on compositions of lunar spinels

The reported study represents an attempt to evaluate experimentally the compositional and textural changes that are likely to be observed in the Fe-Ti-Cr spinels of lunar igneous rocks by subsequent thermal metamorphism. The Apollo 12 igneous rock, 12018,43, was chosen for this investigation because an earlier study of another fraction of this rock by El Goresy et al. (1971) has reported an almost continuous trend of spinel compositions between Cr-Ulvoespinel and Ti-chromite. The nature of the compositional changes in the heated spinels (and ilmenites) is found to be such that the changes cannot be explained by intragranular adjustments alone. In the heated sample, pyroxene grains adjacent to the high-Ti spinels show a decrease in FeO, and an increase in MgO and Al2O3 at the interface. This may account for the MgO depletion and a part of the FeO enrichment in the high-Ti spinels. It is believed that the heating experiment demonstrates that thermal metamorphism of lunar basalts is likely to modify the compositions of their preexisting spinels (and ilmenites).

Misra, K. C.↗
NASA NTRS1977

Grain size, petrographic, and FMR studies of the double core 60009/10 - A study of soil evolution

Six samples from the upper core 60010 of the double drive core 60009/60010 were analyzed for grain size distribution, petrographic particle types and abundances, magnetic fraction, and ferromagnetic resonance. It was found that the magnetic fraction of these soils is not equivalent to the agglutinate fraction, and magnetic separation partitions high-FeO agglutinate from low-FeO agglutinates. Various maturity indices are in essential agreement. The deposition of most or all of the core could have occurred in a single event. If that is the case, the core units have no time-stratigraphic significance and do not reflect individual cratering events.

Mckay, D. S.↗
NASA NTRS1979

Trace elements in the Allende meteorite. IV - Amoeboid olivine aggregates

INAA data for Ca, Sc, Hf, La, Ce, Sm, Eu, Tb, Yb, Lu, Os, Ir, Ru, Na, Cl, Br, Fe, Mn, Cr, Co, Au, As, and Sb are presented for ten amoeboid aggregates from the Allende meteorite. Only one lacks olivine. Seven of the remainder, as a group, have cosmic proportions of refractory lithophile and siderophile elements and appear to have formed when coarse-grained Allende inclusion material underwent partial reaction with a low-temperature nebular gas and mixture with FeO-rich olivine. The other two have highly fractionated abundances of refractory elements relative to one another compared to Cl chondrites, including Group II REE patterns, and probably formed by the mixing of fine-grained Allende inclusion material with FeO-rich olivine. Non-refractory siderophile components are also different in composition in each type of amoeboid olivine aggregate.

Grossman, L.↗
NASA NTRS1980

Metamorphism of the H-group chondrites - Implications from compositional and textural trends in chondrules

The paper discusses element bulk compositions of 373 chondrules from 18 H3 to H6 chondrites determined by broad-beam electron probe analysis. Bulk chondrule FeO and Al2O3 amounts increase and TiO2 and Cr2O3 decrease with increasing petrologic type; normative faylite, albite, and plagioclase amounts increase through the petrologic sequence. Chondrule diameters correlate with phenocryst sizes in porphyritic chondrules of type 3 chondrites, but this correlation is diminished in the higher petrologic types. The compositional trends in chondrules through the petrologic sequence are attributed to diffusion and equilibration among chondrules, and between chondrules and matrix in response to increasing degrees of thermal metamorphism. It is suggested that H-group chondrites are formed by accretion of high-temperature (chondrules) and low-temperature (matrix) materials. Internal reheating of the parent materials to different temperatures caused compositional equilibration, grain coarsening, and reduction of FeO to Fe(0) by carbon.

Lux, G.↗
NASA NTRS1980

Oxidation state of the atmosphere and crust of Venus from Pioneer Venus results

Recent spacecraft observations of Venus permit a detailed model of sulfur chemistry in the atmosphere-lithosphere system. Pioneer Venus experiments confirm that, as predicted, COS and H2S are dominant over SO2 in the lower atmosphere, and that the equilibrium concentrations of S2 and S3 are significant. Many criteria serve to bracket the oxidation state of the crust: it is nearly certain that the S2(2-)/SO4(2-) buffer regulates the oxygen fugacity, and that FeO is at least as abundant as F2O3 in crustal silicates. A highly oxidized crust (as, for example, would result from O2 absorption complementary to escape of vast amounts of H2) is incompatible with the gas-phase sulfur chemistry. If the Pioneer Venus mass spectrometer estimates of the abundance of sulfur gases are correct, earth-like models for the bulk composition of Venus are seriously in error, and a far lower FeO content is required for Venus.

Lewis, J. S.↗
NASA NTRS1980

Origins and size distribution of metallic iron particles in the lunar regolith

The metallic iron concentration has been measured in three ranges of metal particle diameters for 79 lunar soils by a combination of static magnetic and ferromagnetic resonance techniques. Based on these measurements, a model has been developed which apportions the total metallic iron content of lunar soils between three components: (1) metallic iron particles produced from the exposure-induced reduction of ferrous iron; they range from 40 to 330 A in diameter and are predominantly associated with agglutinate glass; (2) metallic iron particles derived from the metallic phases of the micrometeorites involved in the formation of agglutinate glass; these particles are mostly greater than 300 A in diameter; and (3) metallic iron particles in the source materials such as bedrock and breccias; these are usually greater than 330 A in diameter. The maximum concentration of metallic iron in lunar regolith is estimated at about 0.7 equiv. wt% in highland regions (approximately 5.0 wt% FeO) and about 1.0 equiv. wt% in mare regions (approximately 15.0 wt% FeO).

Morris, R. V.↗
NASA NTRS1983

Chondrules and other components in C, O, and E chondrites Similarities in their properties and origins

Three types of chondrules are described that are common to H3, LL3, CM2, CO3, and CV3 chondrites. Low- and high-FeO, porphyritic olivine chondrules contain olivine with Fa0.3-8 and Fa5-50 respectively, and can easily be distinguished petrographically. Poikilitic pyroxene chondrules have 1-20 vol pct olivine (Fa0.2-8) enclosed by low-Ca pyroxene (Fs0.5-7), and also occur in E chondrites. These three types formed in separate nebular regions which had dimensions and spacings such that a few percent of the chondrules that collided to form compound chondrules were of different types. Sorting of chondrule precursor material and mixing of chondrule types probably account for most variations in bulk and mineral chemistry among chondrite groups. Metallic Fe,Ni grains containing 0.1-1 percent Cr, Si, and P are present in low-FeO olivine chondrules from all type 2 and least metamorphosed type 3 chondrites. Metal compositions reflect reduction during chondrule formation in the nebula, not nebular condensation. Opaque matrices in type 3 ordinary and carbonaceous chondrites are somewhat similar in composition and mineralogy, and probably have related origins. It is concluded that chondrules in all known chondrite groups share similar nebular origins.

Scott, E. R. D.↗
NASA NTRS1984

The Colony meteorite and the possible existence of a new chemical subgroup of CO3 chondrites

The Colony meteorite, found in Oklahoma around 1975, has an unrecrystallized texture and contains heterogeneous olivine and low Ca pyroxene, kamacite with low Ni and Co and high Cr, amoeboid inclusions with low FeO and MnO, and numerous small chondrules with clear pink glass. These characteristics are shared by members of the least metamorphosed subgroup of CO3 chondrites. Colony contains a fine grained matrix that has higher FeO and K2O and lower MgO and Na2O than normal CO3 matrices. Allan Hills A77307 is another unmetamorphosed meteorite that has many petrologic similarities to normal CO chondrites, including matrix abundance, mineral compositions and chondrule size. However, it differs from them in its abundance of magnetite and presence of iron carbides. The olivine and low Ca pyroxene compositional distributions of Colony and A77307 are very similar. The shapes of the thermoluminescence glow curves of Colony and A77307 are very similar, but differ significantly from those of normal CO chondrites. It is suggested that Colony and A77307 represent a distinct chemical subgroup of CO3 chondrites, characterized by low Ni, Co, S, Ca, Mg, Mn and, possibly, high Cd.

Rubin, A. E.↗
NASA NTRS1985

Venus, Earth and Mars: Present bounds on similarities and differences in bulk composition

The bulk compositions of the terrestrial planets are constrained in part by rigorous bounds derivable from geophysical data and from chemical data obtained in situ or by remote sensing. In large part, however, the bulk compositions are constrained only by the inferred plausibility of assumptions made about the processes responsible for producing planets. Present data are consistent with Venus, Earth and Mars all having solar ratios of the major, non-volatile elements. The mantle of Mars has a higher FeO content than the Earth's present upper mantle. The FeO content of the Venus mantle is poorly constrained. Abundances of minor elements are virtually unconstrained by geophysical data and only weakly constrained by existing chemical data. Inferences drawn from SNC meteorites suggest that Mars may be enriched in most volatiles relative to the Earth. Simple models in which volatiles are added in a single component probably do not accurately predict bulk volatile inventories of the planets.

Goettel, K. A.↗
NASA NTRS1986

Fe-Mg-Mn relations of ureilite olivines and pyroxenes and the genesis of ureilites

Microprobe analyses of ureilite and pigeonite cores are studied. The Fe/Mn-Fe/Mg relationship in the olivine core is examined. It is observed that magnetic processs such as fractional crystallization and partial melting, and FeO reduction contribute to the olivine core composition. The study of the Mg/Mn and Fe/Mn distributions reveals that these two distributions are not in equilibrium in the olivine and pigeonite cores. The effect of a reducing agent, carbon, on the ureilite genesis is investigated. It is concluded that fractional crystallization and FeO reduction are the major processes of ureilite genesis.

Mittlefehldt, D. W.↗