Modal mineralogy of carbonaceous chondrites by X‐ray diffraction and Mössbauer spectroscopy

Abstract— Carbonaceous chondrites are among the most analyzed geological materials on Earth. However, despite this attention, and unlike most terrestrial rocks, little is known on the abundance of individual phases within them. Here, we show how a combination of several novel X‐ray diffraction (XRD) techniques (including a high‐brightness X‐ray MicroSource®), and Mössbauer spectroscopy, allows a complete modal mineralogy to be ascertained from even the most highly unequilibrated, fine‐grained chondrites for all minerals of abundance >1 wt%. Knowledge of the modal mineralogy of a sample also allows us to calculate grain density. We analyzed Allende, Murchison, Tagish Lake, and Orgueil. Based on our modal data, the grain density estimates for Allende, Murchison, and Orgueil are close to literature values. In the case of Tagish Lake, there is no published grain density, although a bulk density measurement does exist. Taking our estimate of grain density, and the measured bulk density, we calculate an exceptionally high porosity of 41% for this meteorite, similar to some chondritic IDPs and in line with a porosity calculated from an entry model for the Tagish Lake fireball. Although it is an oxidized CV, magnetite is present in Allende at a level of <0.5 wt% or <0.3 vol%, a result that is substantiated by several other instrumental studies. This may be an oxidized meteorite, but that oxidation is not manifested in abundant magnetite. In addition, we note appreciable fayalitic olivine in Orgueil, detected by both XRD and Mössbauer. We employed MicroSource® XRD to look at heterogeneity in mineral abundance in Orgueil and found substantial variation, with phyllosilicates varying inversely with olivine. The data suggest that Orgueil was initially composed primarily of anhydrous materials, which have been partially, but not completely, altered. Although the data are preliminary, comparison between our XRD modal assessment, bulk chemistry, grain density, and Mössbauer data, suggests that our estimates of mineral abundance are robust. The advent of MicroSource® XRD allows similar modal data to be acquired from samples as small as a few hundred micrograms.     

Weathering of ordinary chondrites from the Atacama Desert,Chile, by Mössbauer spectroscopy and synchrotron radiation X‐ray diffraction

Some terrestrial areas have climatic and geomorphologic features that favor the preservation, and therefore, accumulation of meteorites. The Atacama Desert in Chile is among the most important of such areas, known as DCA. This desert is the driest on Earth, one of the most arid, uninhabitable localities with semiarid, arid, and hyper‐arid conditions. The meteorites studied here were collected from within the DCA of San Juan and Pampa de Mejillones, located, respectively, in the Central Depression and the Coastal Range of the Atacama Desert. ⁵⁷Fe Mössbauer spectroscopy was used for quantitative analysis of the degree of weathering of the meteorites, through the determination of the proportions of the various Fe‐bearing phases and in particular the amount of oxidized iron in terrestrial alteration products. The abundance of ferric ions in weathered chondrites can be related to specific precursor compositions and to the level of terrestrial weathering. The aim of the study was the identification, quantification, and differentiation of the weathering products in the ordinary chondrites found in the San Juan and the Pampa de Mejillones areas of the Atacama Desert. The ⁵⁷Fe Mössbauer spectroscopy study was complemented by synchrotron radiation X‐ray diffraction and magnetic susceptibility measurements. The results allow a clear differentiation of the rate of weathering in meteorite samples collected from the San Juan versus the Pampa de Mejillones areas of the Atacama Desert.     

A study of ordinary chondrites by Mössbauer spectroscopy with high‐velocity resolution

Abstract— An improvement in the velocity resolution and quality of Mössbauer spectra has been applied to a group of ordinary chondrites. This improvement permitted us to carry out a more detailed study of the iron bearing phases in these samples than has previously been possible. Mössbauer spectra of 11 ordinary chondrites of L and H chemical groups were measured using 4096 channels and presented for further analysis in 1024 channels. Subspectra of the metal grains of several chondrites demonstrated the presence of at least two magnetic sextets related to the main Fe(Ni, Co) phases. Moreover, Mössbauer study of extracted metal grains from Tsarev L5 revealed three sextets and one singlet spectral components related to various α‐Fe(Ni, Co), α‘‐Fe(Ni, Co), α₂‐Fe(Ni, Co), and γ‐Fe(Ni, Co) phases. Each subspectrum of olivine and pyroxene in Mössbauer spectra of ordinary chondrites was fitted by superposition of two quadrupole doublets related to M1 and M2 sites in minerals for the first time. An analysis of relative areas and Mössbauer hyperfine parameters was performed and some differences for L and H chondrites as well as for M1 and M2 sites were observed. Mössbauer parameters of troilite and oxidized iron were analyzed. In contrast to a previous study with 512‐channel spectra, the presence of oxidized iron was found in all chondrites.     

Application of Mössbauer spectroscopy,multidimensional discriminant analysis,and Mahalanobis distance for classification of equilibrated ordinary chondrites

Mössbauer spectra of equilibrated ordinary chondrites consist of two doublets due to paramagnetic iron present in olivines and pyroxenes and two sextets due to magnetically ordered iron present in metallic phases and troilite. The spectral areas of the different mineralogical phases found by Mössbauer spectroscopy in meteorites are proportional to the number of iron atoms in this mineralogical phase. This property of Mössbauer spectra can be the basis for constructing a method for the classification of ordinary chondrites. This idea was first explored at the Mössbauer Laboratory in Kanpur. This group suggested a qualitative method based on 2‐dimensional plots of Mössbauer spectral areas and thus classified properly some meteorites. We constructed a quantitative method using Mössbauer spectral areas, multidimensional discriminant analysis, and Mahalanobis distance (4M method) to determine the probability of a meteorite to be of type H, L, or LL. Based on 59 Mössbauer spectra, we calculated by the 4M method, S _cluster , the level of similarity of the Goronyo meteorite to the clusters. On the plot of ferrosilite versus fayalite, the point representing Goronyo is located on the border between H and L areas. Calculated by the 4M method, the meteorite Goronyo is 32% similar to type H, 75% to type L, and 11% to type LL. Additional mineralogical analyses suggested that the Goronyo meteorite would be classified as type L, although it was originally reported as type H in the Meteoritical Bulletin Database.     

Fe Mössbauer spectroscopy as a tool in astrobiology

The element Fe and Fe-bearing minerals occur ubiquitously throughout the field of astrobiology. Cycling between the various oxidation states of Fe provides a source of energy available for life. Banded iron formations may record the rise of oxygenic photosynthesis. The distribution of Fe between Fe-bearing minerals and its oxidation states can help to characterize and understand ancient environments with respect to the suitability for life by constraining the primary rock type and the redox conditions under which it crystallized, the extent of alteration and weathering, the type of alteration and weathering products, and the processes and environmental conditions for alteration and weathering. Fe Mössbauer spectroscopy is a powerful tool to investigate Fe-bearing compounds. It can identify Fe-bearing minerals, determine Fe oxidation states with high accuracy, quantify the distribution of Fe between mineralogical phases, and provide clues about crystallinity and particle sizes. Two miniaturized Mössbauer spectrometers are on board of the NASA Mars Exploration Rovers Spirit and Opportunity. The Fe-bearing minerals goethite, an iron oxide-hydroxide, and jarosite, an iron hydroxide sulfate, were identified by Mössbauer spectroscopy in Gusev Crater and at Meridiani Planum, respectively, providing in situ proof of an aqueous history of the two landing sites and constraints on their habitability. Hematite identified by Mössbauer spectroscopy at both landing sites adds further evidence for an aqueous history. On Earth, Mössbauer spectroscopy was used to monitor possibly microbially-induced changes of Fe-oxidation states in basaltic glass samples exposed at the Loihi Seamount, a deep sea hydrothermal vent system, which might be analogous to possible extraterrestrial habitats on ancient Mars or the Jovian moon Europa today.     

Rapid weathering in Holbrook: An iron-57 Mössbauer spectroscopy study

Abstract— Samples of Holbrook (an L6 chondrite that fell in Arizona in 1912) were analysed by ⁵⁷Fe Mössbauer spectroscopy to determine the proportion of the total Fe that had been converted to Fe³⁺ by weathering processes. Although samples recovered in 1912 showed negligible (<1%) alteration, a spectrum recorded from a specimen recovered in 1968 showed that 9.7% of the total Fe was present as Fe³⁺. Given the existence of samples in similar semiarid environments with terrestrial ages >40 ka, a linear rate of weathering is unrealistic, rapidly producing very high levels of oxidation in samples with low terrestrial ages. However if weathering follows an approximate power law, then we can model a rapid initial phase and the levels of oxidation that are more typical in samples with much longer terrestrial residence times recovered from Roosevelt County. Our analysis, together with work on terrestrial age dated samples, indicates that hot desert weathering of ordinary chondrites is at least a two-stage process, with an initial rapid phase lasting <500 years before oxidation is passivated.     

A Mössbauer spectroscopy and X‐ray diffraction study of ordinary chondrites: Quantification of modal mineralogy and implications for redox conditions during metamorphism

Abstract— We present a method that combines Mössbauer spectroscopy and X‐ray diffraction to quantify the modal mineralogy of unequilibrated ordinary chondrites (UOCs). Despite being a fundamental tool in the interpretation of geological systems, there are no modal mineralogical data available for these meteorites. This is due to their fine‐grained nature, highly heterogeneous silicate mineralogy, and the presence of poorly characterized phases. Consequently, it has not been possible to obtain accurate modal mineralogy by conventional techniques such as point counting. Here we use Mössbauer spectroscopy as a preliminary identification technique and X‐ray diffraction provides the quantification for a suite of recent UOC falls. We find the most primitive UOCs to contain a significant amount of phyllosilicate material that was converted during metamorphism to form ferromagnesian silicates. A complete suite of Antarctic samples is analyzed by each method to observe mineralogical trends and these are compared with trends shown by recent falls. The fact that mineralogical relationships shown by finds and falls are in agreement allows us to be confident that we are observing the products of pre‐terrestrial alteration. Mössbauer spectroscopy reveals evidence of steadily increasing reduction with metamorphism in the UOCs. Because this technique allows comparisons to be made between UOCs and EOCs, our reduction sequence can be combined with other evidence showing progressive oxidation in the EOCs. This yields an integrated model of changing redox conditions on equilibrating ordinary chondrite parent bodies.     

Mineralogy and 57Fe Mössbauer spectroscopy of opaque phases in the Neuschwanstein EL6 chondrite

Abstract— This study presents compositional data and ⁵⁷Fe Mössbauer spectra, taken at 295 K and 85 K, of two fragments of the enstatite (EL6) chondrite Neuschwanstein that fell near the famous Neuschwanstein castle (Bavaria, southern Germany) on April 6, 2002. Main silicate minerals are enstatite (Fs 2) and plagioclase (An 20), the main opaque minerals are kamacite and troilite. Small amounts of oldhamite, daubreelite, and schreibersite have been found. The presented Mössbauer data are the first data gathered for an EL6 chondrite. The dominant parts of each Mössbauer spectrum consist of two six‐line patterns due to the presence of ferromagnetic phases kamacite and troilite. In contrast to other chondrites, peaks of other iron species in the central parts of the spectra are missing due to an extremely low content of Fe‐bearing paramagnetic components. The hyperfine interaction parameters for kamacite are internal magnetic hyperfine field H_hf = 333.2 kOe, isomer shift (relative to a metallic Fe foil) IS = 0.01 mm/s, quadrupole splitting QS = 0 mm/s, line width W = 0.41 mm/s. The data for troilite are H_hf = 305.5 kOe, IS = 0.75 mm/s, QS = ?0.85 mm/s, W = 0.34 mm/s.     

Axtell and Allende: A Mössbauer spectroscopic study

Abstract— Mössbauer spectra showed the CV3 oxidized subgroup meteorites Allende and Axtell to be similar in olivine content and in a surprising lack of pronounced magnetic components, but different in Fe³⁺ phases. One atypical Allende sample showed an 8% area under the curve for magnetite, which is still less than a reported value for a CV3 reduced subgroup member. Allende's unusual Fe³⁺ spectral region distinguishes it from most other stony meteorites and is difficult to fit to known mineral parameters.     

Systematics of Mössbauer absorption areas in ordinary chondrites and applications to a newly fallen meteorite in Jodhpur,India

Abstract— Mössbauer absorption areas corresponding to ⁵⁷Fe in olivine, pyroxene, troilite, and the metallic phase in ordinary chondrites are shown to exhibit certain systematic behaviors. H chondrites occupy 2 distinct regions on the plot of metallic phase absorption area versus silicate absorption area, while L/LL chondrites fall in a separate region. Similar separation is also observed when pyroxene absorption area is plotted against olivine absorption area. The one‐dimensional plot for the ratio of olivine area to pyroxene area separates L and LL chondrites. Based on these systematics, a newly fallen meteorite at Jodhpur, India is suggested to be an LL chondrite.     

Ferric iron in SNC meteorites as determined by Mössbauer spectroscopy: Implications for martian landers and martian oxygen fugacity

Abstract— Mössbauer spectra of martian meteorites are currently of great interest due to the Mössbauer spectrometers on the Athena mission MER rovers as well as the European Space Agency Mars Express mission, with its Beagle 2 payload. Also, considerable current effort is being made to understand the oxygen fugacity of martian magmas because of the effect of fO₂ on mineral chemistry and crystallization processes. For these 2 reasons, the present study was conceived to acquire room temperature Mössbauer spectra of mineral separates and whole rock samples of 10 SNC meteorites. The results suggest that mineral identification using remote application of this technique will be most useful when the phases present have distinctive parameters arising from Fe in very different coordination polyhedra; for example, pyroxene coexisting with olivine can be discriminated easily, but opx versus cpx cannot. The MER goal of using Mössbauer spectroscopy to quantify the relative amounts of individual mineral species present will be difficult to satisfy if silicates are present because the lack of constraints on wt% FeO contents of individual silicate phases present will make modal calculations impossible. The remote Mössbauer spectroscopy will be most advantageous if the rocks analyzed are predominantly oxides with known stoichiometries, though these phases are not present in the SNCs. As for the detection of martian oxygen fugacity, no evidence exists in the SNC samples studied of a relationship between Fe³⁺ content and fO₂ as calculated by independent methods. Possibly, all of the Fe³⁺ observed in olivine is the result of dehydrogenation rather than oxidation, and this process may also be the source of all the Fe³⁺ observed in pyroxene. The observed Fe³⁺ in pyroxene also likely records an equilibrium between pyroxene and melt at such low fO₂ that little or no Fe³⁺ would be expected.     

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.     

Anomalous Mössbauer parameters in the second generation regolith Ghubara meteorite

Abstract— We conducted Mössbauer spectroscopic studies on the Ghubara meteorite which had been described as at least two‐generation regolith breccia on the macro scale. The isomer shift and quadrupole splitting of the Fe‐Ni part are quite different from those obtained in ordinary chondrites, reflecting shock effects. We observed a large amount of magnetite that may have come from weathering of, primarily, the silicate fraction. We found very similar iron mineralogy in the Densmore meteorite.     

Classification of the Didwana‐Rajod meteorite: A Mössbauer spectroscopic study

Abstract— Mössbauer spectroscopic studies of the Didwana‐Rajod chondrite, which fell on 1991 August 12 in western Rajasthan, India, are presented. The results are compared with the Mössbauer data of several enstatite and ordinary chondrites including the Dhajala chondrite for which Mössbauer data were acquired during the present study. The Didwana‐Rajod chondrite's iron phases and its oxidation states strongly suggest that it should be classified as an H‐type ordinary chondrite instead of the earlier suggestion (based on petrographic studies) that it could be an enstatite chondrite. The present study demonstrates that Mössbauer spectroscopy is a very powerful technique for aiding in the classification of meteorites.     

Weathering of Fe-bearing minerals under Martian conditions, investigated by Mössbauer spectroscopy

The surface of Mars is covered by weathered material. Mars' rusty red colour in particular is commonly ascribed to ferric iron-bearing minerals. The planet's surface is generally iron rich. Mössbauer spectroscopy is a powerful tool for quantitative mineralogical analysis of Fe-bearing minerals. Consequently, the miniaturized Mössbauer spectrometer MIMOS II is part of the payload of NASA's twin Mars Exploration Rovers “Spirit” and “Opportunity”, and ESA's ill-fated Mars Express lander “Beagle 2”. Both Mars Exploration Rovers are currently conducting successful surface operations on Mars. In this paper, we give a brief insight into mission operations with respect to the reconstruction of local weathering scenarios at the landing sites, which in turn will help to illuminate the climatic history of the planet. Mössbauer spectra obtained in preparation of the mission from the SNC meteorites Nakhla, Dar al Gani 476, and Sayh al Uhaymir, show weathering and other alteration features. Preliminary results of laboratory weathering experiments on Fe-bearing minerals (olivine and pyroxene) show the importance of analysing individual minerals to understand weathering of more complex mineral assemblages like, e.g., basalt.     

Depth-profiles and surface enrichment of the halogens in four Antarctic H5 chondrites and in two non-Antarctic chondrites

Abstract— Depth-profiles of F, Cl, Br and I concentrations were determined in four different Antarctic H5 chondrites from the Allan Hills and in the two chondrites Allende (C3) and Holbrook (L6). Pieces of the meteorites were studied by analysis of stepwise removed layers of 0.5–1.0 mm thickness up to a depth of 9 mm. Neutron activation analysis and ion-selective potentiometry were used for the determination of Cl, Br, I and for F, respectively. The Antarctic meteorites show higher concentrations of the halogens at the surface compared to the interior. The highest enrichment factors are found for I and Cl and the lowest for Br. In contrast, F shows the steepest concentration gradient and is only enriched in the first 2.5 mm below the surface. The other halogens have penetrated deeper into the meteorites. The measured enrichments at the surfaces are not correlated to the visible degree of weathering. The analysed non-Antarctic meteorites, which were recovered shortly after their observed fall, demonstrate similar halogen concentrations at the surface, including the fusion crust, as in the interior. Based on these results we present a model to estimate the degree of contamination and the relation to the duration of exposure at the surface of the Antarctic ice.     

Glassy magnetic cronstedtite signatures in Mukundpura CM2 chondrite based on magnetic and Mössbauer studies

We have studied the Mukundpura CM2 meteorite for magnetic properties as a function of temperature and magnetic field, as well as its Mössbauer spectrum, at room and low temperatures (up to 5 K). We find that the high temperature paramagnetic phase is followed by two magnetic transitions: a weak transition near 125 K and a strong transition at 8 K. The weak (125 K) magnetic phase can be attributed to complex Fe²⁺–Fe³⁺ constituents present in the meteorite. The absence of the characteristic sextet corresponding to magnetite in Mossbauer spectrum indicates that this magnetic phase is not magnetite, which, if present, must be in insignificant amount. The 8 K magnetic ordering is superimposed with weak ferromagnetic ordering, showing spin‐glass transition. The Mössbauer spectrum taken at 5 K substantiates the observed spin‐glassy nature, as very large hyperfine field ~32 T is recorded, causing localized subordering leading to spin‐glass behavior. The Mössbauer spectra also confirm that iron is mainly present in serpentine‐group minerals, both in ferrous and ferric states. The complete serpentinization of basic silicates indicates aggressive hydrous alteration. These results show that the observed spin‐glass signature is a characteristic feature of the cronstedtite phase in CM meteorites. This feature is unique to carbonaceous CM chondrites and could be used for nondestructive, quick, and independent classification of this rare class of meteorites. Furthermore, the absence of olivine and the presence of cronstedtite in Mossbauer spectra show that the degree of aqueous alteration observed is the most severe in Mukundpura CM2 meteorite, as compared to many other CM2 meteorites. The degree of aqueous alteration in CM2 carbonaceous chondrites increases in the sequence: Paris, Murchison, Murray, Mighei, Nogoya, Cold Bokkeveld, and Mukundpura.     

Olivine zoning and retrograde olivine‐orthopyroxene‐metal equilibration in H5 and H6 chondrites

Abstract— Electron microprobe studies of several H5 and H6 chondrites reveal that olivine crystals exhibit systematic Fe‐Mg zoning near olivine‐metal interfaces. Olivine Fa concentrations decrease by up to 2 mol% toward zoned taenite + kamacite particles (formed after relatively small amounts of taenite undercooling) and increase by up to 2 mol% toward zoneless plessite particles (formed after ?200 °C of taenite undercooling). The olivine zoning can be understood in terms of localized olivine‐orthopyroxene‐metal reactions during cooling from the peak metamorphic temperature. The silicate‐metal reactions were influenced by solid‐state metal phase transformations, and the two types of olivine zoning profiles resulted from variable amounts of taenite undercooling at temperatures <700 °C. The relevant silicate‐metal reactions are modeled using chemical thermodynamics. Systematic olivine Fe‐Mg zoning adjacent to metal is an expected consequence of retrograde silicate‐metal reactions, and the presence of such zoning provides strong evidence that the silicate and metallic minerals evolved in situ during cooling from the peak metamorphic temperature.     

Molecular and isotopic indicators of alteration in CR chondrites

Abstract— The CR group of carbonaceous chondrites may represent some of the most primitive extraterrestrial materials available for analysis. However, in contrast to other chondrite groups, the CR organic fraction is poorly characterized. The carbonaceous chondrite literature shows that relatively anhydrous thermal processing results in a condensed, poorly alkylated, O‐poor macromolecular material, while for aqueous processing the converse is true. Such characteristics can be used to discern the alteration histories of the carbonaceous chondrites. We have performed bulk elemental and isotopic analysis and flash pyrolysis on four CR chondrites (Renazzo, Al Rais, Elephant Moraine [EET] 87770, and Yamato [Y‐] 790112) to determine the nature of their organic component. Renazzo, Al Rais, and Y‐790112 release qualitatively similar pyrolysis products, although there are some variations. Al Rais' macromolecular structure contains substantially higher relative abundances of alkylated and oxidized species and relatively lighter δ¹⁵N, suggesting that it has endured more extensive aqueous processing than the other CR chondrites. Renazzo appears relatively unprocessed, with a low degree of alkylation, a lack of detectable nitrogen‐bearing components, and low methylnaphthalene ratio. EET 87770's low abundance of alkylated species suggests its macromolecular structure may be relatively condensed, with condensation potentially assisted by a period of mild thermal alteration.     

A high spatial resolution synchrotron Mössbauer study of the Tazewell IIICD and Esquel pallasite meteorites

Metallic phases in the Tazewell IIICD iron and Esquel pallasite meteorites were examined using ⁵⁷Fe synchrotron Mössbauer spectroscopy. Spatial resolution of ~10–20 μm was achieved, together with high throughput, enabling individual spectra to be recorded in less than 1 h. Spectra were recorded every 5–10 μm, allowing phase fractions and hyperfine parameters to be traced along transects of key microstructural features. The main focus of the study was the transitional region between kamacite and plessite, known as the “cloudy zone.” Results confirm the presence of tetrataenite and antitaenite in the cloudy zone as its only components. However, both phases were also found in plessite, indicating that antitaenite is not restricted exclusively to the cloudy zone, as previously thought. The confirmation of paramagnetic antitaenite as the matrix phase of the cloudy zone contrasts with recent observations of a ferromagnetic matrix phase using X‐ray photoemission electron spectroscopy. Possible explanations for the different results seen using these techniques are proposed.