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Analysis of Cation Composition in Dolomites on the Intact Particles Sampled from Asteroid Ryugu
Abstract
Characterization of the elemental distribution of samples with rough surfaces has been strongly desired for the analysis of various natural and artificial materials. Particularly for pristine and rare analytes with micrometer sizes embedded on specimen surfaces, non-invasive and matrix effect-free analysis is required without surface polishing treatment. To satisfy these requirements, we proposed a new method employing the sequential combination of two imaging modalities, i.e., microenergy-dispersive X-ray fluorescence (micro-XRF) and Raman micro-spectroscopy. The applicability of the developed method is tested by the quantitative analysis of cation composition in micrometer-sized carbonate grains on the surfaces of intact particles sampled directly from the asteroid Ryugu. The first step of micro-XRF imaging enabled a quick search for the sparsely scattered and micrometer-sized carbonates by the codistributions of Ca²⁺ and Mn²⁺ on the Mg²⁺- and Fe²⁺-rich phyllosilicate matrix. The following step of Raman micro-spectroscopy probed the carbonate grains and analyzed their cation composition (Ca²⁺, Mg²⁺, and Fe²⁺ + Mn²⁺) in a matrix effect-free manner via the systematic Raman shifts of the lattice modes. The carbonates were basically assigned to ferroan dolomite bearing a considerable amount of Fe²⁺ + Mn²⁺ at around 10 atom %. These results are in good accordance with the assignments reported by scanning electron microscopy–energy-dispersive X-ray spectroscopy, where the thin-sectioned and surface-polished Ryugu particles were applicable. The proposed method requires neither sectioning nor surface polishing; hence, it can be applied to the remote sensing apparatus on spacecrafts and planetary rovers. Furthermore, the non-invasive and matrix effect-free characterization will provide a reliable analytical tool for quantitative analysis of the elemental distribution on the samples with surface roughness and chemical heterogeneity at a micrometer scale, such as art paintings, traditional crafts with decorated shapes, as well as sands and rocks with complex morphologies in nature.
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The Hayabusa2 spacecraft explored asteroid Ryugu and brought its surface materials to Earth. Ryugu samples resemble Ivuna-type (CI) chondrites—the most chemically primitive meteorites—and contain secondary phyllosilicates and carbonates, which are indicative of aqueous alteration. Understanding the conditions (such as temperature, redox state and fluid composition) during aqueous alteration is crucial to elucidating how Ryugu evolved to its present state, but little is known about the temporal changes in these conditions. Here we show that calcium carbonate (calcite) grains in Ryugu and Ivuna samples have variable ¹⁸O/¹⁶O and ¹³C/¹²C ratios that are, respectively, 24–46‰ and 65–108‰ greater than terrestrial standard values, whereas those of calcium–magnesium carbonate (dolomite) grains are much more homogeneous, ranging within 31–36‰ for oxygen and 67–75‰ for carbon. We infer that the calcite precipitated first over a wide range of temperatures and oxygen partial pressures, and that the proportion of gaseous CO2/CO/CH4 molecules changed temporally. By contrast, the dolomite formed later in a more oxygen-rich and thus CO2-dominated environment when the system was approaching equilibrium. The characteristic isotopic compositions of secondary carbonates in Ryugu and Ivuna are not observed for other hydrous meteorites, suggesting a unique evolutionary pathway for their parent asteroid(s).
Carbonaceous meteorites are thought to be fragments of C-type (carbonaceous) asteroids. Samples of the C-type asteroid (162173) Ryugu were retrieved by the Hayabusa2 spacecraft. We measure the mineralogy, bulk chemical and isotopic compositions of Ryugu samples. They are mainly composed of materials similar to carbonaceous chondrite meteorites, particularly the CI (Ivuna-type) group. The samples consist predominantly of minerals formed in aqueous fluid on a parent planetesimal. The primary minerals were altered by fluids at a temperature of 37 ± 10°C, 5.2 − 0.8 + 0.7 (Stat.) − 2.1 + 1.6 (Syst.) million years after formation of the first solids in the Solar System. After aqueous alteration, the Ryugu samples were likely never heated above ~100°C. The samples have a chemical composition that more closely resembles the Sun’s photosphere than other natural samples do.
Carbonates are ubiquitous minerals carrying important information on aqueous environments where they precipitated on the Earth and space. While their ideal chemical formulae are denoted as simple as MCO 3 or M 1 M 2 (CO 3 ) 2 (M: metal cations), natural carbonates generally form solid-solution series and their compositions deviate from the ideal formulae. Since their cation composition due to the substitution provides a sensitive indicator for chemical and thermodynamic environments of aqueous solutions where they precipitated, their composition analysis has been widely carried out from the environmental/geochemical/astrochemical aspects. However, in widely used back-scattered electron and energy dispersion X-Ray analyses, samples should be generally sliced and/or their surface be polished prior to the measurements. For analyzing rare samples with small sizes, such as ones sampled from deep-sea and/or meteorites and asteroids, a non-destructive method without any pretreatments has been strongly desired. Here, a novel analytical method for discriminating various carbonates with Raman micro-spectroscopy is demonstrated, showing that the biaxial plot of the peak frequencies of their lattice modes linearly moves upon partial substitution of the cations. The cation substitution leads to linear movement in the biaxial map, and the slopes of the movement were different for Mg ²⁺ -Fe ²⁺ and Mn ²⁺ -Fe ²⁺ substitutions. This finding suggests that the micro-Raman analysis would be a non-destructive analytical method for evaluating the relative amount of Mg ²⁺ , Fe ²⁺ , and Mn ²⁺ in dolomite-ankerite-kutnohorite solid-solution series, as well as Mg ²⁺ /Fe ²⁺ ratio for magnesite-breunnerite-siderite. It would be helpful for analyzing the present and past terrestrial and cosmochemical environments.
Graphical abstract
C-type asteroids ¹ are considered to be primitive small Solar System bodies enriched in water and organics, providing clues to the origin and evolution of the Solar System and the building blocks of life. C-type asteroid 162173 Ryugu has been characterized by remote sensing 2–7 and on-asteroid measurements 8,9 with Hayabusa2 (ref. ¹⁰ ). However, the ground truth provided by laboratory analysis of returned samples is invaluable to determine the fine properties of asteroids and other planetary bodies. We report preliminary results of analyses on returned samples from Ryugu of the particle size distribution, density and porosity, spectral properties and textural properties, and the results of a search for Ca–Al-rich inclusions (CAIs) and chondrules. The bulk sample mainly consists of rugged and smooth particles of millimetre to submillimetre size, confirming that the physical and chemical properties were not altered during the return from the asteroid. The power index of its size distribution is shallower than that of the surface boulder observed on Ryugu ¹¹ , indicating differences in the returned Ryugu samples. The average of the estimated bulk densities of Ryugu sample particles is 1,282 ± 231 kg m ⁻³ , which is lower than that of meteorites ¹² , suggesting a high microporosity down to the millimetre scale, extending centimetre-scale estimates from thermal measurements 5,9 . The extremely dark optical to near-infrared reflectance and spectral profile with weak absorptions at 2.7 and 3.4 μm imply a carbonaceous composition with indigenous aqueous alteration, matching the global average of Ryugu 3,4 and confirming that the sample is representative of the asteroid. Together with the absence of submillimetre CAIs and chondrules, these features indicate that Ryugu is most similar to CI chondrites but has lower albedo, higher porosity and more fragile characteristics.
A portable Raman device with a 532 nm excitation laser and a portable infrared spectrometer with ATR (Attenuated Total Reflection) mode were used to analyse the spectral features associated with the identification and compositional variation of Ca-Mg-Fe-Mn natural carbonate minerals with a calcite structure (calcite, ankerite, dolomite, siderite, rhodochrosite, and magnesite). A systematic study of the variations of the peak positions with various compositional ratios was carried out. Most of the band positions were shifted to lower wavenumbers with increasing ionic radius or atomic mass of the divalent cations but the band of the translational lattice (T) mode in Raman and the symmetric bending (ν4) band in the mid-infrared were the most sensitive. Therefore, the elemental variation of the Ca-Mg-Fe-Mn ratio in this carbonate series can be estimated from Raman and infrared band positions from spectra acquired with portable spectrometers.
Asteroid (162173) Ryugu is the target object of Hayabusa2, an asteroid exploration and sample return mission led by Japan Aerospace Exploration Agency (JAXA). Ground-based observations indicate that Ryugu is a C-type near-Earth asteroid with a diameter of less than 1 km, but the knowledge of its detailed properties is still very limited. This paper summarizes our best understanding of the physical and dynamical properties of Ryugu based on remote sensing and theoretical modeling. This information is used to construct a design reference model of the asteroid that is used for formulation of mission operations plans in advance of asteroid arrival. Particular attention is given to the surface properties of Ryugu that are relevant to sample acquisition. This reference model helps readers to appropriately interpret the data that will be directly obtained by Hayabusa2 and promotes scientific studies not only for Ryugu itself and other small bodies but also for the Solar System evolution that small bodies shed light on.
X-ray fluorescence (XRF) analysis is a well-established analytical technique with a long research history. Many applications have been reported in various fields, such as in the environmental, archeological, biological, and forensic sciences as well as in industry. This is because XRF has a unique advantage of being a nondestructive analytical tool with good precision for quantitative analysis. Recent advances in XRF analysis have been realized by the development of new x-ray optics and x-ray detectors. Advanced x-ray focusing optics enables the making of a micro x-ray beam, leading to micro-XRF analysis and XRF imaging. A confocal micro-XRF technique has been applied for the visualization of elemental distributions inside the samples. This technique was applied for liquid samples and for monitoring chemical reactions such as the metal corrosion of steel samples in the NaCl solutions. In addition, a principal component analysis was applied for reducing the background intensity in XRF spectra obtained during XRF mapping, leading to improved spatial resolution of confocal micro-XRF images. In parallel, the authors have proposed a wavelength dispersive XRF (WD-XRF) imaging spectrometer for a fast elemental imaging. A new two dimensional x-ray detector, the Pilatus detector was applied for WD-XRF imaging. Fast XRF imaging in 1 s or even less was demonstrated for Euro coins and industrial samples. In this review paper, these recent advances in laboratory-based XRF imaging, especially in a laboratory setting, will be introduced.
Magnesite, siderite and ferromagnesites Mg1−x
Fe
x
CO3 (x = 0.05, 0.09, 0.2, 0.4) were characterized using in situ Raman spectroscopy at high pressures up to 55 GPa. For the Mg–Fe-carbonates, the Raman peak positions of six modes (T, L, ν4, ν1, ν3 and 2ν2) in the dependence of iron content in the carbonates at ambient conditions are presented. High-pressure Raman spectroscopy shows that siderite undergoes a spin transition at ~40 GPa. The examination of the solid solutions with compositions Mg0.6Fe0.4CO3, Mg0.8Fe0.2CO3, Mg0.91Fe0.09CO3 and Mg0.95Fe0.05CO3 indicates that with increase in the amount of the Fe spin transition pressure increases up to ~45 GPa.
Raman spectroscopy has been used to distinguish the individual carbonate minerals belonging to the calcite, dolomite, and aragonite structural groups. With the use of the in situ laser microprobe technique, it is demonstrated that particle-size effects do not hinder the mineral identification and that high precision in line position is achieved. Spectra can be obtained from samples in any form and provide rapid, nondestructive analyses on a microscopic scale of the hard-to-discriminate carbonate minerals.
Samples along the dolomite-ankerite join were synthesized using a piston-cylinder apparatus and the double-capsule method. Some of the ankerite samples may be disordered. Thermal analysis and X-ray diffraction showed that all samples can be completely decomposed to uniquely defined products under calorimetric conditions (770 °C, Oâ), and a well-constrained thermodynamic cycle was developed to determine the enthalpy of formation. The energetics of ordered and disordered ankerite solid solutions were estimated using data from calorimetry, lattice-energy calculations, and phase equilibria. The enthalpies of formation of ordered dolomite and disordered end-member ankerite from binary carbonates, determined by calorimetry, are -9.29 {+-} 1.97 and 6.98 {+-} 2.08 kJ/mol, respectively. The enthalpy of formation of ordered ankerite appears to become more endothermic with increasing Fe content, whereas the enthalpy of formation of disordered ankerite becomes more exothermic with increasing Fe content, whereas the enthalpy of formation of disordered ankerite becomes more exothermic with increasing Fe content. The enthalpy of disordering in dolomite (approximately 25 kJ/mol) is much larger than that in pure ankerite, CaFe(COâ)â (approximately 10 kJ/mol), which may explain the nonexistence of ordered CaFe(COâ)â. 24 refs., 3 figs., 3 tabs.
Stromatolite structures in Early Archean carbonate deposits form an important clue for the existence of life in the earliest part of Earth's history. Since Mars is thought to have had similar environmental conditions early in its history, the question arises as to whether such stromatolite structures also evolved there. Here, we explore the capability of Raman spectroscopy to make semiquantitative estimates of solid solutions in the Ca-Mg-Fe(+Mn) carbonate system, and we assess its use as a rover-based technique for stromatolite characterization during future Mars missions. Raman microspectroscopy analysis was performed on a set of carbonate standards (calcite, ankerite, dolomite, siderite, and magnesite) of known composition. We show that Raman band shifts of siderite-magnesite and ankerite-dolomite solid solutions display a well-defined positive correlation (r(2) > 0.9) with the Mg# = 100 x Mg/(Mg + Fe + Mn + Ca) of the carbonate analyzed. Raman shifts calibrated as a function of Mg# were used in turn to evaluate the chemical composition of carbonates. Raman analysis of a suite of carbonates (siderite, sidero-magnesite, ankerite, and dolomite) of hydrothermal and sedimentary origin from the ca. 3.2 Ga old Barite Syncline, Barberton greenstone belt, South Africa, and from the ca. 3.5 Ga old Dresser Formation, Pilbara Craton, Western Australia, show good compositional agreement with electron microprobe analyses. These results indicate that Raman spectroscopy can provide direct information on the composition and structure of carbonates on planetary surfaces.
Dolomite (CaMg(CO3)2) is an abundant carbonate mineral contained in sedimentary rocks and plays significant roles in water and carbon cycle in geo/cosmochemical environments. Since the cation compositions of carbonates are sensitive to the aqueous environment where they were precipitated and persisted, quantitative analysis of their cation compositions provides valuable information on the aqueous environments and their changes. The difficulty for the analysis of natural dolomite is that Mg2+ is continuously substituted by Fe2+ or Mn2+, and hence they sometimes possess micrometer-scale heterogeneity. Such heterogeneity carries quite important information on the gradual changes in aqueous environments due to changes in thermodynamic conditions and/or aqueous chemical compositions. In the present study, we explored a new quantitative scale to assess such heterogeneity of cation composition in natural dolomite and ferroan dolomite by combining X-ray fluorescence (XRF) and Raman spectroscopy. While the Fe + Mn content differed spot-by-spot, it was found that the Raman wavenumber and Fe + Mn content linearly correlated with each other. Since the spatial resolution of micro-Raman spectroscopy is as high as 1 μm, it does not require vacuum conditions, and is free from so-called matrix effect faced in other methods utilizing X-Rays and electron beams, the proposed qualitative analytical scale can provide a useful tool to assess the cation compositions in dolomites found in nature.
Carbonates play a crucial role in the water and carbon cycles of both geochemical and cosmochemical environments. As carbonates do not exist homogeneously with other minerals in rocks and sands of various sizes, an analytical method that simultaneously satisfies non-destructivity and high spatial resolution has been desired. Further, the ability of semi-quantitative analysis with carbonates-selectivity and without any pre-treatments is added, for its applicability would be extended to remote sensing for deep sea and outer spaces. Here, we focused on the application of micro-Raman spectroscopy, where the vibrational wavenumbers of the translational (T) and librational (L) modes of carbonates are sensitively related to their cation composition. By comparing the semi-quantitative information obtained by X-ray fluorescence spectroscopy, it was found that these vibrational wavenumbers are approximately linearly related to the cation composition. Consequently, a conversion matrix was proposed to estimate the cation composition from the T and L mode vibrational wavenumbers. This method is universally applicable to any cation composition in carbonates, with no background information on the analyte required. To improve the accuracy, conversion matrices were further optimized to three solid-solution series of carbonates. It is worth noting that the proposed conversion matrices are free from matrix effects and do not depend on the total amount of carbonate in a sample. Therefore, the proposed method provides a useful analytical basis for remote sensing of the cation composition of carbonates, both in terrestrial and extra-terrestrial environments.
The Hayabusa2 spacecraft explored C-type near-Earth asteroid (162173) Ryugu and returned asteroidal materials, collected during two touchdown operations, to the Earth as the first sample from carbonaceous-type asteroid. The sample container, in which ~5 g of Ryugu sample was enclosed, was safely opened in the clean chamber system with no severe exposure to the terrestrial atmosphere. In the course of preparation operation of the sample container, two dark-colored millimeter- to sub-millimeter-sized particles were found outside the sealing part of the sample container. Because they look similar to the Ryugu particles inside the sample container, the particles were named as Q particles (Q from questionable). In this study, we investigated Q particles (Q001 and Q002) mineralogically and petrographically to compare them with potential contaminants (the ablator material of the reentry capsule and fine sand particles at the capsule landing site), Ryugu sample, and CI chondrites. The Q particles show close resemblance to Ryugu sample and CI chondrites, but have no evidence of terrestrial weathering that CI chondrites experienced. We therefore conclude that the Q particles are originated from Ryugu and were expelled from the sample catcher (sample storage canister) in space prior to the enclosure operation of the sample catcher in the sample container. The most likely scenario is that the Q particles escaped from the sample catcher during the retrieval of the sample collection reflector, which was the necessary operation for the sample container closing.
Samples of the carbonaceous asteroid Ryugu were brought to Earth by the Hayabusa2 spacecraft. We analyzed seventeen Ryugu samples measuring 1-8 mm. CO2-bearing water inclusions are present within a pyrrhotite crystal, indicating that Ryugu's parent asteroid formed in the outer Solar System. The samples contain low abundances of materials that formed at high temperatures, such as chondrules and Ca, Al-rich inclusions. The samples are rich in phyllosilicates and carbonates, which formed by aqueous alteration reactions at low temperature, high pH, and water/rock ratios < 1 (by mass). Less altered fragments contain olivine, pyroxene, amorphous silicates, calcite, and phosphide. Numerical simulations, based on the mineralogical and physical properties of the samples, indicate Ryugu's parent body formed ~ 2 million years after the beginning of Solar System formation.
To date, only five natural carbonate minerals of calcite structure have been studied by Raman spectroscopy. These include calcite (CaCO3), magnesite (MgCO3), siderite (FeCO3), smithsonite (ZnCO3), and rhodochrosite (MnCO3). Thus far, only synthetic compounds of otavite (CdCO3), spherocobaltite (CoCO3), and gaspeite (NiCO3) have been investigated by Raman spectroscopy. However, the Raman spectra of natural otavite, spherocobaltite, and gaspeite have yet to be interpreted and compared with the Raman spectra of the other five natural carbonate minerals of calcite structure. This work has been undertaken to fill this gap and provide a comparison and interpretation of Raman spectra representative of all the eight natural carbonate minerals of calcite structure. The data here show that the carbonate Eg (T) phonon shifts are due to influences from the nearest neighbor distance; that is, M‐O, and different ionic radii of the divalent metal cation, as shown graphically by a strong correlation (r2 = 0.87 and 0.91, respectively). Using this graphical approach, we have developed a Raman spectroscopic model based on the equation, y = −2.067x + 356.2 (±5 pm) to calculate the ionic radii of the divalent metal cation present within the mineral and hence affording the identification and discrimination of calcite‐group minerals based on the band position of the Eg (T) mode. Only five natural carbonate minerals of calcite structure, that is calcite, magnesite, siderite, smithsonite, and rhodochrosite, have been studied by Raman spectroscopy. However, the Raman spectra of otavite and spherocobaltite have yet to be interpreted. Here we show that the carbonate Eg (T) phonon shifts are due to nearest neighbor distance and different ionic radii, which show strong correlation and can be used to identify carbonate minerals of calcite structure.
Meteorites and impact glasses have been largely analysed using different techniques, but most studies have been focused on their geological–mineralogical characterization and isotopic ratios, mainly of a destructive nature. However, much more information can be gained by applying novel non-destructive analytical procedures and techniques that have been scarcely used to analyse these materials. This overview presents some new methodologies to study these materials and compares these new approaches with the commonly used ones. Techniques such as X-Ray Fluorescence (XRF) and Laser Induced Breakdown Spectroscopy (LIBS), for elemental characterization, the hyphenated Raman spectroscopy-SEM/EDS and the combination of them, allow extracting simultaneous information from elemental, molecular and structural data of the studied sample; furthermore, the spectroscopic image capabilities of such techniques allow a better understanding of the mineralogical distribution.
A review is presented of the current technical capabilities and analytical applications of synchrotron X-ray sources. Applications in areas such as agriculture, toxic waste, organic-inorganic systems, geochemical processes involving coal and ore deposits, and atmospheric aerosols are presented (123 references).
The theoretical formulas of the fluorescent x-ray intensity (the primary, the secondary and the tertiary fluorescent x-rays) are obtained and actual calculations are made for nickel-iron, iron-chromium, and nickel-iron-chromium alloys. In the calculation, the continuous intensity distribution of the irradiating x-rays for the wavelength is taken into account. The theoretical results agree with the experiments very well, the deviations being 1% at most, and it is concluded that the theoretical estimation of the fluorescent x-ray intensity emitted from samples of various composition is possible. The matrix effect, absorption effect, and enhancement effect are evaluated from the present theory. In the enhancement effect, secondary fluorescent x-rays are quite significant (for instance, the chromium secondary fluorescent x-rays from Cr 2% and Fe 98% alloy reach the 55% of the chromium primary fluorescent x-rays and they can not be neglected), but the tertiary fluorescent x-rays are only a few per cent. The usual approximation methods, where the irradiating x-rays are assumed as monochromatic rays and the secondary fluorescent rays are not taken into consideration are also discussed and their meaning is made clear.
Carbonate minerals in fourteen CM chondrites and two CI chondrites have been analyzed by electron microprobe to provide a better understanding of the aqueous processes that affected carbonaceous chondrite parent bodies. Calcites in CM chondrites and dolomites and magnesites in CI chondrites display the compositions expected of stable phases formed at low temperatures. Dolomites in CM chondrites, identified here for the first time in five members of the group, have small amounts of excess Ca which may reflect metastable growth. The distribution of Fe between dolomite and coexisting serpentine differs in the two chondrite groups. If the distributions reflect an approach to chemical equilibrium, then the difference implies higher alteration temperatures for the CI group than the CM group in agreement with the results of previously published oxygen isotope thermometry and mineral solubility modeling of the alteration process. Dolomite Fe contents are relatively uniform in the two chondrite groups. Dolomite Mn contents, by contrast, vary widely. The variations may reflect transport-controlled coprecipitation of Mn resulting from a heterogeneous distribution of the element in the anhydrous precursor material. If this interpretation is correct, then the altering fluids were essentially immobile while hydration reactions proceeded on the meteorite parent bodies. The near closed-system character of the alteration process, long known from bulk chemical analyses of the meteorites, is a direct consequence of the limited mobility of dissolved species.
A mixture of elements irradiated by a sufficiently energetic X-ray beam absorbs the incident X-rays and re-emits other X-rays, the wavelengths of which are characteristic of the elements in the sample, and the intensities of which may be correlated with their concentrations. The problem is to correlate Ifi, the intensity of the X-ray spectrum emitted by an element of atomic number Zi with c, μ, and τ (concentration, absorption coefficient, and emission coefficient, respectively) of the elements in the sample. The correlation is complicated by the fact that the fluorescent radiation from elements of higher Z will excite additional radiation from elements of lower Z.Using integral methods, s mathematical analysis of the absorption-re-emission process yields explicit closed formulae, when the incident beam is monochromatic, for Ifi(c, μ, τ) in terms of logarithms and ψ-functions. A preliminary investigation suggests that the theory of means may offer a theoretical solution when the incident beam is polychromatic. Graphical methods make it possible to invert the formulae and express c in terms of Ifi, which makes chemical analysis possible. The use of a reference sample of known composition in the same elements as the sample in question, makes it possible to derive a close approximation to the chemical analysis when the incident beam is polychromatic. A brief comparison of computed and measured intensities from samples of known composition shows a good agreement.The report closes with appendices giving mathematical details, a numerical table of ψ(x), (0 ⩽ x ⩽ 1), and the fluorescence yields for some elements.
CM chondrites are aqueously altered rocks that contain ∼9 wt% H2O⁺ (i.e., indigenous water) bound in phyllosilicates; also present are clumps of serpentine-tochilinite intergrowths (previously called “poorly characterized phases” or PCP), pentlandite and Ni-bearing pyrrhotite. We studied 11 CM chondrites that span the known range from least altered to most altered. We used various petrologic properties (many previously identified) that provide information regarding the degree of aqueous alteration. There are no known unaltered or slightly altered CM chondrites (e.g., rocks containing numerous chondrules with primary igneous glass). Some CM properties result from processes associated with early and intermediate stages of the alteration sequence (i.e., hydration of matrix, alteration of chondrule glass, and production of large PCP clumps). Other petrologic properties reflect processes active throughout the alteration sequence; these include oxidation of metallic Fe–Ni, alteration of chondrule phenocrysts, changes in PCP composition (reflecting an increase in the phyllosilicate/sulfide ratio), and changes in carbonate mineralogy (reflecting the development of dolomite and complex carbonates at the expense of Ca carbonate).
Six new Raman spectra of carbonates of calcite structure (D63d) are presented and compared with the previously reported siderite and calcite spectra. Correction on the assignment of the electronic Raman in siderite was done by this comparative study. In calcite a new line was observed and assigned as an Eg+A1g mode. Some samples were prepared by hydrothermal synthesis and the technique is described.
All CI chondrites are regolith breccias consisting of various types of chemically and mineralogically distinct mineral and lithic fragments (or units). In the CI chondrite Ivuna, for example, four different lithological units were identified and are referred to as lithology I, II, III, and IV. So far, lithologies III and IV have been identified in Orgueil as well. It appears that at least Ivuna and Orgueil consist of the same basic lithologies in different proportions. Carbonates in CIs occur as individual grains within such lithic units or exist as large fragments between them. Carbonate fragments are remnants of former carbonate veins and, in contrast to individual carbonate grains, are not genetically linked to lithological units. Four different types of carbonates (dolomite, breunnerite, calcite, siderite) occur in CIs and they constitute, on average, 5 vol% of each studied section. In this study, carbonates in the CI chondrites Orgueil, Ivuna, Alais, and Tonk were studied petrographically, mineralologically, and chemically. The results clearly indicate that, in contrast to most previous studies, compositional differences exist between dolomites within and among CI chondrites. From these differences it can be derived that (1) several episodes of alteration occurred on the CI parent body, (2) physicochemical conditions during carbonate formation must have been different among CIs, and (3) CI carbonates obviously were formed at low temperatures in equilibrium with surrounding fluid(s). While local compositional changes in fluid(s) on a micrometer to millimeter scale (as reflected by dolomite compositions within CI chondrites) were most likely controlled by the availability of Ca2+ Mg2+, Fe2+, and especially Mn2+ ions in the aqueous solutions, more widespread compositional changes on a meter (or even larger) scale were controlled by variable pH, Eh, CO2 partial pressure, and, especially, temperature conditions (as reflected by the compositional variability of dolomites among CIs).
University of Arizona Press
- A J Brearley