Parent Body Aqueous Alteration Research Articles

Aragonite, breunnerite, calcite and dolomite in the CM carbonaceous chondrites: High fidelity recorders of progressive parent body aqueous alteration

Carbonate minerals in CM carbonaceous chondrite meteorites, along with the silicates and sulphides with which they are intergrown, provide a detailed record of the nature and evolution of parent body porosity and permeability, and the chemical composition, temperature and longevity of aqueous solutions. Fourteen meteorites were studied that range in petrologic subtype from mildly aqueously altered CM2.5 to completely hydrated CM2.0. All of them contain calcite, whereas aragonite occurs only in the CM2.5–CM2.2 meteorites and dolomite in the CM2.2–CM2.0. All of the aragonite crystals, and most of the calcite and dolomite grains, formed during early stages of parent body aqueous alteration by cementation of pores produced by the melting of tens of micrometre size particles of H2O-rich ice. Aragonite was the first carbonate to precipitate in the CM2.5 to CM2.2 meteorites, and grew from magnesium-rich solutions. In the least altered of these meteorites the aragonite crystals formed in clusters owing to physical restriction of aqueous fluids within the low permeability matrix. The strong correlation between the petrologic subtype of a meteorite, the abundance of its aragonite crystals and the proportion of them that have preserved crystal faces, is because aragonite was dissolved in the more altered meteorites on account of their higher permeability, and/or greater longevity of the aqueous solutions. Dolomite and breunnerite formed instead of aragonite in some of the CM2.1 and CM2.2 meteorites owing to higher parent body temperatures. The pore spaces that remained after precipitation of aragonite, dolomite and breunnerite cements were occluded by calcite. Following completion of cementation, the carbonates were partially replaced by phyllosilicates and sulphides. Calcite in the CM2.5–CM2.2 meteorites was replaced by Fe-rich serpentine and tochilinite, followed by Mg-rich serpentine. In the CM2.1 and CM2.0 meteorites dolomite, breunnerite and calcite were replaced by Fe-rich serpentine and Fe–Ni sulphide, again followed by Mg-rich serpentine. The difference between meteorites in the mineralogy of their replacive sulphides may again reflect greater temperatures in the parent body regions from where the more highly altered CMs were derived. This transition from Fe-rich to Mg-rich carbonate replacement products mirrors the chemical evolution of parent body solutions in response to consumption of Fe-rich primary minerals followed by the more resistant Mg-rich anhydrous silicates. Almost all of the CMs examined contain a second generation of calcite that formed after the sulphides and phyllosilicates and by replacement of remaining anhydrous silicates and dolomite (dedolomitization). The Ca and CO2 required for this replacive calcite is likely to have been sourced by dissolution of earlier formed carbonates, and ions may have been transported over metre-plus distances through high permeability conduits that were created by impact fracturing.

Evolution of organic matter in Orgueil, Murchison and Renazzo during parent body aqueous alteration: In situ investigations

Chondrites accreted the oldest solid materials in the solar system including dust processed in the protoplanetary disk and diverse organic compounds. After accretion, asteroidal alteration may have impacted organic particles in various ways. To constrain these processes, we conducted a comprehensive study of organics disseminated within the matrices of the three carbonaceous chondrite falls, Renazzo (CR2), Murchison (CM2) and Orgueil (CI). By combining synchrotron-based STXM and TEM analyses on FIB sections of samples previously characterized by NanoSIMS, we investigated the influence of aqueous alteration on the morphology, isotopic signature, molecular structure, spatial distribution, and mineralogical environment of the organic matter within the matrices. Two different populations of materials are distinguishable: sub-micrometric individual grains, likely dominated by insoluble compounds and diffuse organic matter, finely interspersed within phyllosilicates and/or (amorphous) nanocarbonates at the nanometer scale. We suggest that this latter component, which is depleted in aromatics and enriched in carboxylic functional groups, may be dominated by soluble compounds. Organic matter in Renazzo (CR) mainly consists of chemically-homogeneous individual grains surrounded by amorphous and nanocrystalline phyllosilicates. Evidence of connectivity between organic grains and fractures indicates that redistribution has occurred: some areas containing diffuse organic matter can be observed. This diffuse organic component is more abundant in Murchison (CM) and Orgueil (CI). This is interpreted as resulting from fluid transport at the micrometer scale and encapsulation within recrystallized alteration phases. In contrast to Renazzo, organic grains in Murchison and Orgueil display strong chemical heterogeneities, likely related to chemical evolution during aqueous alteration. The observations suggest that the altering fluid was a brine with elevated concentrations of both organic and inorganic soluble components. Ultimately, when water was consumed by aqueous alteration reactions or lost from the system, soluble organic compounds accumulated in the immediate vicinity of the precipitated carbonates and phosphates. Additionally, the nanometer scale organic/phyllosilicate relationships provide a petrological environment where some of the initially accreted organic matter could have been modified through clay-mediated reactions.

UV to far-IR reflectance spectra of carbonaceous chondrites – I. Implications for remote characterization of dark primitive asteroids targeted by sample-return missions

We analyze here a wide sample of carbonaceous chondrites from historic falls (e.g. Allende, Cold Bokkeveld, Kainsaz, Leoville, Murchison, Murray and Orgueil), and from NASA Antarctic collection in order to get clues on the role of aqueous alteration in promoting the reflectance spectra diversity evidenced in the most primitive chondrite groups. We particularly focus in the identification of spectral features and behavior that can be used to remotely identify primitive carbonaceous asteroids. The selected meteorite specimens are a sample large enough to exemplify how laboratory reflectance spectra of rare groups of carbonaceous chondrites exhibit distinctive features that can be used to remotely characterize the spectra of primitive asteroids. Our spectra cover the full electromagnetic spectrum from 0.2 to 25 microns by using two spectrometers. First one is a UV-NIR spectrometer that covers the 0.2 to 2 microns window, while the second one is an Attenuated Total Reflectance IR spectrometer covering the 2 to 25 microns window. In particular, laboratory analyses in the UV-NIR window allow obtaining absolute reflectance by using standardized measurement procedures. We obtained reflectance spectra of specimens belonging to the CI, CM, CV, CR, CO, CK, CH, R, and CB groups of carbonaceous chondrites plus some ungrouped ones, and allows identifying characteristic features and bands for each class, plus getting clues on the influence of parent body aqueous alteration. These laboratory spectra can be compared with the remote spectra of asteroids, but the effects of terrestrial alteration forming (oxy)hydroxides need to be considered.

Nature and degree of aqueous alteration in CM and CI carbonaceous chondrites

AbstractWe investigated the petrologic, geochemical, and spectral parameters that relate to the type and degree of aqueous alteration in nine CM chondrites and one CI (Ivuna) carbonaceous chondrite. Our underlying hypothesis is that the position and shape of the 3 μm band is diagnostic of phyllosilicate mineralogy. We measured reflectance spectra of the chondrites under dry conditions (elevated temperatures) and vacuum (10−8 to 10−7 torr) to minimize adsorbed water and mimic the space environment, for subsequent comparison with reflectance spectra of asteroids. We have identified three spectral CM groups in addition to Ivuna. “Group 1,” the least altered group as determined from various alteration indices, is characterized by 3 μm band centers at longer wavelengths, and is consistent with cronstedtite (Fe‐serpentine). “Group 3,” the most altered group, is characterized by 3 μm band centers at shorter wavelengths and is consistent with antigorite (serpentine). “Group 2” is an intermediate group between group 1 and 3. Ivuna exhibits a unique spectrum that is distinct from the CM meteorites and is consistent with lizardite and chrysotile (serpentine). The petrologic and geochemical parameters, which were determined using electron microprobe analyses and microscopic observations, are found to be consistent with the three spectral groups. These results indicate that the distinct parent body aqueous alteration environments experienced by these carbonaceous chondrites can be distinguished using reflectance spectroscopy. High‐quality ground‐based telescopic observations of Main Belt asteroids can be expected to reveal not just whether an asteroid is hydrated, but also details of the alteration state.

The oxygen isotope evolution of parent body aqueous solutions as recorded by multiple carbonate generations in the Lonewolf Nunataks 94101 CM2 carbonaceous chondrite

The CM2 carbonaceous chondrite LON 94101 contains aragonite and two generations of calcite that provide snapshots of the chemical and isotopic evolution of aqueous solutions during parent body alteration. Aragonite was the first carbonate to crystallize. It is rare, heterogeneously distributed within the meteorite matrix, and its mean oxygen isotope values are δ18O 39.9±0.6‰, Δ17O −0.3±1.0‰ (1σ). Calcite precipitated soon afterwards, and following a fall in solution Mg/Ca ratios, to produce small equant grains with a mean oxygen isotope value of δ18O 37.5±0.7‰, Δ17O 1.4±1.1‰ (1σ). These grains were partially or completely replaced by serpentine and tochilinite prior to precipitation of the second generation of calcite, which occluded an open fracture to form a millimetre-sized vein, and replaced anhydrous silicates within chondrules and the matrix. The vein calcite has a mean composition of δ18O 18.4±0.3‰, Δ17O −0.5±0.5‰ (1σ). Petrographic and isotopic results therefore reveal two discrete episodes of mineralisation that produced calcite generations with contrasting δ18O, and mean Δ17O values. The aragonite and equant calcite crystallized over a relatively brief period early in the aqueous alteration history of the parent body, and from static fluids that were evolving chemically in response to mineral dissolution and precipitation. The second calcite generation crystallized from solutions of a lower Δ17O, and a lower δ18O and/or higher temperature. As two generations of calcite whose petrographic characteristics and oxygen isotopic compositions are similar to those in LON 94101 occur in at least one other CM2, multiphase carbonate mineralisation could be the typical outcome of the sequence of chemical reactions during parent body aqueous alteration. It is equally possible however that the second generation of calcite formed in response to an event such as impact fracturing and concomitant fluid mobilisation that affected a large region of the common parent body of several CM2 meteorites. These findings show that integrated petrographic, chemical and isotopic studies can provide new insights into the mechanisms of parent body alteration including the spatial and temporal dynamics of the aqueous system.

The soluble organic compounds of the Bells meteorite: Not a unique or unusual composition

The Bells meteorite is a CM2 chondrite that has long been considered anomalous for having mineralogical and isotopic differences with CMs together with an overall affinity to CIs in its matrix. We extracted a fragment of the only Bells stone collected unweathered with water and solvents and studied the meteorite’s soluble organic composition. We found Bells to contain abundant organic compounds, which are predominantly O-containing such as hydroxy- and di-carboxylic acids, and a scarcity of amino acids and other N-containing compounds. Amines were not detected and ammonia is less abundant than in both the Murchison and Ivuna meteorites. Overall, Bells’ soluble organic composition is more similar to that of Ivuna than of Murchison. The observation that Bells’ amino acid suite shares a distinct distribution of characteristic molecular species with other stones that are thought to have experienced extensive parent body aqueous alteration, such as the Orgueil, Ivuna and recently analyzed GRO 95577 CR1 meteorites, seems to allow the suggestion that such a composition is secondary to prolonged aqueous alteration processes that superseded some of the initial compositional distinctions determined by the asteroidal environments.

Ca-carbonate in the Orgueil (CI) carbonaceous chondrite: Mineralogy, microstructure and implications for parent body history

The Orgueil CI carbonaceous chondrite is a breccia and some of its constituent clasts contain Ca-carbonate grains whose mineralogy is undetermined, but may yield new information on the history of its asteroidal or cometary parent body. Characterisation of one such clast shows that in addition to Ca-carbonate it contains magnetite, olivine and orthopyroxene grains that are supported within a finely crystalline saponite–serpentine–ferrihydrite groundmass. The Ca-carbonate grains are typically rounded, less than 10 μm in diameter, and backscatter Kikuchi patterns identify all those analysed as calcite. Electron backscatter diffraction orientation contrast maps show that most calcites have sub-μm sized e-twins, some of which are cut by corroded grain margins. These microstructures demonstrate that the clast experienced very mild shock during aqueous alteration and probably accompanying impact ‘gardening’ of the parent body regolith. The sample studied hosts several other millimeter sized clasts and a fine grained clastic matrix that are free of Ca-carbonate, olivine and orthopyroxene although can contain apatite, dolomite and pyrrhotite. Within one of these clasts is a network of phyllosilicate–magnetite veins that are inferred to have acted as fluid flow conduits during parent body aqueous alteration. Sulphur-rich reaction rims within the same clast are likely to have formed during post-fall remobilization and crystallization of pre-terrestrial sulphates. This study provides good evidence for alteration of the CI carbonaceous chondrites in a dynamic parent body regolith.

Aragonite in the Murray (CM2) carbonaceous chondrite: Implications for parent body compaction and aqueous alteration

Abstract— The matrix of the CM2 carbonaceous chondrite Murray contains rare micrometer‐sized prismatic crystals of aragonite that formed during late‐stage parent body aqueous alteration. The aragonite was identified by X‐ray microanalysis coupled with electron backscatter diffraction (EBSD), TEM selected area electron diffraction and cathodoluminescence spectroscopy. The sixteen crystals found all occur within loose and elongate submillimeter‐sized clusters and one cluster is present in each of the two thin sections studied. Orientation determinations using EBSD show that the c axes of aragonite crystals within each cluster lie roughly in a plane, itself aligned approximately parallel to the long axis of the host cluster. Aragonite is inferred to have crystallized after calcite but before completion of static/impact‐related compaction. The clusters developed by growth of aragonite within films of aqueous fluids that had a relatively high Mg/Ca ratio. These fluids were focused within zones of high porosity and permeability along a weak compactional fabric in the matrix and this fabric is also likely to have influenced the orientations of aragonite crystals as they grew. These results suggest that aragonite probably occurs in most of those carbonaceous chondrites that have undergone moderate degrees of parent body aqueous alteration and may provide further insights into the evolution of pore fluid compositions and volumes and the chronology of asteroidal evolution.

The preservation state of organic matter in meteorites from Antarctica

Abstract— The recovery of large numbers of meteorites from Antarctica has dramatically increased the amount of extraterrestrial material available for laboratory studies of solar system origin and evolution. Yet, the great age of Antarctic meteorites raises the concern that significant amounts of terrestrial weathering has corrupted their pre‐terrestrial record. Organic matter found in carbonaceous chondrites is one of the components most susceptible to alteration by terrestrial processes. To assess the effects of Antarctic weathering on both non‐Antarctic and Antarctic chondritic organic matter, a number of CM chondrites have been analyzed. Mössbauer spectroscopy has been used to ascertain pre‐terrestrial and terrestrial oxidation levels, while pyrolysis‐gas chromatography‐mass spectrometry was used to determine the constitution of any organic matter present. Increased oxidation levels for iron bearing minerals within the non‐Antarctic chondrites are likely to be a response to increased amounts of parent body aqueous alteration. Parent body processing also appears to remove ether bonds from organic material and alkyl side chains from its constituent units. The iron in Antarctic chondrites is generally more oxidized than that in their non‐Antarctic counterparts, reflecting terrestrial weathering. Antarctic weathering of chondritic organic matter appears to proceed in a similar way to parent body aqueous alteration and simply enhances the organic responses observed in the non‐Antarctic data set. Degradation of the record of preterrestrial processes in Antarctic chondrites should be taken into account when interpreting data from these meteorites.

Investigating the variations in carbon and nitrogen isotopes in carbonaceous chondrites

The carbonaceous chondrites contain significant amounts of carbon- and nitrogen-bearing components, the most abundant of which is organic matter. Stepped combustion data of whole rock and HF/HCl residues of carbonaceous chondrites reveal that the organic material can be subdivided operationally into three components: (1) free organic matter (FOM), which is readily extractable from whole-rock meteorites and is enriched in 13C and 15N; (2) labile organic matter (LOM), which has a macromolecular structure but is liberated by hydrous pyrolysis; LOM is the parent structure for some FOM and is also enriched in 13C and 15N; and (3) refractory organic matter (ROM), which is also macromolecular but is virtually unaffected by hydrous pyrolysis and is relatively depleted in 13C and 15N. The macromolecular entities (LOM and ROM) are by far the most abundant organic components present, and as such, the relative abundances of the 13C- and 15N-enriched LOM and the 13C- and 15N-depleted ROM will have a major influence on the overall isotopic composition of the whole-rock meteorite. Laboratory experiments designed to simulate the effects of parent body aqueous alteration indicate that this form of processing removes LOM from the macromolecular material, allowing ROM to exert a stronger influence on the overall isotopic compositions. Hence, aqueous alteration of macromolecular materials on the meteorite parent body may have a significant control on the stable isotopic compositions of whole-rock carbonaceous chondrites. The enstatite chondrites are also carbon rich but have been subjected to high levels of thermal metamorphism on their parent body. Stepped combustion data of HF/HCl residues of enstatite chondrites indicate, that if they and carbonaceous chondrites inherited a common organic progenitor, metamorphism under reducing conditions appears to incorporate and preserve some of the 13C enrichments in LOM during graphitisation. However, when metamorphism is at its most extreme, the 15N enrichments in LOM are lost.

Mineralogy and petrology of amoeboid olivine inclusions in CO3 chondrites: Relationship to parent‐body aqueous alteration

Abstract— Petrographic and mineralogic studies of amoeboid olivine inclusions (AOIs) in CO3 carbonaceous chondrites reveal that they are sensitive indicators of parent‐body aqueous and thermal alteration. As the petrologic subtype increases from 3.0 to 3.8, forsteritic olivine (Fa0–1) is systematically converted into ferroan olivine (Fa60–75). We infer that the Fe, Si and O entered the assemblage along grain boundaries, forming ferroan olivine that filled fractures and voids. As temperatures increased, Fe+2 from the new olivine exchanged with Mg+2 from the original AOI to form diffusive haloes around low‐FeO cores. Cations of Mn+2, Ca+2 and Cr+3 were also mobilized.The systematic changes in AOI textures and olivine compositional distributions can be used to refine the classification of CO3 chondrites into subtypes. In subtype 3.0, olivine occurs as small forsterite grains (Fa0–1), free of ferroan olivine. In petrologic subtype 3.2, narrow veins of FeO‐rich olivine have formed at forsterite grain boundaries. With increasing alteration, these veins thicken to form zones of ferroan olivine at the outside AOI margin and within the AOI interior. By subtype 3.7, there is a fairly broad olivine compositional distribution in the range Fa63–70, and by subtype 3.8, no forsterite remains and the high‐Fa peak has narrowed, Fa64–67. Even at this stage, there is incomplete equilibration in the chondrite as a whole (e.g., data for coarse olivine grains in Isna (CO3.8) chondrules and lithic clasts show a peak at Fa39). We infer that the mineral changes in AOI identified in the low petrologic types required aqueous or hydrothermal fluids whereas those in subtypes ?3.3 largely reflect diffusive exchange within and between mineral grains without the aid of fluids.

The oxygen isotopic composition of water from Tagish Lake: Its relationship to low‐temperature phases and to other carbonaceous chondrites

Abstract— The fall and recovery of the Tagish Lake meteorite in British Columbia in January 2000 provided a unique opportunity to study relatively pristine samples of carbonaceous chondrite material. Measurements of the oxygen isotopic composition of water extracted under stepped pyrolysis from a bulk sample of this meteorite have allowed us to make comparisons with similar data obtained from CI and CM chondrites and so further investigate any relationships that may exist between these meteorites. The much lower yield of water bearing a terrestrial signature in Tagish Lake is indicative of the pristine nature of the meteorite. The relationship between the isotopic composition of this water and reported isotopic values for carbonates, bulk matrix and whole rock have been used to infer the extent and conditions under which parent‐body aqueous alteration occurred. In Tagish Lake the difference in Δ17O isotopic composition between the water and other phases is greater than that found in either CM or CI chondrites suggesting that reaction and isotopic exchange between components was more limited. This in turn suggests that in the case of Tagish Lake conditions during the processes of aqueous alteration on the parent body, which ultimately controlled the formation of new minerals, were distinct from those on both CI and CM parent bodies.

Aromatic Moieties in Meteorites: Relics of Interstellar Grain Processes?

The carbonaceous chondrite meteorites contain a record of the formation of the solar system, part of which is present within organic matter. This organic matter is predominantly aromatic, and its sources remain controversial. The δ13C values for individual free and macromolecular aromatic moieties from Cold Bokkeveld and Murchison suggest that these units originate from radiation-induced "circle" reactions involving simultaneous bond synthesis and cracking. Large carbon isotope fractionations and a deuterium enrichment for these entities suggest that these reactions occurred in a dense interstellar cloud. The juxtaposition of the synthesis and cracking products implies that the reactions occurred in a restricting medium, the most likely candidate for which is the icy organic mantles of interstellar grains. In contrast, the δ13C record in aromatic moieties from Orgueil is mostly obscured, possibly due to the increased levels of parent body aqueous alteration experienced by this meteorite. These novel observations are consistent with the interstellar-parent body hypothesis, where the final form of meteoritic organic matter results from the transfiguration of interstellar organic precursors by aqueous reactions on the meteorite parent body.

Oxygen isotope studies of carbonaceous chondrites

The carbonaceous chondrites display the widest range of oxygen isotopic composition of any meteorite group, as a consequence of the interaction of primordial isotopic reservoirs in the solar nebula. These isotopic variations can be used to identify the reservoirs and to determine conditions and loci of their interactions. We present a comprehensive set of whole-rock analyses of CV, CO, CK, CM, CR, CH, and CI chondrites, as well as selected components of some of these meteorites. A simple model is developed which describes the isotopic behavior during parent-body aqueous alteration processes. The process of thermal dehydration also produces a recognizable effect in the oxygen isotopic composition.

Aqueous alteration of carbonaceous chondrites: Evidence for preaccretionary alteration—A review

Abstract— In most groups of carbonaceous chondrites, minerals occur that are formed due to aqueous alteration in the nebula and/or within meteorite parent bodies. For determining the evolution of materials in the early solar system, it is of significant importance to clearly identify evidence for either nebular or planetary aqueous alteration. Therefore, results from the study of chondrites have fundamental implications for ideas concerning nebular dynamics, gas‐solid interactions in the nebula, and accretionary processes.Considering the topic of this review, it is important to define nebular and parent body processes. The solar nebula activity should include condensation processes of high‐ and low‐temperature components as well as processes of chemical fractionation and grain‐size sorting, mixing of solids and gas, and interactions between early formed solids with the remaining gas; but it should exclude processes that occurred in small uncompacted protoplanetary objects that may have been totally destroyed again before accretion of the final meteorite parent bodies. Therefore, the term “preaccretionary” instead of “nebula” is used in this paper to include all these processes that may have occurred in small precursor planetesimals.Currently, there is no doubt that parent body aqueous alteration is a fundamental process in the evolution of several groups of carbonaceous chondrites. However, due to textural and mineralogical observations and chemical analyses, strong arguments have been found also indicating preaccretionary aqueous alteration of distinct components in carbonaceous chondrites. In this paper, evidence for preaccretionary aqueous alteration in carbonaceous chondrites and their components taken from previous studies is discussed in detail.The strongest evidence for preaccretionary alteration comes from studies of CM chondrites. The survival of highly unequilibrated mineral assemblages in accretionary rims, and sharp contacts between chondrule glass and surrounding phyllosilicates, are only two important arguments for preaccretionary alteration features among many others discussed in the paper. Similar observations were also made in CR, CH and related chondrites. Due to the small abundance of water‐bearing phases in CO and CV chondrites, the origin of phyllosilicates in these groups is less clear. A preaccretionary origin of hydrous phases in Ca‐Al‐rich inclusions (CAIs) has also been suggested by several scientists. In CI chondrites, no strong indications for such processes have been found, mainly due to heavy brecciation and severe parent body alteration.

Disordered biopyriboles, amphibole, and talc in the Allende meteorite: products of nebular or parent body aqueous alteration?

Transmission electron microscope observations of the Allende carbonaceous chondrite provided evidence of widespread hydrous phases replacing enstatite in chondrules. Calcic amphibole and talc occur in thin (less than 0.3 micrometer) crosscutting veins and as alteration products of primary chondrule glass in contraction cracks within the enstatite. In addition, talc and disordered biopyriboles were found replacing enstatite grains along cracks and fractures. Although rare hydrous phases have been reported in calcium- and aluminum-rich inclusions in the Allende meteorite, these observations suggest that aqueous fluids played a much more significant role in the mineralogical and geochemical evolution of Allende than has previously been thought.