In situ experimental formation and growth of Fe nanoparticles and vesicles in lunar soil

We report the results of the first dynamic, in situ heating of lunar soils to simulate micrometeorite impacts on the lunar surface. We performed slow‐ and rapid‐heating experiments inside the transmission electron microscope to understand the chemical and microstructural changes in surface soils resulting from space‐weathering processes. Our slow‐heating experiments show that the formation of Fe nanoparticles begins at ~575 °C. These nanoparticles also form as a result of rapid‐heating experiments, and electron energy‐loss spectroscopy measurements indicate the Fe nanoparticles are composed entirely of Fe⁰, suggesting this simulation accurately mimics micrometeorite space‐weathering processes occurring on airless body surfaces. In addition to Fe nanoparticles, rapid‐heating experiments also formed vesiculated textures in the samples. Several grains were subjected to repeated thermal shocks, and the measured size distribution and number of Fe nanoparticles evolved with each subsequent heating event. These results provide insight into the formation and growth mechanisms for Fe nanoparticles in space‐weathered soils and could provide a new methodology for relative age dating of individual soil grains from within a sample population.     

Detection of ferric iron in an exsolved lunar pyroxene using electron energy loss spectroscopy (EELS): Implications for space weathering and redox conditions on the Moon

To shed light on the mechanism of formation of nanophase iron particles (npFe) in space-weathered materials from airless bodies, we analyzed exsolved and unexsolved space-weathered lunar pyroxenes from Apollo 17 sample 71501. The exsolved pyroxene allowed for the observation of the effects of space weathering on similar mineral phases with variable composition. Using coordinated scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy (EELS), we determined that two coexisting pyroxenes in the exsolved grain showed systematic variations in response to space weathering, despite equivalent exposure conditions. The npFe in the space-weathered rim of augite lamellae were smaller and fewer than the npFe in the rim of pigeonite lamellae. EELS spectrum imaging revealed the presence and heterogeneous distribution of Fe⁰, Fe²⁺, and Fe³⁺ in the exsolved pyroxene. Metallic iron occurred in the npFe, a mixture of Fe²⁺ and Fe³⁺ occurred in the pigeonite lamellae, and the augite lamellae contained virtually all Fe³⁺. Approximately 50% of the total Fe measured in the exsolved pyroxene grain was ferric. Partitioning of Fe²⁺ and Fe³⁺ among the lamellae is invoked to explain the difference in npFe development in pigeonite and augite. The results of this study, the first to identify Fe³⁺ in a crystalline lunar ferromagnesian silicate, have implications for our understanding of how space weathering might proceed in oxidized phases. Furthermore, the discovery of an Fe³⁺-rich pyroxene also supports attribution of the 0.7 μm absorption feature observed in Galileo Solid State Imager data to oxidized Fe in clinopyroxenes.     

Iron oxidation state in impact glass from the K/T boundary at Beloc,Haiti, by high‐resolution XANES spectroscopy

Abstract— We examined the local iron environment in nine impact glasses from the Cretaceous‐Tertiary (K/T) boundary section at Beloc, Haiti, which formed as the result of impact melting during the Chicxulub impact event. The samples have been analyzed by Fe K‐edge high‐resolution X‐ray absorption near edge structure (XANES) spectroscopy to obtain data on both the Fe oxidation state and the coordination number. The pre‐edge peak of our high‐resolution XANES spectra display noticeable variations indicative of significant changes in the Fe oxidation state spanning a wide range from about 20 to 75 mol% trivalent Fe. All data plot along the same trend, falling between two mixing lines joining a point calculated as the mean of a group of tektites studied so far (consisting of four‐ and five‐coordinated Fe²⁺) to ^[4]Fe³⁺ and ^[5]Fe³⁺, respectively. Thus, the XANES spectra can be interpreted as a mixture of ^[4]Fe²⁺, ^[5]Fe²⁺, ^[4]Fe³⁺, and ^[5]Fe³⁺. There is no evidence for six‐fold coordinated Fe; however, its presence in small amounts cannot be excluded from XANES data alone. Our observations can be explained by two possible scenarios: either these impact glasses formed under very reducing conditions and, because of their small size, were easily oxidized in air while still molten, or they formed under a variety of different oxygen fugacities resulting in different Fe oxidation states. In the first case, the oxidation state and coordination number would imply similar formation conditions as splash‐form tektites, followed by progressive oxidation.     

Yellow impact glass from the K/T boundary at Beloc (Haiti): XANES determination of the Fe oxidation state and implications for formation conditions

Abstract— We determined the iron oxidation state and coordination number in five samples of yellow impact glass from the Cretaceous‐Tertiary (K/T) boundary section at Beloc, Haiti, which formed as the result of impact melting during the Chicxulub impact event. The samples were analyzed by Fe K‐edge XANES spectroscopy and the results were compared with published data on eight black impact glasses and one high Si‐K impact spherule from the same impact layer. The pre‐edge peak of our high‐resolution XANES spectra displays evident variations indicative of significant changes in the Fe oxidation state, spanning a wide range from about 75 to 100 mole% Fe³⁺. Yellow K/T glasses have significantly higher Fe³⁺/(Fe²⁺ + Fe³⁺) ratios compared to black K/T impact glasses (from 20 to 75 mole% Fe³⁺) and high Si‐K glass (20 mole% Fe³⁺). In particular, all the pre‐edge peak data on these three types of impact glasses plot between two mixing lines joining a point calculated as the mean of a group of tektites studied so far (consisting of ^[4]Fe²⁺ and ^[5]Fe²⁺) to ^[4]Fe³⁺ and ^[5]Fe³⁺, respectively. Thus, the XANES spectra of the yellow K/T glasses can be interpreted as a mixture of ^[4]Fe^{2+, [5]}Fe^{2+, [4]}Fe³⁺, and ^[5]Fe³⁺. Our observations can be explained by a very large range of oxygen fugacity conditions during melt formation. Furthermore, there is a clear positive relationship between the Fe³⁺/(Fe²⁺ + Fe³⁺) ratio and the Ca content of these glasses, suggesting that the Fe oxidation state was influenced by the relative contribution of Ca‐sulfate‐ and Ca‐carbonate‐bearing sedimentary rocks at the impact site.     

Polarized absorption spectra of single crystals of lunar pyroxenes and olivines

Measurements have been made of the polarized absorption spectra (360-2200 nm.) of compositionally zoned pyroxene minerals in rocks 10045, 10047 and 10058 and olivines in rocks 10020 and 10022. Specimens in the form of petrographic thin sections were mounted on polarizing microscopes equipped with three-axis universal stage attachments and inserted into a Cary 17 spectrophotometer. The Apollo 11 pyroxenes with relatively high Ti/Fe ratios were chosen initially to investigate the presence of crystal field spectra of Fe²⁺ and Ti³⁺ ions in the minerals.Broad intense bands at about 1000 and 2100 nm. arise from spin-allowed, polarization-dependent transitions in Fe²⁺ ions in pyroxenes. Several weak sharp peaks occur in the visible region. Peaks at 402, 425, 505, 550 and 585 nm. represent spin-forbidden transitions in Fe²⁺ ions, while broader bands at 460–470 nm. and 650–660 nm. are attributed to Ti³⁺ ions. Charge transfer bands, which in terrestrial pyroxenes often extend into the visible region, are displaced to shorter wavelengths in lunar pyroxenes. This feature correlates with the absence of Fe³⁺ ions in these minerals. The magnitudes of the intensity ratios: band 465 nm. (Ti³⁺) to band 1000 nm. (Fe²⁺) are similar to Ti/Fe ratios from lunar pyroxene bulk chemical analyses, suggesting that an appreciable amount of titanium occurs as Ti³⁺ ions in the lunar pyroxenes. The 505 nm. spin-forbidden peak in Fe²⁺, together with absorption at 465 nm. by Ti³⁺, contribute to the pink or pale reddish-brown colors of lunar pyroxenes in transmitted lights.The absorption spectral measurements not only provide information on the redox behavior and crystal chemistry of lunar pyroxenes, but also form a basis for interpreting spectral reflectivity properties of lunar rocks and the Moon's surface.     

Iron oxidation state in the Fe‐rich layer and silica matrix of Libyan Desert Glass: A high‐resolution XANES study

Abstract— Libyan Desert Glass (LDG) is an enigmatic type of glass that occurs in western Egypt in the Libyan Desert. Fairly convincing evidence exists to show that it formed by impact, although the source crater is currently unknown. Some rare samples present dark‐colored streaks with variable amounts of Fe, and they are supposed to contain a meteoritic component. We have studied the iron local environment in an LDG sample by means of Fe K‐edge highresolution X‐ray absorption near edge structure (XANES) spectroscopy to obtain quantitative data on the Fe oxidation state and coordination number in both the Fe‐poor matrix and Fe‐rich layers. The pre‐edge peak of the high‐resolution XANES spectra of the sample studied displays small but reproducible variations between Fe‐poor matrix and Fe‐rich layers, which is indicative of significant changes in the Fe oxidation state and coordination number. Comparison with previously obtained data for a very low‐Fe sample shows that, while iron is virtually all trivalent and in tetrahedral coordination (^[4]Fe³⁺) in the low‐Fe sample, the sample containing the Fe‐rich layers display a mixture of tetra‐coordinated trivalent iron (^[4]Fe³⁺) and penta‐coordinated divalent iron (^[5]Fe²⁺), with the Fe in the Fe‐rich layer being more reduced than the matrix. From these data, we conclude the following: a) the significant differences in the Fe oxidation state between LDG and tektites, together with the wide intra‐sample variations in the Fe‐oxidation state, confirm that LDG is an impact glass and not a tektite‐like glass; b) the higher Fe content, coupled with the more reduced state of the Fe, in the Fe‐rich layers suggests that some or most of the Fe in these layers may be directly derived from the meteoritic projectile and that it is not of terrestrial origin.     

Polyhedral serpentine grains in CM chondrites

Abstract— We used high‐resolution transmission electron microscopy (HRTEM), electron tomography, electron energy‐loss spectroscopy (EELS), and energy‐dispersive spectroscopy (EDS) to investigate the structure and composition of polyhedral serpentine grains that occur in the matrices and fine‐grained rims of the Murchison, Mighei, and Cold Bokkeveld CM chondrites. The structure of these grains is similar to terrestrial polygonal serpentine, but the data show that some have spherical or subspherical, rather than cylindrical morphologies. We therefore propose that the term polyhedral rather than polygonal be used to describe this material. EDS shows that the polyhedral grains are rich in Mg with up to 8 atom% Fe. EELS indicates that 70% of the Fe occurs as Fe³⁺. Alteration of cronstedtite on the meteorite parent body under relatively oxidizing conditions is one probable pathway by which the polyhedral material formed. The polyhedral grains are the end‐member serpentine in a mineralogic alteration sequence for the CM chondrites.     

The effects of space weathering on Apollo 17 mare soils: Petrographie and chemical characterization

Abstract— The lunar soil characterization consortium, a group of lunar‐sample and remote‐sensing scientists, has undertaken the extensive task of characterization of the finest fractions of lunar soils, with respect to their mineralogical and chemical makeup. These compositional data form the basis for integration and modeling with the reflectance spectra of these same soil fractions. This endeavor is aimed at deciphering the effects of space weathering of soils on airless bodies with quantification of the links between remotely sensed reflectance spectra and composition. A beneficial byproduct is an understanding of the complexities involved in the formation of lunar soil. Several significant findings have been documented in the study of the <45 μm size fractions of selected Apollo 17 mare soils. As grain size decreases, the abundance of agglutinitic glass increases, as does the plagioclase, whereas the other minerals decrease. The composition of the agglutinitic glass is relatively constant for all size fractions, being more feldspathic than any of the bulk compositions; notably, TiO₂ is substantially depleted in the agglutinitic glass. However, as grain size decreases, the bulk composition of each size fraction continuously changes, becoming more Al‐rich and Fe‐poor, and approaches the composition of the agglutinitic glasses. Between the smallest grain sizes (10–20 and < 10 μm), the I_S/FeO values (amount of total iron present as nanophase Fe⁰) increase by greater than 100% (>2x), whereas the abundance of agglutinitic glass increases by only 10–15%. This is evidence for a large contribution from surface‐correlated nanophase Fe⁰ to the I_S/FeO values, particularly in the <10 μm size fraction. The surface nanophase Fe⁰ is present largely as vapor‐deposited patinas on the surfaces of almost every particle of the mature soils, and to a lesser degree for the immature soils (Keller et al., 1999a). It is reasoned that the vapor‐deposited patinas may have far greater effects upon reflectance spectra of mare soils than the agglutinitic Fe⁰.     

Determination of the Fe oxidation state of the Chassigny kaersutite: A microXANES spectroscopic study

Abstract— In order to elucidate the formation of low‐H kaersutites in Martian meteorites, the Fe³⁺/ΣFe ratio of Chassigny kaersutites in magmatic inclusions was directly determined by the synchrotron microXANES analysis. XANES analysis for standard kaersutites with known Fe³⁺/ΣFe ratios shows a linear relationship between centroid energy positions of XANES pre‐edge spectra and the Fe³⁺/ΣFe ratio. Based on the linear relationship, the Fe³⁺/ΣFe ratio of Chassigny kaersutites is estimated to be about 0.05. The low Fe³⁺/ΣFe ratio clearly suggests that low‐H kaersutites in Chassigny are not likely to be formed by the oxidation‐dehydrogenation reactions. The low‐H content of the Chassigny kaersutites is mainly due to the presence of a Ti oxy‐component.     

Druse clinopyroxene in D'Orbigny angritic meteorite studied by single‐crystal X‐ray diffraction,electron microprobe analysis,and Mössbauer spectroscopy

Abstract— The crystal structure of druse clinopyroxene from the D'Orbigny angrite, (Ca_0.944 Fe²⁺_0.042 Mg_0.010Mn_0.004) (Mg_0.469Fe²⁺_0.317Fe³⁺_0.035Al_0.125Cr_0.010Ti_0.044) (Si_1.742Al_0.258) O₆, a = 9.7684(2), b = 8.9124(2), c = 5.2859(1) Å, β = 105.903(1)°, V = 442.58 ų, space group C2/c, Z = 2, has been refined to an R₁ index of 1.92% using single‐crystal X‐ray diffraction data. The unit formula, calculated from electron microprobe analysis, and the refined site scattering values were used to assign site populations. The distribution of Fe²⁺and Mg over the M1 and M2 sites suggests a closure temperature of 1000 °C. Mössbauer spectroscopy measurements were done at room temperature on a single crystal and a powdered sample. The spectra are adequately fit by a Voigt‐based quadrupole‐splitting distribution model having two generalized sites, one for Fe²⁺with two Gaussian components and one for Fe³⁺with one Gaussian component. The two ferrous components are assigned to Fe²⁺at the M1 site, and arise from two different next‐nearest‐neighbor configurations of Ca and Fe cations at the M2 site: (3Ca,0Fe) and (2Ca,1Fe). The Fe³⁺/Fe_tot ratio determined by Mössbauer spectroscopy is in agreement with that calculated from the electron microprobe analysis. The results are discussed in connection with the redox and thermal history of D'Orbigny.     

On the spectral reflectance and maturation darkening of lunar soils

Optical absorption and diffuse reflectance spectra were obtained for simulated lunar glasses of four different compositions, both in their as-quenched (reduced) states and following mild subsolidus oxidation. The transmission spectra, when normalized by the FeO content of the glasses, differed from one another only in the relative intensity of an unresolved band in the UV. For fixed melting conditions the strength of this band in the as-quenched glasses increased with increasing FeO, or with increasing TiO₂ for a fixed FeO content. Electron spin resonance (ESR) experiments have demonstrated the absence of Fe³⁺ or Ti³⁺ and the presence of metallic iron in these materials; all other transition-group elements were excluded in preparation. The unresolved UV absorption edge in the as-quenched reduced glasses is therefore tentatively ascribed to Fe²⁺Ti⁴⁺ intervalency charge transfer transitions. A similar UV edge was also produced by oxidation, leading to the conclusion that the assignment of this band would be ambiguous in the absence of an independent determination of the valence states of Fe and Ti. The relationship between the transmission spectra of polished samples and the reflectance spectra of sieved powders of the same materials is shown to be well described by the Kubelka-Munk approximation. Using this insight, it is possible to understand the spectral characteristics both of oxidation darkening of synthetic glass powders and of maturation darkening of lunar soils in terms of (1) the growth of the aforementioned charge transfer band(s) and (2) the development of opaque surface phases. It is shown that mechanism (1) is of primary importance in lunar highland materials and that mechanism (2) dominates in mare materials. The present results, coupled with previous findings, suggest that lunar soil maturation darkening may result from vitrification only if accompanied by (a) enrichment in the elements Fe and Ti, (b) changes in valence states of these elements, (c) partial crystallization of opaque phases such as iron, ilmenite or magnetite, or (d) a combination of (a), (b), and (c).     

The iron record of asteroidal processes in carbonaceous chondrites

The valence of iron has been used in terrestrial studies to trace the hydrolysis of primary silicate rocks. Here, we use a similar approach to characterize the secondary processes, namely thermal metamorphism and aqueous alteration, that have affected carbonaceous chondrites. X‐ray absorption near‐edge structure spectroscopy at the Fe‐K‐edge was performed on a series of 36 CM, 9 CR, 10 CV, and 2 CI chondrites. While previous studies have focused on the relative distribution of Fe⁰ with respect to oxidized iron (Fe_ox = Fe²⁺ + Fe³⁺) or the iron distribution in some specific phases (e.g., Urey–Craig diagram; Urey and Craig 1953), our measurements enable us to assess the fractions of iron in each of its three oxidation states: Fe⁰, Fe²⁺, and Fe³⁺. Among the four carbonaceous chondrites groups studied, a correlation between the iron oxidation index (IOI = [2(Fe²⁺) + 3(Fe³⁺)]/[Fe_TOT]) and the hydrogen content is observed. However, within the CM group, for which a progressive alteration sequence has been defined, a conversion of Fe³⁺ to Fe²⁺ is observed with increasing degree of aqueous alteration. This reduction of iron can be explained by an evolution in the mineralogy of the secondary phases. In the case of the few CM chondrites that experienced some thermal metamorphism, in addition to aqueous alteration, a redox memory of the aqueous alteration is present: a significant fraction of Fe³⁺ is present, together with Fe²⁺ and sometimes Fe⁰. From our data set, the CR chondrites show a wider range of IOI from 1.5 to 2.5. In all considered CR chondrites, the three oxidation states of iron coexist. Even in the least‐altered CR chondrites, the fraction of Fe³⁺ can be high (30% for MET 00426). This observation confirms that oxidized iron has been integrated during formation of fine‐grained amorphous material in the matrix (Le Guillou and Brearley 2014; Le Guillou et al. 2015; Hopp and Vollmer 2018). Last, the IOI of CV chondrites does not reflect the reduced/oxidized classification based on metal and magnetite proportions, but is strongly correlated with petrographic types. The valence of iron in CV chondrites therefore appears to be most closely related to thermal history, rather than aqueous alteration, even if these processes can occur together (Krot et al. 2004; Brearley and Krot 2013).     

Bearing strength of lunar soil

Bearing load vs penetration curves have been measured on a 1.3 g sample of lunar soil from the scoop of the Surveyor 3 soil mechanics surface sampler, using a circular indentor 2 mm in diameter. Measurements were made in an Earth laboratory, in air. This sample provided a unique opportunity to evaluate earlier, remotely controlled, in-situ measurements of lunar surface bearing properties. Bearing capacity, measured at a penetration equal to the indentor diameter, varied from 0.02–0.04 N cm^–2 at bulk densities of 1.15 g cm^–3 to 30-100 N cm^–2 at 1.9 g cm^–3. Deformation was by compression directly below the indentor at bulk densities below 1.61 g cm^–3, by outward displacement at bulk densities over 1.62 g cm^–3. Preliminary comparison of in-situ remote measurements with those on returned material indicates good agreement if the lunar regolith at Surveyor 3 has a bulk density of 1.6 g cm^–3 at 2.5 cm. depth; definitive comparison awaits both better data on bulk density of the undisturbed lunar soil and additional mechanical-property measurements on returned material.     

Near‐infrared spectra of clinopyroxenes: Effects of calcium content and crystal structure

Abstract– Pyroxenes are among the most common minerals in the solar system and are ideally suited for remote geochemical analysis because of the sensitivity of their distinctive spectra to mineral composition. Fe²⁺ is responsible for the dominant pyroxene absorptions in the visible and near‐infrared, but substitutions of other cations such as Ca²⁺ change the crystal structure and site geometries and thus the crystal field splitting energies of the Fe cations. To define spectral systematics resulting from major pyroxene cations (Ca²⁺, Mg²⁺, and Fe²⁺), we focus on a suite of pyroxenes synthesized with only Ca²⁺, Mg²⁺, and Fe²⁺ in the two octahedral sites, specifically examining the effect of Ca²⁺ on pyroxene absorption bands. The modified Gaussian model is used to deconvolve pyroxene spectra into component bands that can then be linked directly to crystal field absorptions. In orthopyroxenes and low‐Ca clinopyroxenes, Ca²⁺‐content has a strong and predictable effect on the positions of the absorption bands. At a threshold of Wo₃₀, the crystal field environment stagnates and the M2 bands cease to change significantly as more Ca²⁺ is added. At Wo₅₀, when most of the M2 sites are filled by Ca²⁺, band positions do not change drastically, although the presence and strengths of the 1 and 2 μm bands are affected by even trace amounts of Fe²⁺ in the M2 site. It is thus apparent that next‐nearest neighbors and the distortions they impose on the pyroxene lattice affect the electronic states around the Fe²⁺ cations and control absorption band properties.     

Ultra‐reduced phases in Apollo 16 regolith: Combined field emission electron probe microanalysis and atom probe tomography of submicron Fe‐Si grains in Apollo 16 sample 61500

The lunar regolith contains a variety of chemically reduced phases of interest to planetary scientists and the most common, metallic iron, is generally ascribed to space weathering processes (Lucey et al. 2006 ). Reports of silicon metal and iron silicides, phases indicative of extremely reducing conditions, in lunar samples are rare (Anand et al. 2004 ; Spicuzza et al. 2011 ). Additional examples of Fe‐silicides have been identified in a survey of particles from Apollo 16 sample 61501,22. Herein is demonstrated the utility of low keV electron probe microanalysis (EPMA), using the Fe Ll X‐ray line, to analyze these submicron phases, and the necessity of accounting for carbon contamination. We document four Fe‐Si and Si⁰ minerals in lunar regolith return material. The new Fe‐Si samples have a composition close to (Fe,Ni)₃Si, whereas those associated with Si⁰ are close to FeSi₂ and Fe₃Si₇. Atom probe tomography of (Fe,Ni)₃Si shows trace levels of C (60 ppma and nanodomains enriched in C, Ni, P, Cr, and Sr). These reduced minerals require orders of magnitude lower oxygen fugacity and more reducing conditions than required to form Fe⁰. Documenting the similarities and differences in these samples is important to constrain their formation processes. These phases potentially formed at high temperatures resulting from a meteorite impact. Whether carbon played a role in achieving the lower oxygen fugacities—and there is evidence of nearby carbonaceous chondritic material—it remains to be proven that carbon was the necessary component for the unique existence of these Si⁰ and iron silicide minerals.     

Australasian microtektites from Antarctica: XAS determination of the Fe oxidation state

The Fe oxidation state and coordination number of 29 impact glass spherules recently recovered from the Transantarctic Mountains (Antarctica) have been determined by X‐ray absorption near edge structure (XANES) spectroscopy. Based on geochemical, isotopic, and fission track data, these spherules are considered as microtektites from the Australasian tektite/microtektite strewn field. Their find location is the farthest so far discovered from the possible source crater region, and their alkali content is the lowest compared with other published data on Australasian microtektite glasses. The Fe³⁺/(Fe²⁺+Fe³⁺) ratio, determined from the analysis of the pre‐edge peak energy position and integrated intensity, is below 0.1 (±0.04) for all the samples, and is comparable to that of most tektites and microtektites from the Australasian strewn field. Also, the pre‐edge peak integrated intensity, which is sensitive to the average Fe coordination geometry, is comparable to that of other Australasian microtektites reported in the literature. The agreement of the Fe oxidation state and coordination number, between the Transantarctic Mountain microtektites (TAM) and the Australasian tektites and microtektites, further confirms the impact origin of these glass spherules and provides an independent suggestion that they represent a major extension southeastward of the Australasian strewn field. The fact that similar redox conditions are observed in tektites and microtektites within the Australasian strewn field regardless of the distance from the source crater area (up to approximately 11000 km) could be an important constraint for better understanding the different processes affecting microtektite formation and transport. The fact that the Fe oxidation state of microtektites does not increase with distance, as in the case of North American microtektites, means that thermal and redox histories of Australasian and TAM microtektites could differ significantly from those of North American microtektites.     

Effect of hot desert weathering on the bulk‐rock iron isotope composition of L6 and H5 ordinary chondrites

Abstract– Although iron isotopes are increasingly used for meteorites studies, no attempt has been made to evaluate the effect of terrestrial weathering on this isotopic tracer. We have thus conducted a petrographic, chemical, and iron isotopic study of equilibrated ordinary chondrites (OC) recovered from hot Moroccan and Algerian Saharan deserts environment. As previously noticed, we observe that terrestrial desertic weathering is characterized by the oxidation of Fe‐Ni metal (Fe⁰), sulfide and Fe²⁺ occurring in olivine and pyroxene. It produces Fe‐oxides and oxyhydroxides that partially replace metal, sulfide grains and also fill fractures. The bulk chemical compositions of the ordinary chondrites studied show a strong Sr and Ba enrichment and a S depletion during weathering. Bulk meteoritic iron isotope compositions are well correlated with the degree of weathering and S, Sr, and Ba contents. Most weathered chondrites display the heaviest isotopic composition, by up to 0.1‰, which is of similar magnitude to the isotopic variations resulting from meteorite parent bodies’ formation and evolution. This is probably due to the release of isotopically light Fe²⁺ to waters on the Earth’s surface. Hence, when subtle Fe isotopic effects have to be studied in chondrites, meteorites with weathering grade above W2 should be avoided.     

Identification of magnetite in lunar regolith breccia 60016: Evidence for oxidized conditions at the lunar surface

Lunar regolith breccias are temporal archives of magmatic and impact bombardment processes on the Moon. Apollo 16 sample 60016 is an “ancient” feldspathic regolith breccia that was converted from a soil to a rock at ~3.8 Ga. The breccia contains a small (70 × 50 μm) rock fragment composed dominantly of an Fe‐oxide phase with disseminated domains of troilite. Fragments of plagioclase (An_95‐97), pyroxene (En_74‐75, Fs_21‐22,Wo_3‐4), and olivine (Fo_66‐67) are distributed in and adjacent to the Fe‐oxide. The silicate minerals have lunar compositions that are similar to anorthosites. Mineral chemistry, synchrotron X‐ray absorption near edge spectroscopy (XANES) and X‐ray diffraction (XRD) studies demonstrate that the oxide phase is magnetite with an estimated Fe³⁺/ΣFe ratio of ~0.45. The presence of magnetite in 60016 indicates that oxygen fugacity during formation was equilibrated at, or above, the Fe‐magnetite or wüstite–magnetite oxygen buffer. This discovery provides direct evidence for oxidized conditions on the Moon. Thermodynamic modeling shows that magnetite could have been formed from oxidization‐driven mineral replacement of Fe‐metal or desulphurisation from Fe‐sulfides (troilite) at low temperatures (<570 °C) in equilibrium with H₂O steam/liquid or CO₂ gas. Oxidizing conditions may have arisen from vapor transport during degassing of a magmatic source region, or from a hybrid endogenic–exogenic process when gases were released during an impacting asteroid or comet impact.     

Chemical composition and iron oxidation state of amorphous matrix silicates in the carbonaceous chondrite Acfer 094

Nanoscale amorphous silicates are a major component in primitive carbonaceous chondrite matrices and anhydrous interplanetary dust particles. Owing to their metastability and sensitive response to reactions with water, this material is of particular interest in understanding nebular and parent body processes in the early solar system. Here we investigated the amorphous silicate matrix (ASM) in the ungrouped carbonaceous chondrite Acfer 094 regarding its texture, chemical composition, and Fe oxidation state. We applied transmission electron microscopy techniques on six, focused ion beam technique-prepared, electron-transparent lamellae of Acfer 094 to determine the textures of this material. Furthermore, we used energy-dispersive X-ray analysis and electron energy loss spectroscopy to quantify the Fe content and the Fe oxidation state of the ASM. Textural investigations reveal differences in sulfide content, porosity, and distribution of the ASM among the samples, as well as evidence for rare recrystallization of phyllosilicate fibers. The chemical composition reveals mobilization of Fe. Furthermore, the determined Fe³⁺/ΣFe ratios of the ASM in the six samples display a homogeneously high oxidation state (0.66–0.73). This high and homogeneous Fe oxidation state in the ASM of Acfer 094 disagrees with its formation as a primary phase in a reduced solar gas and must have been induced in a later stage process. Most likely, this process was aqueous alteration on the Acfer 094 parent body, which led to hydration and oxidation of the ASM, which is supported by textural and chemical evidence of aqueous alteration.     

Alkali‐feldspathic material entrained in Fe,S‐rich veins in a monomict ureilite

Abstract— The Elephant Moraine (EET) 96001 ureilite contains a remarkable diversity of feldspars, which occur as tiny (no more than 60 μm maximum dimension) grains within a few Fe,S‐rich (now weathered to mostly Fe oxide) veins. Molar S: Fe ratio in the veins averages 0.08 ± 0.02. The veins meander and feature large fluctuations in apparent width; they appear to have entered this monomict breccia by a gentle, percolative process, not by violent impact injection. The feldspars are accompanied by a diverse suite of K‐rich (and generally also Ti‐rich) feldspathic glasses, and also major proportions of silica and pyroxene, which is largely fassaitic. A rhönite‐like phase is also found, and, as inclusions in one of the fassaites, a Cr‐poor spinel‐like phase. The feldspars mostly feature remarkably high K/Na compared to feldspars of comparable An from polymict ureilites. The EET 96001 feldspathic component was probably once part of a thin basaltic crust on a ureilite asteroid. The spinel included in one of the fassaites formed at remarkably high f0₂ (apparent oxidation state of iron: ～41 atom% Fe³⁺), suggesting that the parent magma possibly assimilated near‐surface water (however, the Fe³⁺ was not directly measured, and has conceivably been affected by terrestrial weathering; also, there is no assurance that this fassaite originated together with the typical feldspar). We speculate that the feldspathic component was mixed into the dense, Fe,S‐rich vein material, and very soon thereafter the Fe,S‐rich vein material was emplaced adjacent to the EET 96001 host ureilite, at an advanced stage in a chaotic catastrophic disruption and partial reassembly process that affected all ureilites. The high‐K nature of the EET 96001 feldspathic component, including the feldspathic glasses, suggests that fractional fusion may not have been as common during ureilite anatexis as has been inferred from recent studies of clast assemblages in polymict ureilites.