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All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

Lateral and Vertical Heterogeneity of Thorium in the Procellarum KREEP Terrane: As Reflected in the Ejecta Deposits of Post-Imbrium Craters

The Procellarum KREEP Terrane displays the highest concentrations of Th on the Moon. However, locations of elevated Th in this region appear to be random. As observed in the 5 deg per pixel equal-area Th data, and made more evident in the preliminary 2 deg data, Th is enhanced around the craters Aristillus, Aristarchus, Kepler, Mairan, the Apennine Bench formation, and the Fra Mauro region, while noticeably and unexpectedly lower in other locations (e.g., Archimedes, Copernicus, Eratosthenes, and Plato). We have examined the composition of the materials present in these regions with the goal of understanding the patchy nature to the distribution of Th and ultimately to decipher the geologic processes that have concentrated the Th. At present time, the published resolution of the Lunar Prospector Th gamma-ray data is low (5 deg per pixel), but this will soon be superceded by significantly higher-resolution data (2 deg per pixel). Even at this improved resolution, however, it is difficult to resolve the units that are the major source of Th. In an attempt to circumvent this problem, we employ the higher-resolution Clementine multispectral data for those regions mentioned above. We use the UV-VIS-derived compositional information and the spectral properties of craters, and their ejecta as drill holes through the mare-basalt surface to investigate the thickness and composition of underlying material. With this information we attempt to piece together the stratigraphy and geologic history of the Imbrium-Procellanim region. We processed the five-band multispectral data from the Clementine Mission (415, 750,900,950, and 1000nm) using ISIS software and calibration parameters developed by the USGS, Flagstaff, Arizona. Final image mosaics are in equal-area sinusoidal projection, and have a resolution of 250 m/pixel. Using the method of we produced maps of FeO and Ti02 composition. Here we examine the Th, FeO, and Ti02 composition and spectral properties of the craters discussed above and their ejecta, with the goal of describing the materials they excavate. One interpretation for the origin of the high-Th material is that subsurface KREEPy materials have been excavated by impact craters. The material excavated may be either volcanic KREEP (e,g., Apennine Bench Formation), KREEPy impact-melt breccia formed by the Imbrium impact (e.g., Fra Mauro Formation), or other KREEP-rich crustal material. Determining which type of material is responsible for the elevated Th and its extent is important to understanding the premare and possibly the prebasin stratigraphy of the Imbrium-Procellarum Region. Merging the 5 deg. Th data with the shaded relief map, we observe that the highest Th concentrations are not related to pre-Imbrium upper crustal materials. The Apennines, Alpes, and Caucasus Mountains represent the pre-Imbrian highlands material and do not express concentrations of Th, FeO, and TiO2 as high as the most Th-fich materials exposed within the Procellarum KREEP Terrane. We observe that, in general, these massifs contain 10-14 wt% FeO and 4-7 ppm Th. Determining whether the Th signal is from KREEP basalts or KREEPy impact-melt breccias cannot be done with the Clementine data because the two rock types are compositionally and mineralogically too similar (e.g., the Th-rich, mafic impact-melt breccias in the Apollo sample collection are dominated by a KREEP-basalt like component. Mapping-the distribution and sizes of craters and whether they display elevated Th concentrations or not, should reveal the depth and thickness of the KREEP-rich materials, and whether they are ubiquitous (i.e., impact-melt breccia) or more randomly distributed; this might be taken as an indicator of localized KREEP-basalt flows. Within the southeastern region of the Imbrium basin, there are two Th hot spots. The first is associated with the crater Aristillus, and the latter with the Apennine Bench Formation. Adjacent to these two hot spots are craters with a lower Th signature: Archimedes and Autolycus. We observe in the ejecta of Aristillus, a region of significantly lower FeO (10-14 wt%) relative to the surrounding mare basalt. The crater Autolycus, 50 km to the south, did not excavate similar low-FeO material. We suggest that the lower-FeO material in the ejecta of Aristillus corresponds to Th-rich material; the FeO content observed in Aristillus ejecta is comparable to that of KREEP basalt or mafic impact melt breccia (10-12 wt% FeO). We determine that this low FeO, Th-rich material is volcanic KREEP, as opposed to Imbrium impact melt, on the basis that the low-Fe material is exposed more prominently in ejecta in the northern portion of Aristillus. Our assumption is that if the layer underlying Aristillus was continuous, a more widespread and uniform low-Fe signature wouldbe observed in the ejecta deposit. Archimedes, 110 km southwest of Aristillus, impacted the northern portion of the Apennine Bench prior to the eruption of KREEP basalt. Archimedes rim material is not as enriched in Th as the Apennine Bench, and there are differences between the two in FeO concentration and in their continuum slope. Archimedes exhibits a much steeperor "redder" continuum slope than the Apennine Bench. This steepslope suggests the presence of glassy material. The glassy material is concentrated around an unnamed crater on the southern rim of Archimedes (4.5W, 28.2N) and along the northern rim of Archimedes. We suggest two possibilities, or a combination of the two, to explain the low-Th signal from Archimedes: (1) The Apennine Bench prior to KREEP basalt eruption was lower in Th (4-7 ppm, e.g., similar to the Apennine massifs) and KREEP basalts are absent in the rim of Archimedes; or (2) the glassy (possibly pyroclastic) material layering the rim of the Archimedes, dilutes any high-Th material present with low-Th material. (Additional information is contained in the original)

Gillis, J. J.↗
NASA NTRS1999

Apollo 17 Soil Characterization for Reflectance Spectroscopy

It is the fine fractions that dominate the observed spectral signatures of bulk lunar soil, and the next to the smallest size fractions are the most similar to the overall properties of the bulk soil. Thus, our Lunar Soil Characterization Consortium has concentrated on understanding the inter-relations of compositional, mineralogical, and optical properties of the <45-micron size fraction and its component sizes (20-44 micron, 10-20 micron, and <10 micron size fractions). To be able to generalize our results beyond the particular sample set studied, it is necessary to quantitatively identify the observed effects of space weathering and evaluate the processes involved. For this, it is necessary to know the chemistry of each size fraction, modal abundances of each phase, average compositions of the minerals and glasses, I(sub s)/FeO values, reflectance spectra, and the physical makeup of the individual particles and their patinas. This characterization includes the important dissection of the pyroxene minerals into four separate populations, with data on both modes and average chemical compositions. Armed with such data, it should be possible to effectively isolate spectral effects of space weathering from spectral properties related to mineral and glass chemistry. Four mare soils from the Apollo 17 site were selected for characterization based upon similarities in bulk composition and their contrasting maturities, ranging from immature to submature to mature. The methodology of our characterization has been discussed previously. Results of the Apollo 17 mare soils, outlined herein, are being prepared for publication in MAPS. As shown, with decreasing grain size, the agglutinitic (impact) glass content profoundly increases. This is the most impressive change for the mare soils. In several soils we have examined, there is an over two-fold increase in the agglutinitic glass contents between the 90-150- micron and the 10-20-micron size fractions. Accompanying this increase in agglutinitic glass is a definite decrease in pyroxenes and to lesser extents, the oxides (ilmenite), volcanic glass, and olivine. Unexpectedly, however, the absolute plagioclase abundances stay relatively constant throughout the different grain sizes, although the abundance of plagioclase relative to the mafic minerals increases with decreasing particle size. These soils were chosen for study based upon their similarities in FeO and Ti02 content, allowing for direct comparisons between evolutions of chemistry between size fractions and among different maturities of soils. The bulk chemistry of these fractions was determined by EMP analyses of fused glass beads. In contrast to the systematic variations in bulk chemistry discussed below, the relatively uniform composition of agglutinitic glass with grain size and soil maturity is illustrated. The composition of the bulk fraction of each size fraction becomes more feldspathic with increasing maturity, with the effect being most pronounced for the finest fractions. The composition of the agglutinitic glass, however, is relatively invariant and more feldspathic (i.e., rich in Al2O3) than even the <10-micron fraction. This relation not only strengthens the "fusion of the finest fraction" (F(sup 3)) hypothesis, but also highlights the important role of plagioclase in the formation of agglutinitic glass. With decreasing grain size, FeO, MgO, and TiO2 contents decrease, whereas CaO, Na2O, and Al2O3 (plag components) increase for all soils. These chemical variations would appear to be coupled with the significant increase in agglutinitic glass and decrease in oxide (ilmenite),pyroxene, and volcanic glass. These changes in chemistry do not appear to be due to distinct changes in the compositions of individual phases but to their abundances. Values of I(sub s)/FeO increase with decreasing grain size, even though the bulk FeO contents decrease. That is, the percentage of the total Fe that is present as nanophase Fe(sup O) has increased substantially in the smaller size fraction. Note that the increase in nanophase FeO in smaller size fractions is significantly greater than the increase in agglutinitic glass content, with its single-domain FeO component. This would seem to indicate that at least some of the FeO is surface correlated. To illustrate this effect, if it is assumed that the nanophase FeO is entirely surface correlated, then equal masses of 15-micron and 6-micron spheres should have about 3x as much FeO in the finer fraction. The recent findings of Kelleret al. of the major role of vapor-deposited, nanophase FeO-containing patinas on most soil particles is a major breakthrough in our understanding of the distribution of FeO within agglutinitic glass and upon grain surfaces. Bidirectional reflectance spectra for a representative Apollo 17 soil (70181) are shown. The size separates all have similar albedo in the blue and follow a regular sequence in which the continuum slope increases, ferrous bands weaken, and albedo, increases with decreasing particle size. The bulk <45-micron soil is typically close to the 10-20 micron spectrum. It is important to note that although the finest fraction (<10 micron) is close in composition to the abundant agglutinitic glass in each size fraction, this size fraction is relatively featureless and does not dominate the spectrum of the bulk <45-micron soil. It has long been suspected that agglutinitic glass, to a large extent, is the product of melting of the finest fraction of the soils, with a dominance of plagioclase. Given the low abundance of pyroxene in the finest fractions of each soil the source of the FeO in these Apollo 17 agglutinitic glasses is not fully identified. We suspect the abundant volcanic glass in these samples may be a significant contributor and this hypothesis will be tested with the suite under study from other Apollo sites.

Taylor, L. A.↗
NASA NTRS2006

Oxygen-isotopic Compositions of Relict and Host Grains in Chondrules in the Yamato 81020 CO3.0 Chondrite

We report the oxygen-isotope compositions of relict and host olivine grains in six high-FeO porphyritic olivine chondrules in one of the most primitive carbonaceous chondrites, CO3.0 Yamato 81020. Because the relict grains predate the host phenocrysts, microscale in situ analyses of O-isotope compositions can help assess the degree of heterogeneity among chondrule precursors and constrain the nebular processes that caused these isotopic differences. In five of six chondrules studied, the DELTA O-17 (=delta O-17 - 0.52 (raised dot) delta O-18) compositions of host phenocrysts are higher than those in low-FeO relict grains; the one exception is for a chondrule with a moderately high-FeO relict. Both the fayalite compositions as well as the O-isotope data support the view that the low-FeO relict grains formed in a previous generation of low-FeO porphyritic chondrules that were subsequently fragmented. It appears that most low-FeO porphyritic chondrules formed earlier than most high-FeO porphyritic chondrules, although there were probably some low-FeO chondrules that formed during the period when most high-FeO chondrules were forming.

Kunihiro, Takuya↗
NASA NTRS2004

Evidence for Differential Comminution/Aeolian Sorting and Chemical Weathering of Martian Soils Preserved in Mars Meteorite EET79001

Impact-melt glasses containing Martian atmospheric gases in Mars meteorite EET79001 are formed from Martian soil fines that had undergone meteoroid-comminution and aeolian sorting accompanied by chemical weathering near Mars surface. Using SiO2 and SO3 as proxy for silicates and salts respectively in Mars soils, we find that SiO2 and SO3 correlate negatively with FeO and MgO and positively with Al2O3 and CaO in these glasses, indicating that the mafic and felsic components are depleted and enriched relative to the bulk host (Lith A/B) respectively as in the case of Moon soils. Though the overall pattern of mineral fractionation is similar between the soil fines on Mars and Moon, the magnitudes of the enrichments/depletions differ between these sample-suites because of pervasive aeolian activity on Mars. In addition to this mechanical processing, the Martian soil fines, prior to impact-melting, have undergone acid-sulfate dissolution under oxidizing/reducing conditions. The S03 content in EET79001,507 (Lith B) glass is approx.18% compared to < 2% in EET79001, 506 (Lith A). SiO2 and SO3 negatively correlate with each other in ,507 glasses similar to Pathfinder soils. The positive correlation found between FeO and SO3 in ,507 glasses as well as Pathfinder rocks and soils is consistent with the deposition of ferric-hydroxysulfate on regolith grains in an oxidizing environment. As in the case of Pathfinder soils, the Al 2O3 vs SiO2 positive correlation and FeO VS S102 negative correlation observed in ,507 glasses indicate that SiO2 from the regolith is mobilized as soluble silicic acid at low pH. The large off-set in the end-member FeO abundance ( SO3=0) between Pathfinder soil-free rock and sulfur-free rock in ,507 glass precursors suggests that the soils comprising the ,507 glasses contain much larger proportion of fine-grained Martian soil fraction that registers strong mafic depletion relative to Lith B. This inference is strongly supported by the Al2O3 - SO3 negative correlation observed in both ,507 glasses and pathfinder soils. Furthermore, the flat MgO-SO3 correlation observed in the case of ,507 glasses shows that the solubilized MgSO4 is mobilized by the aqueous solutions leaving behind the rock-residue with approx.2-3% MgO. This value is similar to the approx.2% MgO found for the soil-free rock at the Pathfinder site. The EET79001 ,506 glasses, in contrast, show that Al2O3 and CaO positively correlate with SO3 indicating that Al is precipitated as amorphous hydroxysulfate at relatively high pH. The FeO - SO3 negative correlation observed in ,506 glasses yields an end-member FeO abundance of approx.21% for the sulfur-free rock, which is consistent with the 22% FeO deduced for the Viking soil-free rock. Further, the FeO and MgO negative correlation with S03 observed in ,506 glasses indicates that the divalent Fe and Mg released from ferromagnesian minerals by acid sulfate dissolution are mobilized away from the reaction sites as soluble sulfates under reducing environment. A similar negative correlation between FeO and SO3 and a positive correlation between Al2O3 and SO3 found in Viking soils suggest that they also had undergone acid-sulfate dissolution under relatively reducing conditions.

Rao, M. N.↗
NASA NTRS2000

Chondrules in the LEW85332 Ungrouped Carbonaceous Chondrite: Fractionation Processes in the Solar Nebula

We studied 14 chondrules separated from LEW85332, an ungrouped type-3 carbonaceous chondrite related to CR chondrites; 23 elements were determined by neutron activation and the chondrules were characterized petrographically. Oxygen isotopic compositions were determined by R. N. Clayton and T. K. Mayeda for seven chondrules. Chondrule abundance ratios tend to form one of two distinct patterns. In low FeO chondrules, refractory lithophile patterns are flat (i.e., unfractionated); siderophile abundances are high and show a small decrease with increasing volatility. Although high FeO chondrules also have flat refractory lithophile abundance patterns, siderophile abundances are highly fractionated; refractory Ir is very low and Fe is very high relative to other siderophiles. We suggest that the low FeO chondrules in LEW85332 formed early in nebular history when metal was intimately mixed with silicates in the chondrule precursors, and that the viscosity of the liquid-solid mix was too high to permit expulsion of the metal by centrifugal action; their porphyritic structures are consistent with incomplete melting, which would result in relatively high viscosities. When the high FeO chondrules formed somewhat later, much of the Fe was oxidized and the melting of precursors was more extensive, FeO and other oxidized siderophiles were retained in the silicate liquid, and metal was lost, possibly expelled from low viscosity chondrule melts. The O isotopic compositions of the chondrules form a linear array of slope 0.93 +/- 0.05 on a three-isotope diagram, parallel to the carbonaceous chondrite anhydrous minerals (CCAM) line and a CR chondrule array, but offset from the latter by -1% in (delta)O-18. Some or all of this offset may reflect incorporation of O from Antarctic water during weathering. Chondrule (Delta)O-17 values correlate positively with FeO, possibly indicating that the (Delta)O-17 of the nebular gas composition increased with time. The chemical and O isotopic data suggest a temporal sequence extending from early, low FeO to late high FeO chondrules.

Wasson, John T.↗
NASA NTRS1984

Bulk composition of the Moon in the context of models for condensation in the solar nebula

The FeO content of the Moon is substantially higher than the present FeO content of the Earth's mantle. If the Moon formed by fission from the Earth's mantle, then the conclusion that the Earth's mantle must have been much richer in FeO at the time of fission appears firm. If the Moon formed independently in geocentric orbit, then the FeO contents of the two bodies should be similar, because both would be accreting from the same source of silicate material. Therefore, Earth's mantle at the time of lunar formation probably had an FeO content quite similar to the present FeO content of the Moon. This conclusion, if valid, has profound implications in two areas: (1) the differentiation history of the Earth's mantle and core; and (2) the processes responsible for governing the bulk compositions of the terrestrial planets. If Earth had more FeO than previously thought, then the composition differences between Earth and Mars are less than previously believed. This suggests that condensation temperature and heliocentric distance may have been less important in governing planetary compositions and other mechanisms, including iron/silicate fractionation may have been more important. The implication of this model for the compositions of the Moon and the other terrestrial planets are discussed.

Goettel, K. A.↗
NASA NTRS1999

Troilite in the Chondrules of Type-3 Ordinary Chondrites: Implications for Chondrule Formation

The presence of primary troilite in chondrules requires that nebular temperatures were <650 K (the 50% condensation temperature of S) at the time of chondrule formation and that chondrules were molten for periods short enough (less than or equal to 10 s) to avoid significant volatilization of S. We examined 226 intact chondrules of all textural types from eight unshocked to weakly shocked ordinary chondrite falls of low petrologic type to determine the origin of troilite in chondrules; 68 chondrules are from LL3.0 Semarkona. There is a high probability that troilite is primary (i.e , was present among the chondrule precursors) if it is completely embedded in a mafic silicate phenocryst, located within one-half radius of the apparent chondrule center and is part of an opaque assemblage with an igneous texture Based on these criteria, 13% of the chondrules in Semarkona and in the set as a whole contain primary troilite. Most of the remaining chondrules contain troilite that is probably primary, but does not meet all three criteria. Troilite occurs next to tetratacnite in some opaque spherules within low-FeO chondrules in Semarkona, implying that the Ni required to form the tetrataenite came from the troilite Troilite can accommodate 5 mg/g Ni at high temperatures (> 1170 K) but much less Ni at lower temperatures; because this is far higher than the metamorphic temperature inferred for Semarkona (approx. 670 K), the troilite must be primary Primary troilite fitting the three criteria occurs in a smaller fraction of low-FeO [FeO/(FeO + MgO) in olivine and/or low-Ca pyroxene not greater than 0.0751 than high-FeO porphyritic chondrules in Semarkona (9% vs 33%) Coarse-grained low-FeO porphyritic chondrules appear to contain somewhat more troilite on average than those of medium grain size We found a few troilite-free, metallic-Fe-Ni-bearing, low-FeO chondrules that contain Na2O-bearing augite and Na2O- and K2O-rich mesostasis; these chondrules were probably formed after ambient nebular temperatures cooled below 910 K (the 50% condensation temperature of Na) and before they reached 650 K Literature reports of rare fayalitic microchondrules in the rims around a few normal-size chondrules suggest that chondrule formation persisted until nebular temperatures cooled below 500 K Secondary troilite occurs in a few percent of Semarkona chondrules as thin veins mobilized by shock; troilite or pyrrhotite in the outer portions of some chondrules occur within opaque assemblages containing magnetite, carbide, Ni-rich sulfide, awaruite, and Co-rich kamacite produced by parent-body hydrothermal alteration.

Rubin, Alan E.↗
NASA NTRS2006

A Relict-Grain-Bearing Porphyritic Olivine Compound Chondrule from LL3.0 Semarkona that Experienced Limited Remelting

Chondrule D8n in LL3.0 Semarkona is a porphyritic olivine (PO) chondrule, 1300 x 1900 microns in size, with a complicated thermal history. The oldest recognizable portion of D8n is a moderately high-FeO, PO chondrule that is modeled as having become enmeshed in a dust ball containing a small, intact, low-FeO porphyritic chondrule and fine-grained material consisting of forsterite, kamacite, troilite, and possibly reduced C. The final chondrule melting event may have been a heat pulse that preferentially melted the low-FeO material and produced a low-FeO, opaque-rich, exterior region, 45-140 microns in thickness, around the original chondrule. Ai one end of the exterior region, a kamacite- and troilite-rich lump 960 pm in length formed. During the final melting event, the coarse, moderately ferroan olivine phenocrysts within the original chondrule appear to have been partly resorbed (These relict phenocrysts have the highest concentrations of FeO, MnO, and Cr2O3-7.5, 0.20, and 0.61 wt%, respectively-in D8n.). Narrow olivine overgrowths crystallized around the phenocrysts following final chondrule melting; their compositions seem to reflect mixing between melt derived from the exterior region and the resorbed margins of the phenocrysts. During the melting event, FeO in the relict phenocrysts was reduced, producing numerous small blebs of Ni-poor metallic Fe along preexisting curvilinear fractures. The reduced olivine flanking the trails of metal blebs has lower FeO than the phenocrysts but virtually identical MnO and Cr2O3 contents. Subsequent parent-body aqueous alteration in the exterior region of the chondrule formed pentlandite and abundant magnetite.

Rubin, Alan E.↗
DOE OSTI2022

Exploring the Origin of Anionic Redox Activity in Super Li-Rich Iron Oxide-Based High-Energy-Density Cathode Materials

Super alkali-rich materials (alkali:transition metal ratio of ≥2:1), such as Li 5 FeO 4 , exhibit the potential to realize anionic redox upon deep delithiation. Li 5 FeO 4 was shown to undergo reversible cycling between Li 4 FeO 3.5 and Li 3 FeO 3.5 with combined cation/anion redox, a remarkable capacity of 189 mAh/g, and no O 2 release. However, the impact of phase transformations on the reaction thermodynamics and the correlation between the structural changes and reaction reversibility remain unclear. In this study, we use first-principles calculations to examine the delithiation and (re)lithiation reactions of Li 5 FeO 4 . We show that the experimentally observed charge and discharge processes go through non-equilibrium pathways. Upon delithiation, the compound undergoes a phase transformation from Li 5 FeO 4 , with tetrahedrally coordinated (T d ) Fe ions, to a delithiated disordered rocksalt structure, with octahedral (O h ) Fe ions. Fe-ion migration has an asymmetric kinetic barrier that makes T d → O h migration facile, whereas the reverse process has a much larger barrier, explaining the difficulties in reaction reversibility. We further elucidate the transition metal and O redox sequences during the charge cycle and identify the complex electrochemistry associated with the dual participation of cationic redox (Fe 3+ /Fe 4+ ) and anionic redox (O 2– /O – /O o ). Armed with this knowledge, we conduct high-throughput screening of known alkali-rich transition metal oxides by evaluating their potential to enable reversible anionic redox, with multiple candidates proposed for further experimental trials. Furthermore, our work provides a useful guide for the further development of super alkali-rich anionic-redox-active electrodes for high-energy-density batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Emergent magnetism and exchange bias effect in iron oxide nanocubes with tunable phase and size

Abstract We report a systematic investigation of the magnetic properties including the exchange bias (EB) effect in an iron oxide nanocube system with tunable phase and average size (10, 15, 24, 34, and 43 nm). X-ray diffraction and Raman spectroscopy reveal the presence of Fe 3 O 4 , FeO, and α -Fe 2 O 3 phases in the nanocubes, in which the volume fraction of each phase varies depending upon particle size. While the Fe 3 O 4 phase is dominant in all and tends to grow with increasing particle size, the FeO phase appears to coexist with the Fe 3 O 4 phase in 10, 15, and 24 nm nanocubes but disappears in 34 and 43 nm nanocubes. The nanocubes exposed to air resulted in an α -Fe 2 O 3 oxidized surface layer whose thickness scaled with particle size resulting in a shell made of α -Fe 2 O 3 phase and a core containing Fe 3 O 4 or a mixture of both Fe 3 O 4 and FeO phases. Magnetometry indicates that the nanocubes undergo Morin (of the α -Fe 2 O 3 phase) and Verwey (of the Fe 3 O 4 phase) transitions at ∼250 K and ∼120 K, respectively. For smaller nanocubes (10, 15, and 24 nm), the EB effect is observed below 200 K, of which the 15 nm nanocubes showed the most prominent EB with optimal antiferromagnetic (AFM) FeO phase. No EB is reported for larger nanocubes (34 and 43 nm). The observed EB effect is ascribed to the strong interfacial coupling between the ferrimagnetic (FiM) Fe 3 O 4 phase and AFM FeO phase, while its absence is related to the disappearance of the FeO phase. The Fe 3 O 4 / α -Fe 2 O 3 (FiM/AFM) interfaces are found to have negligible influence on the EB. Our findings shed light on the complexity of the EB effect in mixed-phase iron oxide nanosystems and pave the way to design exchange-coupled nanomaterials with desirable magnetic properties for biomedical and spintronic applications.

Physics↗
NASA NTRS1990

High pressure-temperature electrical conductivity of magnesiowustite as a function of iron oxide concentration

The electrical conductivity of (Mg, Fe)O magnesiowustite containing 9 and 27.5 mol pct FeO has been measured at simultaneously high pressures (30-32 GPa) and temperatures using a diamond anvil cell heated with a continuous wave Nd:YAG laser and an external resistance heater. The conductivity depends strongly on the FeO concentration at both ambient and high pressures. At the pressures and temperatures of about 30 GPa and 2000 K, conditions expected in the lower mantle, the magnesiowustite containing 27.5 percent FeO is 3 orders of magnitude more conductive than that containing 9 percent FeO. The activation energy of magnesiowustite decreases with increasing iron concentration from 0.38 (+ or - 0.09) eV at 9 percent FeO to 0.29 (+ or - 0.05) eV at 27.5 percent FeO.

Li, Xiaoyuan↗
NASA NTRS2006

Evidence in CO3.0 Chondrules for a drift in the O Isotopic Composition of the Solar Nebula

Several recent studies have shown that materials such as magnetite that formed in asteroids tend to have higher Delta O-17 (=delta O-17 -0.52 delta O-18) values than those recorded in unaltered chondrules. Other recent studies have shown that, in sets of chondrules from carbonaceous chondrites, Delta O-17 tends to increase as the FeO contents of the silicates increase. We report a comparison of the O isotopic composition of olivine phenocrysts in low-FeO ( Fal5) type II porphyritic chondrules in the highly primitive C03.0 chondrite Yamato-81020. In agreement with a similar study of chondrules in C03.0 ALH A77307 by Jones et al., Delta O-17 tends to increase with increasing FeO. We find that Delta O-17 values are resolved (but only marginally) between the two sets of olivine phenocrysts. In two of the high-FeO chondrules, the difference between Delta O-17 of the late-formed, high-FeO phenocryst olivine and those in the low-FeO cores of relict grains is well-resolved (although one of the relicts is interpreted to be a partly melted amoeboid olivine inclusion by Yurimoto and Wasson). It appears that, during much of the chondrule-forming period, there was a small upward drift in the Delta O-17 of nebular solids and that relict cores preserve the record of a different (and earlier) nebular environment.

Wasson, John T.↗
NASA NTRS2011

Iron Redox Systematics of Martian Magmas

Martian magmas are known to be FeO-rich and the dominant FeO-bearing mineral at many sites visited by the Mars Exploration rovers (MER) is magnetite [1]. Morris et al. [1] propose that the magnetite appears to be igneous in origin, rather than of secondary origin. However, magnetite is not typically found in experimental studies of martian magmatic rocks [2,3]. Magnetite stability in terrestrial magmas is well understood, as are the stability of FeO and Fe2O3 in terrestrial magmas [4,5]. In order to better understand the variation of FeO and Fe2O3, and the stability of magnetite (and other FeO-bearing phases) in martian magmas we have undertaken an experimental study with two emphases. First we document the stability of magnetite with temperature and fO2 in a shergottite bulk composition. Second, we determine the FeO and Fe2O3 contents of the same shergottite bulk composition at 1 bar and variable fO2 at 1250 C, and at variable pressure. These two goals will help define not only magnetite stability, but pyroxene-melt equilibria that are also dependent upon fO2.

Righter, K.↗
NASA NTRS2012

Unusual Iron Redox Systematics of Martian Magmas

Martian magmas are known to be FeO-rich and the dominant FeO-bearing mineral at many sites visited by the Mars Exploration rovers (MER) is magnetite. Morris et al. proposed that the magnetite appears to be igneous in origin, rather than of secondary origin. However, magnetite is not typically found in experimental studies of martian magmatic rocks. Magnetite stability in terrestrial magmas is well understood, as are the stabilities of FeO and Fe2O3 in terrestrial magmas. In order to better understand the variation of FeO and Fe2O3, and the stability of magnetite (and other FeO-bearing phases) in martian magmas, we have undertaken an experimental study with two emphases. First, we determine the FeO and Fe2O3 contents of super- and sub-liquidus glasses from a shergottite bulk composition at 1 bar to 4 GPa, and variable fO2. Second, we document the stability of magnetite with temperature and fO2 in a shergottite bulk composition.

Danielson, L.↗
NASA NTRS2013

Pyroclastic Deposits in the Floor-fractured Crater Alphonsus

Alphonsus, the 118 km diameter floor-fractured crater, is located immediately east of Mare Nubium. Eleven pyroclastic deposits have been identified on the crater's floor. Early telescopic spectra suggest that the floor of Alphonsus is noritic, and that the pyroclastic deposits contain mixtures of floor material and a juvenile component including basaltic glass. Head and Wilson contend that Nubium lavas intruded the breccia zone beneath Alphonsus, forming dikes and fractures on the crater floor. In this model, the magma ascended to the level of the mare but cooled underground, and a portion broke thru to the surface in vulcanian (explosive) eruptions. Alternatively, the erupted material could be from a source unrelated to the mare, in the style of regional pyroclastic deposits. High-resolution images and spectroscopy from the Moon Mineralogy Mapper (M3), Diviner Lunar Radiometer, and Lunar Reconnaissance Orbiter Camera Narrow Angle Camera (NAC) provide data to test these formation models. Spectra from M3 confirm that the crater floor is primarily composed of noritic material, and that the Nubium lavas are basaltic. Spectra from the three largest pyroclastic deposits in Alphonsus are consistent with a minor low- Ca pyroxene component in a glass-rich matrix. The centers of the 2 micron absorption bands have wavelengths too short to be of the same origin as the Nubium basalts. Diviner Christiansen feature (CF) values were used to estimate FeO abundances for the crater floor, Nubium soil, and pyroclastic deposits. The estimated abundance for the crater floor (7.5 +/- 1.4 wt.%) is within the range of FeO values for Apollo norite samples. However, the estimated FeO abundance for Nubium soil (13.4 +/- 1.4 wt.%) is lower than those measured in most mare samples. The difference may reflect contamination of the mare soil by highland ejecta. The Diviner-derived FeO abundance for the western pyroclastic deposit is 13.8 +/- 3.3 wt.%. This is lower than the values for mare soil samples, but within the range of analyzed pyroclastic glasses. The NAC images of the pyroclastic vents highlight their bright wall materials. The M3 spectra of the southeastern vent indicate that this bright material is noritic, likely crater floor material exposed by explosive eruption. These observations address the hypothesis that Nubium lavas intruded the fracture network beneath Alphonsus, leading to localized vulcanian-style eruptions. This model implies that the eruption products should be dominated by crystalline basalt fragments similar in elemental composition and mineralogy to mare lavas. The bright noritic material exposed in the vent walls is consistent with explosive eruptions. The estimated FeO abundances for the pyroclastic deposits are too low to be consistent with FeO abundances measured in mare basalts, but are within the range of pyroclastic glass samples. The visible- to near-infrared (VIS-NIR) spectra of the pyroclastic deposits and Nubium soils are significantly different, suggesting that the pyroclastics are unrelated to the mare basalts. The pyroclastic spectra are consistent with Fe-bearing glass plus small amounts of noritic wall rock. Similar glassy materials dominate regional pyroclastic deposits, suggesting a deep source for the pyroclastics observed in Alphonsus.

Allen, Carlton C.↗
DOE OSTI2024

Revealing Structural Evolution of Nickel Phosphide-Iron Oxide Core–Shell Nanocatalysts in Alkaline Medium for the Oxygen Evolution Reaction

Metal phosphide-containing materials have emerged as a potential candidate of non-precious metal-based catalysts for alkaline oxygen evolution reaction (OER). While it is known that metal phosphide undergoes structural evolution, considerable debate persists regarding the effects of dynamics on the surface activation and morphological stability of the catalysts. In this study, we synthesize NiP x -FeO x core-shell nanocatalysts with an amorphous NiP x core designed for enhanced OER activity. Using ex-situ X-ray absorption spectroscopy, we elucidate the local structural changes as a function of cyclic voltammetry cycles. Our studies suggest that the presence of corner-sharing octahedra in the FeO x shell improves structural rigidity through interlayer cross-linking, thereby inhibiting the diffusion of OH - /H 2 O. Thus, the FeO x shell preserves the amorphous NiP x core from rapid oxidation to Ni 3 (PO 4 ) 2 and Ni(OH) 2 . On the other hand, the incorporation of Ni from the core into the FeO x shell facilitates absorption of hydroxide ions for OER. As a result, the Ni/Fe(OH) x at the surface oxidizes to the active γ-(oxy)hydroxide phase under the applied potentials, promoting OER. This intriguing synergistic behavior holds significance as such synthetic route involving the FeO x shell can be extended to other systems, enabling manipulation of surface adsorption and diffusion of hydroxide ions. These findings also demonstrate that nanomaterials with core-shell morphology can be tuned to leverage the strength of each metallic component for improved electrochemical activities.

25 ENERGY STORAGE↗
DOE OSTI2022

Metal–Metal Oxide Catalytic Interface Formation and Structural Evolution: A Discovery of Strong Metal–Support Bonding, Ordered Intermetallics, and Single Atoms

In-depth investigation of metal–metal oxide interactions and their corresponding evolution is of paramount importance to heterogeneous catalysis as it allows the understanding and maneuvering of the structure of catalytic motifs. Herein, using a series of core/shell metal/iron oxide (M/FeO x , M = Pd, Pt, Au) nanoparticles and through a combination of in situ and ex situ electron and X-ray investigations, we revealed anomalous and dissimilar M–FeO x interactions among different systems under reducing conditions. Further, Pd interacts strongly with FeO x after high-temperature reductive treatment, featured by the formation of Pd single atoms in the FeO x matrix and increased Pd–Fe bonding, while Pt transforms into ordered PtFe intermetallics and Pt single atoms immediately upon the coating of FeO x . In contrast, Au does not manifest strong bonding with FeO x . As a proof of concept of tailoring metal–metal oxide interactions for catalysis, optimized Pd/FeO x demonstrates 100% conversion and 86.5% selectivity at 60 °C for acetylene semihydrogenation.

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

Cleavable quaternary oxychlorides with high magnetic ordering temperatures

Quaternary oxychlorides derived from Ruddlesden–Popper 3d transition metal oxides offer a route to cleavable crystals with bulk antiferromagnetic ordering temperatures reaching at least 550 K. Here, we study the magnetic, optical, and mechanical behavior of Sr 2 FeO 3 Cl, Ca 2 FeO 3 Cl, Ca 3 Fe 2 O 5 Cl 2 , and Sr 3 Fe 2 O 5 Cl 2 . Through optical absorption measurements, we show that these antiferromagnetic semiconductors have optical band gaps of ≈2.1(1) eV. The magnetic ordering symmetries and temperatures were probed by neutron powder diffraction and Mössbauer spectroscopy on polycrystalline samples, demonstrating Néel temperatures (T N ) near room temperature in the single layer Sr 2 FeO 3 Cl (T N ≈ 311 K) and Ca 2 FeO 3 Cl (T N ≈ 360 K), and the double-layer compound Sr 3 Fe 2 O 5 Cl 2 has T N ≈ 545 K. The high-spin moments of Fe 3+ lie within the basal plane and the magnetic structures are compensated within each magnetic layer and characterized by magnetic propagation vectors k = ($\frac{1}{2}$ $\frac{1}{2}$ 0). Magnetization results demonstrate the quasi-2D nature of the magnetism, with a broad maximum in the susceptibility near 2T N for Sr 2 FeO 3 Cl. Scotch tape tests and mechanical exfoliation onto SiO 2 confirm the micaceous nature of these crystals with cleavage down to a single unit cell (two magnetic layers) achieved for Sr 3 Fe 2 O 5 Cl 2 . In conclusion, this paper highlights strong antiferromagnetic interactions, semiconducting band gaps, and cleavability of quaternary Fe-based oxychlorides and motivates future work on crystals and exfoliated flakes of these and related oxyhalide systems.

36 MATERIALS SCIENCE↗