Unconfined shock experiments: A pilot study into the shock‐induced melting and devolatilization of calcite

We shocked calcite in an unconfined environment by launching small marble cylinders at 0.8–5.5 km s^?1 into aluminum or copper plates, producing shock stresses between 5 and 79 GPa. The resulting 5–20 mm craters contained intimately mixed clastic and molten projectile residues over the entire pressure range, with melting commencing already at 5 GPa. Stoichiometrically pure calcite melts were not observed as all melts contained target metal. Some of these residues were distinctly depleted in CO₂ and some contained even tiny CaO crystals, thus illustrating partial to complete loss of CO₂. We interpret a thin seam of finely crystalline calcite to be the product of back reactions between CaO and CO₂. The amount of carbonate residue in these craters, especially those at low velocities (<2 km s^?1), is dramatically less than that of silicate impactors in similar cratering experiments, and we suggest that this is due to substantial outgassing of CO₂. Similarly, the volume of carbonate melts relative to the volume of limestone or dolomite in many terrestrial crater structures seems insignificant as well, as is the volume of carbonate melt compared to the volume of impact melts derived from silicates. These volume considerations suggest that volatilization of CO₂ is the dominant process in carbonate‐containing targets. Because we have difficulties in explaining naturally occurring calcite melts by shock processes in dolomite‐dominated targets, we speculate—essentially via process of elimination—that such carbonate melt blebs might be condensation products from an impact‐produced vapor cloud.     

Devolatilization or melting of carbonates at Meteor Crater,AZ?

We have investigated the carbonates in the impact melts and in a monolithic clast of highly shocked Coconino sandstone of Meteor Crater, AZ to evaluate whether melting or devolatilization is the dominant response of carbonates during high‐speed meteorite impact. Both melt‐ and clast‐carbonates are calcites that have identical crystal habits and that contain anomalously high SiO₂ and Al₂O₃. Also, both calcite occurrences lack any meteoritic contamination, such as Fe or Ni, which is otherwise abundantly observed in all other impact melts and their crystallization products at Meteor Crater. The carbon and oxygen isotope systematics for both calcite deposits suggest a low temperature environment (<100 °C) for their precipitation from an aqueous solution, consistent with caliche. We furthermore subjected bulk melt beads to thermogravimetric analysis and monitored the evolving volatiles with a quadrupole mass spectrometer. CO₂ yields were <5 wt%, with typical values in the 2 wt% range; also total CO₂ loss is positively correlated with H₂O loss, an indication that most of these volatiles derive from the secondary calcite. Also, transparent glasses, considered the most pristine impact melts, yield 100 wt% element totals by EMPA, suggesting complete loss of CO₂. The target dolomite decomposed into MgO, CaO, and CO₂; the CO₂ escaped and the CaO and MgO combined with SiO₂ from coexisting quartz and FeO from the impactor to produce the dominant impact melt at Meteor Crater. Although confined to Meteor Crater, these findings are in stark contrast to Osinski et al. (2008) who proposed that melting of carbonates, rather than devolatilization, is the dominant process during hypervelocity impact into carbonate‐bearing targets, including Meteor Crater.     

Transmission electron microscopy of minerals in the martian meteorite Allan Hills 84001

Abstract— We have studied carbonate and associated oxides and glasses in a demountable section of Allan Hills 84001 (ALH 84001) using optical, scanning, and transmission electron microscopy (TEM) to elucidate their origins and the shock history of the rock. Massive, fracture‐zone, and fracture‐filling carbonates in typical locations were characterized by TEM, X‐ray microanalysis, and electron diffraction in a comprehensive study that preserved textural and spatial relationships. Orthopyroxene is highly deformed, fractured, partially comminuted, and essentially unrecovered. Lamellae of diaplectic glass and other features indicate shock pressures >30 GPa. Bridging acicular crystals and foamy glass at contacts of orthopyroxene fragments indicate localized melting and vaporization of orthopyroxene. Carbonate crystals are >5 mm in size, untwinned, and very largely exhibit the R3c calcite structure. Evidence of plastic deformation is generally found mildly only in fracture‐zone and fracture‐filling carbonates, even adjacent to highly deformed orthopyroxene, and appears to have been caused by low‐stress effects including differential shrinkage. High dislocation densities like those observed in moderately shocked calcite are absent. Carbonate contains impactderived glasses of plagioclase, silica, and orthopyroxene composition indicating brief localized impact heating. Stringers and lenses of orthopyroxene glass in fracture‐filling carbonate imply flow of carbonates and crystallization during an impact. Periclase (MgO) occurs in magnesite as 30–50 nm crystals adjacent to voids and negative crystals and as ?1 μm patches of 3 nm crystals showing weak preferred orientation consistent with (111)_MgO//(0001)_carb, as observed in the thermal decomposition of CaCO₃ to CaO. Magnetite crystals that are epitaxially oriented at voids, negative crystals, and microfractures clearly formed in situ. Fully embedded, faceted magnetites are topotactically oriented, in general with (111)_mag//(0001)_carb, so that their oxygen layers are aligned. In optically opaque rims, magnetites are more irregularly shaped and, except for the smallest crystals, poorly aligned. All magnetite and periclase crystals probably formed by exsolution from slightly non‐stoichiometric, CO₂‐poor carbonate following impact‐induced thermal decomposition. Any magnetites that existed in the rock before shock heating could not have preserved evidence for biogenic activity.     

Evidence for shock‐induced anhydrite recrystallization and decomposition at the UNAM‐7 drill core from the Chicxulub impact structure

Drill core UNAM‐7, obtained 126 km from the center of the Chicxulub impact structure, outside the crater rim, contains a sequence of 126.2 m suevitic, silicate melt‐rich breccia on top of a silicate melt‐poor breccia with anhydrite megablocks. Total reflection X‐ray fluorescence analysis of altered silicate melt particles of the suevitic breccia shows high concentrations of Br, Sr, Cl, and Cu, which may indicate hydrothermal reaction with sea water. Scanning electron microscopy and energy‐dispersive spectrometry reveal recrystallization of silicate components during annealing by superheated impact melt. At anhydrite clasts, recrystallization is represented by a sequence of comparatively large columnar, euhedral to subhedral anhydrite grains and smaller, polygonal to interlobate grains that progressively annealed deformation features. The presence of voids in anhydrite grains indicates SO_x gas release during anhydrite decomposition. The silicate melt‐poor breccia contains carbonate and sulfate particles cemented in a microcrystalline matrix. The matrix is dominated by anhydrite, dolomite, and calcite, with minor celestine and feldspars. Calcite‐dominated inclusions in silicate melt with flow textures between recrystallized anhydrite and silicate melt suggest a former liquid state of these components. Vesicular and spherulitic calcite particles may indicate quenching of carbonate melts in the atmosphere at high cooling rates, and partial decomposition during decompression at postshock conditions. Dolomite particles with a recrystallization sequence of interlobate, polygonal, subhedral to euhedral microstructures may have been formed at a low cooling rate. We conclude that UNAM‐7 provides evidence for solid‐state recrystallization or melting and dissociation of sulfates during the Chicxulub impact event. The lack of anhydrite in the K‐Pg ejecta deposits and rare presence of anhydrite in crater suevites may indicate that sulfates were completely dissociated at high temperature (T > 1465 °C)—whereas ejecta deposited near the outer crater rim experienced postshock conditions that were less effective at dissociation.     

Carbonates in CM chondrites: Complex formational histories and comparison to carbonates in CI chondrites

Abstract– CM chondrites are primitive solar‐system materials that have undergone high degrees of aqueous alteration, resulting in the formation of secondary minerals including carbonates. Two different carbonate minerals (calcite/aragonite and dolomite) together constitute 1.4–2.8 vol% of CM chondrites. In contrast, CI chondrites contain four different carbonate minerals: calcite/aragonite, dolomite, breunnerite, and siderite. CI chondrites have abundant dolomite, a mineral that seems to be absent in the most aqueously altered CM chondrites. In this study, carbonates in seven CM chondrites (Y‐791198, LaPaz Icefield 04796, Cold Bokkeveld, Nogoya, Queen Alexandra Range 93005, Allan Hills 83100, and Meteorite Hills 01070) were studied petrographically and by electron microprobe. The results indicate that carbonate formation in CM chondrites differs from that in CI chondrites and is more complex than previously recognized. Our studies of CM chondrites indicate that (1) carbonates formed on the parent asteroid in an aqueous environment that gradually changed in composition, (2) at some stage, Ca and Mg activities in the environment were high enough to form metastable dolomite, and (3) dolomites disappeared in the most aqueously altered CM chondrites.     

Silicate liquid immiscibility in impact melts

We have investigated silicate emulsions in impact glasses and impact melt rocks from the Wabar (Saudi Arabia), Kamil (Egypt), Barringer (USA), and Tenoumer (Mauritania) impact structures, and in experimentally generated impact glasses and laser-generated glasses (MEMIN research unit) by scanning electron microscopy, electron microprobe analysis, and transmission electron microscopy. Textural evidence of silicate liquid immiscibility includes droplets of one glass disseminated in a chemically distinct glassy matrix; sharp phase boundaries (menisci) between the two glasses; deformation and coalescence of droplets; and occurrence of secondary, nanometer-sized quench droplets in Si-rich glasses. The compositions of the conjugate immiscible liquids (Si-rich and Fe-rich) are consistent with phase separation in two-liquid fields in the general system Fe₂SiO₄–KAlSi₃O₈–SiO₂–CaO–MgO–TiO₂–P₂O₅. Major-element partition coefficients are well correlated with the degree of polymerization (NBO/T) of the Si-rich melt: Fe, Ca, Mg, and Ti are concentrated in the poorly polymerized, Fe-rich melt, whereas K, Na, and Si prefer the highly polymerized, Si-rich melt. Partitioning of Al is less pronounced and depends on bulk melt composition. Thus, major element partitioning between the conjugate liquids closely follows trends known from tholeiitic basalts, lunar basalts, and experimental analogs. The characteristics of impact melt inhomogeneity produced by melt unmixing in a miscibility gap are then compared to impact melt inhomogeneity caused by incomplete homogenization of different (miscible or immiscible) impact melts that result from shock melting of different target lithologies from the crater's melt zone, which do not fully homogenize and equilibrate due to rapid quenching. By taking previous reports on silicate emulsions in impact glasses into account, it follows that silicate impact melts of variable composition, cooling rate, and crystallization history might readily unmix during cooling, thereby rendering silicate liquid immiscibility a much more common process in the evolution of impact melts than previously recognized.     

Partial melting of the Indarch (EH4) meteorite: A textural,chemical, and phase relations view of melting and melt migration

Abstract— To test whether aubrites can be formed by melting of enstatite chondrites and to understand igneous processes at very low O fugacities, we have conducted partial melting experiments on the Indarch (EH4) chondrite at 1000–1500 °C. Silicate melting begins at 1000 °C, and Indarch is completely melted by 1500 °C. The metal-sulfide component melts completely at 1000 °C. Substantial melt migration occurs at 1300–1400 °C, and metal migrates out of the silicate charge at 1450 °C and ～50% silicate partial melting. As a group, our experiments contain three immiscible metallic melts (Si-, P-, and C-rich), two immiscible sulfide melts (Fe- and FeMgMnCa-rich), and silicate melt. Our partial melting experiments on the Indarch (EH4) enstatite chondrite suggest that igneous processes at low fO₂ exhibit several unique features. The complete melting of sulfides at 1000 °C suggests that aubritic sulfides are not relics. Aubritic oldhamite may have crystallized from Ca and S complexed in the silicate melt. Significant metal-sulfide melt migration might occur at relatively low degrees of silicate partial melting. Substantial elemental exchange occurred between different melts (e.g., S between sulfide and silicate, Si between silicate and metal), a feature not observed during experiments at higher fO₂. This exchange may help explain the formation of aubrites from known enstatite chondrites.     

The detection of carbonate in the martian soil at the Phoenix Landing site: A laboratory investigation and comparison with the Thermal and Evolved Gas Analyzer (TEGA) data

Data collected by Phoenix Lander’s Thermal and Evolved Gas Analyzer (Phoenix-TEGA) indicate carbonate thermal decomposition at both low and high temperatures. The high-temperature thermal decomposition is consistent with calcite, dolomite, or ankerite, (3–6 wt.%) or any combination of these phase or, presumably, solid solutions of these phases having intermediate composition. The low-temperature thermal decomposition is consistent with the presence of magnesite or siderite, their solid solutions, or any combination of magnesite and siderite, and possibly other carbon-bearing phases (e.g., organics). The carbonate concentration for the low temperature release, assuming magnesite–siderite, is ～1.0 wt.%. This revised interpretation of the Phoenix-TEGA data resulted from new laboratory measurements of carbonate decomposition at a Phoenix-like 12 mbar atmospheric pressure. Phoenix carbonate was inherited in ejecta from the Vastitas Borealis and Scandia regions, inherited from material deposited by aeolian processes, and/or formed in situ at the Phoenix Landing site (pedogenesis). Inherited carbonate implies multiple formation pathways may be represented by carbonates at the Phoenix Landing site. Soil carbonates and associated moderate alkalinity indicate that the soil pH is favorable for microbial activity at the Phoenix Landing site and presumably throughout the martian northern plains.     

Impact glasses in fallout suevites from the Ries impact structure,Germany: An analytical SEM study

Abstract— t‐Impact‐generated glasses from fallout suevite deposits at the Ries impact structure have been investigated using analytical scanning electron microscopy. Approximately 320 analyses of glass clasts were obtained. Four glass types are distinguished on the basis of composition and microtextures. Type 1 glasses correspond to the aerodynamically shaped glass bombs studied previously by many workers. Major oxide concentrations indicate the involvement of granitic rocks, amphibolites, and minor Al‐rich gneisses during melting. Type 2 glasses are chemically heterogeneous, even within individual clasts, with variations of several wt% in most of the major oxides (e.g., 57–70 wt% SiO₂). This suggests incomplete mixing of: 1) mineral‐derived melts or 2) whole rock melts from a wide range of lithologies. Aluminium‐rich clinopyroxene and Fe‐Mg‐rich plagioclase quench crystals are present in type 1 and 2 glasses, respectively. Type 3 glasses contain substantial amounts of H₂O (?12–17 wt%), low SiO₂ (50–53 wt%), high Al₂O₃ (17–21 wt%), and high CaO (5–7 wt%) contents. This suggests an origin due to shock melting of part of the sedimentary cover. Type 4 glasses form a ubiquitous component of the suevites. Based on their high SiO₂ content (?85–100 wt%), the only possible protolith are sandstones in the lowermost part of the sedimentary succession. Calcite forms globules within type 1 glasses, with which it develops microtextures indicative of liquid immiscibility. Unequivocal evidence also exists for liquid immiscibility between what are now montmorillonite globules and type 1, 2, and 4 glasses, indicating that montmorillonite was originally an impact melt glass. Clearly, the melt zone at the Ries must have incorporated a substantial fraction of the sedimentary cover, as well as the underlying crystalline basement rocks. Impact melts were derived from different target lithologies and these separate disaggregated melts did not substantially mix in most cases (type 2, 3, and 4 glasses and carbonate melts).     

Carbonate-silicate liquid immiscibility upon impact melting: Ries Crater,Germany

Abstract— The 24 km diameter Ries impact crater in southern Germany is one of the most studied impact structures on Earth. The Ries impactor struck a Triassic to Upper Jurassic sedimentary sequence overlying Hercynian crystalline basement. At the time of impact (14.87 × 0.36 Ma; Storzer et al., 1995), the 350 m thick Malm limestone was present only to the south and east of the impact site. To the north and west, the Malm had been eroded away, exposing the underlying Dogger and Lias. The largest proportion of shocked target material is in the impact-melt-bearing breccia suevite. The suevite had been believed to be derived entirely from the crystalline basement. Calcite in the suevite has been interpreted as a postimpact hydrothermal deposit. From optical inspection of 540 thin sections of suevite from 32 sites, I find that calcite in the suevite shows textural evidence of liquid immiscibility with the silicate impact melt. Textural evidence of liquid immiscibility between silicate and carbonate melt in the Ries suevite includes carbonate globules within silicate glass, silicate globules embedded in carbonate, deformable and coalescing carbonate spheres within silicate glass, sharp menisci or cusps and budding between silicate and carbonate melt, fluidal textures and gas vesicles in carbonate schlieren, a quench crystallization sequence of the carbonate, spinifex textured quenched carbonate, separate carbonate spherules in the suevite mineral-fragment matrix, and inclusions of mineral fragments suspended in carbonate blebs. Given this evidence of liquid immiscibility, the carbonate in the suevite therefore has—like the silicate melt—a primary origin by impact-shock melting. Evidence of carbonate-silicate liquid immiscibility is abundant in the suevites from the southwest to east of the Ries crater. The rarer suevites to the west to northeast of the crater are nearly devoid of carbonate melts. This correspondence between the occurrence of outcropping limestones at the target surface and the formation of carbonate melt indicates that the Malm limestones are the source rocks of the carbonate impact melt. This correspondence shows that the suevites preserve a compositional memory of their source rocks. From the regional distribution of suevites with or without immiscible carbonate melts, it is inferred that the Ries impactor hit the steep Albtrauf escarpment at its toe, in an oblique impact from the north.     

The origin of carbonates in impact melt-bearing breccias from Site M0077 at the Chicxulub impact structure,Mexico

Carbonates from the impact melt-bearing breccia in the 2016 IODP/ICDP Expedition 364 drill core at Site M0077 were systematically documented and characterized petrographically and geochemically. Calcite, the only carbonate mineral present, is abundant throughout this deposit as five distinct varieties: (1) subangular carbonate clasts (Type A); (2) subround/irregular carbonate clasts with clay altered rims (Type B); (3) fine-crystalline matrix calcite (Type C); (4) void-filling sparry calcite (Type D); and (5) microcrystalline carbonate with flow textures (Type E). Quantitative geochemical analysis shows that calcite in all carbonate varieties are low in elemental impurities (<2.0 cumulative wt% on average); however, relative concentrations of MgO and MnO vary, which provides distinction between each variety: MgO is highest in calcite from Types A, B, and C carbonates (0.2–0.8 wt% on average); MnO is highest in calcite from Types B, C, and D carbonates (0.2–1.3 wt% on average); and calcite from Type E carbonate is most pure (<0.1 wt% on average MgO and MnO, cumulatively). Based on textural and geochemical variations between carbonate types, we interpret that some of the carbonate target rocks melted during impact and were immiscible within the silicate-dominated melt sheet prior to the resurgence of seawater. Type B clasts were formed by molten fuel–coolant interaction, as the incoming seawater eroded through the melt sheet and encountered carbonate melt (Type E). Post-impact meteoric-dominated hydrothermal activity produced the Mn-elevated calcite from Type C and D carbonates, and altered the Type B clasts to be elevated in Mn and host a clay-rich rim.     

Mineralogy and petrology of the angrite Northwest Africa 1296

Abstract— We report on a new angrite, Northwest Africa (NWA) 1296, a fine‐grained rock with a magmatic texture of rapid cooling. Dendritic olivine (?Fo₅₀) crystallized first in association with anorthite microcrysts (An_98–100) forming composite chains separated from one another by intergrown Al‐Fe diopside‐hedenbergite pyroxenes. In addition, some olivines with lower Mg# and increased CaO (up to 12%) are found between the chains as equant microphenocrysts. Pyroxenes and olivines are both normally zoned from Mg# = 0.52 to less than 0.01 in the rims. Ca‐rich olivines are surrounded by, intergrown with, or replaced by subcalcic kirschsteinite. They appear after plagioclase crystallization stopped, at the end of the crystallization sequence. Minor phases are pyrrhotite, F‐apatite, and titanomagnetite. Pyroxene is the last silicate phase to grow, interstitial to idiomorphic olivine‐kirschsteinite. Numerous small vesicles and some channels are filled with microcristalline carbonate. The mode (vol%) is about 28% olivine, 3% kirschsteinite, 32% anorthite, 34% pyroxene, and 3% of the minor phases—close to that reported previously for D'Orbigny and Sahara (SAH) 99555. The bulk chemical composition of NWA 1296 is similar to D'Orbigny and SAH 99555; NWA 1296 differs by its texture and mineralogy, which are interpreted as resulting from rapid crystallization—an evidence of impact melting. Angrites cannot be produced by partial melting of a CV source because segregation of a “planetary” core is necessary to explain the low FeO/MgO ratio of magnesian olivines. Neither the odd Ca/Al ratio nor the very low SiO₂ content can be explained by conventional partial melting scenarios. We suggest that carbonate is the key to angrite genesis. This is supported by the striking similarities with terrestrial melilitites (low SiO₂, superchondritic Ca/Al ratio, presence of carbonate). The lack of alkalies could be the result of either loss after impact melting or absence of alkalies in the source.     

Chemical compositions of impact melt breccias and target rocks from the Tenoumer impact crater,Mauritania

Abstract— The impact melt breccias from the Tenoumer crater (consisting of a fine‐grained intergrowth of plagioclase laths, pyroxene crystals, oxides, and glass) display a wide range of porosity and contain a large amount of target rock clasts. Analyses of major elements in impact melt rocks show lower contents of SiO₂, Al₂O₃, and Na₂O, and higher contents of MgO, Fe₂O₃, and CaO, than the felsic rocks (i.e., granites and gneisses) of the basement. In comparison with the bulk analyses of the impact melt, the glass is strongly enriched in Si‐Al, whereas it is depleted both in Mg and Fe; moreover, the impact melt rocks are variably enriched or depleted in some REE with respect to the felsic and mafic bedrock types. Gold is slightly enriched in the impact melt, and Co, Cr, and Ni abundances are possibly due to a contribution from mafic bedrock. Evidences of silicate‐carbonate liquid immiscibility, mainly as spherules and globules of calcite within the silicate glass, have been highlighted. HMX mixing calculation confirm that the impact melt rocks are derived from a mixing of at least six different target lithologies outcropping in the area of the crater. A large contribution is derived from granitoids (50%) and mica schist (17–19%), although amphibolites (?15%), cherty limestones (?10%), and ultrabasites (?6%) components are also present. The very low abundances of PGE in the melt rock seem to come mainly from some ultrabasic target rocks; therefore, the contamination from the meteoritic projectile appears to have been negligible.     

Carbonate abundances and isotopic compositions in chondrites

We report the bulk C abundances, and C and O isotopic compositions of carbonates in 64 CM chondrites, 14 CR chondrites, 2 CI chondrites, LEW 85332 (C2), Kaba (CV3), and Semarkona (LL3.0). For the unheated CMs, the total ranges of carbonate isotopic compositions are δ¹³C ≈ 25–75‰ and δ¹⁸O ≈ 15–35‰, and bulk carbonate C contents range from 0.03 to 0.60 wt%. There is no simple correlation between carbonate abundance and isotopic composition, or between either of these parameters and the extent of alteration. Unless accretion was very heterogeneous, the uncorrelated variations in extent of alteration and carbonate abundance suggests that there was a period of open system behavior in the CM parent body, probably prior to or at the start of aqueous alteration. Most of the ranges in CM carbonate isotopic compositions can be explained by their formation at different temperatures (0–130 °C) from a single fluid in which the carbonate O isotopes were controlled by equilibrium with water (δ¹⁸O ≈ 5‰) and the C isotopes were controlled by equilibrium with CO and/or CH₄ (δ¹³C ≈ ?33‰ or ?20‰ for CO‐ or CH₄‐dominated systems, respectively). However, carbonate formation would have to have been inefficient, otherwise carbonate compositions would have resembled those of the starting fluid. A quite similar fluid composition (δ¹⁸O ≈ ?5.5‰, and δ¹³C ≈ ?31‰ or ?17‰ for CO‐ or CH₄‐dominated systems, respectively) can explain the carbonate compositions of the CIs, although the formation temperatures would have been lower (~10–40 °C) and the relative abundances of calcite and dolomite may play a more important role in determining bulk carbonate compositions than in the CMs. The CR carbonates exhibit a similar range of O isotopes, but an almost bimodal distribution of C isotopes between more (δ¹³C ≈ 65–80‰) and less altered samples (δ¹³C ≈ 30–40‰). This bimodality can still be explained by precipitation from fluids with the same isotopic composition (δ¹⁸O ≈ ?9.25‰, and δ¹³C ≈ ?21‰ or ?8‰ for CO‐ or CH₄‐dominated systems, respectively) if the less altered CRs had higher mole fractions of CO₂ in their fluids. Semarkona and Kaba carbonates have some of the lightest C isotopic compositions of the meteorites studied here, probably because they formed at higher temperatures and/or from more CO₂‐rich fluids. The fluids responsible for the alteration of chondrites and from which the carbonates formed were almost certainly accreted as ices. By analogy with cometary ices, CO₂ and/or CO would have dominated the trapped volatile species in the ices. The chondrites studied are too oxidized for CO‐dominated fluids to have formed in their parent bodies. If CH₄ was the dominant C species in the fluids during carbonate formation, it would have to have been generated in the parent bodies from CO and/or CO₂ when oxidation of metal by water created high partial pressures of H₂. The fact that the chondrite carbonate C/H₂O mole ratios are of the order predicted for CO/CO₂‐H₂O ices that experienced temperatures of >50–100 K suggests that the chondrites formed at radial distances of <4–15 AU.     

QUE 94204: A primitive enstatite achondrite produced by the partial melting of an E chondrite‐like protolith

Abstract– Queen Alexandra Range (QUE) 94204, an enstatite achondrite, is a coarse‐grained, highly recrystallized, chondrule‐free and unbrecciated rock dominated (about 70 vol%) by anhedral, equigranular crystals of orthoenstatite of nearly endmember composition (Fs_0.1–0.4, Wo_0.3–0.4) with interstitial plagioclase, kamacite, and troilite. Abundance of approximately 120° triple junctions and the close association of metal–sulfide and plagioclase‐rich melts indicate that QUE 94204 has undergone limited partial melting with inefficient melt extraction. Mineral chemistry indicates a high degree of thermal metamorphism. Kamacite in QUE 94204 contains between 2.09 and 2.55 wt% Si, similar to highly metamorphosed EL chondrites. Plagioclase has between 4.31 and 6.66 wt% CaO, higher than other E chondrites but closer in composition to plagioclase from metamorphosed EL chondrites. QUE 94204 troilite contains up to 2.55 wt% Ti, consistent with extensive thermal metamorphism of an E chondrite‐like precursor. Results presented in this study indicate that QUE 94204 is the result of low degree, (about 5–20 vol%, probably toward the lower end of this range) partial melting of an E chondrite protolith. Textural and chemical evidence suggests that during the metamorphism of QUE 94204, melts formed first at the Fe,Ni‐FeS cotectic near approximately 900 °C, followed by plagioclase‐pyroxene silicate partial melts near approximately 1100 °C. Neither the Fe,Ni‐FeS nor the plagioclase‐pyroxene melts were efficiently segregated or extracted. QUE 94204 belongs to a grouplet of similar “primitive enstatite achondrites” that are analogous to the acapulcoites‐lodranites, but that have resulted from the partial melting of an E chondrite‐like protolith.     

CLAST-LADEN MELT-ROCK FRAGMENT IN THE ADAMS COUNTY,COLORADO, H5 CHONDRITE

The Adams County, Colorado, H5 chondrite contains a lithic fragment, 1 cm in size, that is texturally and mineralogically quite different from the chondritic host. It is composed of: a groundmass of fine-grained euhedral to subhedral olivine (3–15 μm) and interstitial glass enclosing larger olivine and pyroxene grains (0.15-0.5 mm; about 15 vol %); an assemblage of enstatite grains (subfragment within) and an assemblage of olivine plus orthopyroxene (a second subfragment); and about 11 vol % grains of mixed troilite and nickel-iron metal. Analyses yielded these results: (i) olivine grains of the fragment groundmass have a compositional range (Fa_12–45) and most grains contain substantial CaO and Cr₂O₃ (～ 0.20 and 0.30 avg. wt%, respectively); interstitial glass has ～ 55 wt% SiO₂; (ii) larger olivine grains of the fragment are similarly high in CaO and Cr₂O₃ and also have a wide FeO/MgO range; one unusual pyroxene is an Mg-rich pigeonite; (iii) the metal is martensite in composition (11–14 wt% Ni); and (iv) major and trace element analyses by INAA indicate an H-group bulk composition for the entire 1 cm lithic fragment. On the basis of its texture and bulk and mineral compositions, the fragment is interpreted to represent unequilibrated H-group material that was partly melted by impact. The Ca- and Cr-enriched groundmass olivine and interstitial glass resulted from rapid crystallization of the chondritic melt. The Ca- and Cr-enriched larger silicate grains, including the enstatite sub-fragment and the pigeonite grain, are residual, unmelted clasts from the target material (this is supported by the presence of similar material in actual H3 chondrites). Further impact brecciation of the clast-laden melt material, and resultant impact-splashing accounts for the presence of the fragment in the H-group Adams County host and documents the coexistence of unequilibrated and equilibrated H-group material as surface regolith on one parent body.     

Rietveld analysis of X‐ray powder diffraction patterns as a potential tool for the identification of impact‐deformed carbonate rocks

Abstract— Previous X‐ray powder diffraction (XRD) studies revealed that shock deformed carbonates and quartz have broader XRD patterns than those of unshocked samples. Entire XRD patterns, single peak profiles and Rietveld refined parameters of carbonate samples from the Sierra Madera impact crater, west Texas, unshocked equivalent samples from 95 miles north of the crater and the Mission Canyon Formation of southwest Montana and western Wyoming were used to evaluate the use of X‐ray powder diffraction as a potential tool for distinguishing impact deformed rocks from unshocked and tectonically deformed rocks. At Sierra Madera dolostone and limestone samples were collected from the crater rim (lower shock intensity) and the central uplift (higher shock intensity). Unshocked equivalent dolostone samples were collected from well cores drilled outside of the impact crater. Carbonate rocks of the Mission Canyon Formation were sampled along a transect across the tectonic front of the Sevier and Laramide orogenic belts. Whereas calcite subjected to significant shock intensities at the Sierra Madera impact crater can be differentiated from tectonically deformed calcite from the Mission Canyon Formation using Rietveld refined peak profiles, weakly shocked calcite from the crater rim appears to be indistinguishable from the tectonically deformed calcite. In contrast, Rietveld analysis readily distinguishes shocked Sierra Madera dolomite from unshocked equivalent dolostone samples from outside the crater and tectonically deformed Mission Canyon Formation dolomite.     

Carbonates in fractures of Martian meteorite Allan Hills 84001: Petrologic evidence for impact origin

Abstract— Carbonates in Martian meteorite Allan Hills 84001 occur as grains on pyroxene grain boundaries, in crushed zones, and as disks, veins, and irregularly shaped grains in healed pyroxene fractures. Some carbonate disks have tapered Mg-rich edges and are accompanied by smaller, thinner and relatively homogeneous, magnesite microdisks. Except for the microdisks, all types of carbonate grains show the same unique chemical zoning pattern on MgCO₃-FeCO₃-CaCO₃ plots. This chemical characteristic and the close spatial association of diverse carbonate types show that all carbonates formed by a similar process. The heterogeneous distribution of carbonates in fractures, tapered shapes of some disks, and the localized occurrence of Mg-rich microdisks appear to be incompatible with growth from an externally derived CO₂-rich fluid that changed in composition over time. These features suggest instead that the fractures were closed as carbonates grew from an internally derived fluid and that the microdisks formed from a residual Mg-rich fluid that was squeezed along fractures. Carbonate in pyroxene fractures is most abundant near grains of plagioclase glass that are located on pyroxene grain boundaries and commonly contain major or minor amounts of carbonate. We infer that carbonates in fractures formed from grain boundary carbonates associated with plagioclase that were melted by impact and dispersed into the surrounding fractured pyroxene. Carbonates in fractures, which include those studied by McKay et al. (1996), could not have formed at low temperatures and preserved mineralogical evidence for Martian organisms.     

An experimental study on kinetically‐driven precipitation of calcium‐magnesium‐iron carbonates from solution: Implications for the low‐temperature formation of carbonates in martian meteorite Allan Hills 84001

Abstract— Spherical carbonate globules of similar composition, size, and radial Ca‐, Mg‐, and Fe‐zonation to those in martian meteorite Allan Hills (ALH) 84001 were precipitated from Mg‐rich, supersaturated solutions of Ca‐Mg‐Fe‐CO₂‐H₂O at 150 °C. The supersaturated solutions (pH ? 6–7) were prepared at room temperature and contained in Teflon^TM‐lined stainless steel vessels, which were sealed and heated to 150 °C for 24 h. Experiments were also conducted at 25 °C and no globules comparable to those of ALH 84001 were precipitated. Instead, amorphous Fe‐rich carbonates were formed after 24 h and Mg‐Fe calcites formed after 96 h. These experiments suggest a possible low‐temperature inorganic origin for the carbonates in martian meteorite ALH 84001.     

Petrographic studies of the impact melts from Meteor Crater,Arizona, USA

Abstract— We investigated the ballistically dispersed melts from Meteor Crater, Arizona, USA to determine the stratigraphic extent of its melt zone from the compositional relationship of melts and target rocks. Most melt particles are crystallized, hydrated, and oxidized; pristine glasses are rare. Hydration and oxidation occurred at ambient temperatures long after the impact. The preserved glasses are generally clear and texturally homogeneous, but unlike typical impact melts, they have unusually heterogeneous compositions, both within individual particles and from sample to sample. For example, the average SiO₂ for individual particles ranges from 43 to 65%. The projectile content is unusually high and it is distributed bimodally, with specific samples containing either 5–10% or 20–30% FeO. These compositional heterogeneities most likely reflect the high carbonate content of the target rocks and the release of copious CO₂ that dispersed the melts, thereby terminating melt flow and mixing. The high projectile content and the CO₂ depleted residue of purely sedimentary rocks produced mafic melts that crystallized fine‐grained olivine and pyroxene. The melts fall into three compositional groups reflecting variable proportions of the major target formations, Moenkopi, Kaibab, and Coconino. Least‐square mixing calculations revealed one group to contain 55% Moenkopi, 40% quartz‐rich, upper Kaibab, and 5% meteorite, suggesting a source depth of <30 m from the pre‐impact surface. The other two melt groups have higher contents of meteorite (15–20%) and Kaibab (50–70%) and contain more SiO₂ than average Kaibab. The additional quartz may have been derived from Coconino or the upper Kaibab, implying melt depths >90 m or <30 m, respectively. Additional studies, especially hydrocode calculations, are needed to better understand the source depth of these melts and their exceptionally high projectile content.