Shock and thermal history of Martian meteorite Allan Hills 84001 from transmission electron microscopy

Abstract— Microstructures in the Allan Hills 84001 meteorite were studied using optical and electron microscopy, putting emphasis on shock effects, which are widespread. Some orthopyroxene exhibits only (100) slip, but more typical grains suffered extensive slip, microfracturing, and frequently contain (100) clino‐inversion lamellae. In fracture zones, shock deformation of orthopyroxene has produced all three effects in profusion, together with intergranular pockets of orthopyroxene glass and intragranular glass lamellae, which were apparently created by shearing on low index planes, usually (100) or {110}. Both types of plane are loci that pseudo‐planar fractures tend to follow. Thus, the glass lamellae, which have not been observed in other meteorites, probably formed by frictional heating during the sliding of microscale corrugated surfaces, one over another, leading to local melting. We infer that the orthopyroxene glass and the fracture zones both formed from shear stresses created by strong shock. Ubiquitous undeformed micrometer and submicrometer euhedral chromites in orthopyroxene and plagioclase glasses and carbonate probably crystallized after shock heating and fracture zone formation. Nanocrystals of eskolaite (Cr₂O₃) coating silica glass grains are probably also a result of shock‐induced thermal decomposition of chromite. Iron sulfides (pyrite and pyrrhotite were identified) tended to be associated with plagioclase glass. A carbonate disk showing no evidence for shock deformation had a substructure of elongated, slightly misoriented subcells in the exterior; interior regions had more eqiaxed subcells. Both microstructures probably formed during growth, but the conditions are undetermined. Chemical composition varied on a micron scale, but the rim of the disk was more ferroan; oxide precipitates and voids were widely distributed as in fracture‐filling carbonates. If the fracture zones and opx glass are the result of strong shock, as we deduce, it is very unlikely that pores could have filled by carbonate long after the fracture zones formed. We infer that the carbonate, like the phosphate, olivine, pyrrhotite, eskolaite, and many euhedral, submicrometer chromites, crystallized during the final stages of the impact that created the fracture zones and glasses with compositions of plagioclase, silica, and orthopyroxene.     

Petrogenesis of Allan Hills 84001: Constraints from impact‐melted feldspathic and silica glasses

Abstract— Compositional and textural relationships of shock‐melted glasses in the Allan Hills (ALH) 84001 meteorite have been examined by optical microscopy, electron microprobe analysis, and compositional mapping. The feldspathic and silica glasses exhibit features which constrain the relative timing of shock events and carbonate deposition in ALH 84001. The feldspathic glasses are stoichiometric and have compositions plausibly described as forming from igneous plagioclase (An_27–39Ab_58–68Or_3–7) or sanidine (Or₅₁Ab₄₆An₃), or from a mixture of these phases (mixed‐feldspar glasses). These observations argue against prior interpretations of feldspathic glasses as unflowed maskelynite, hydrothermal precipitates or alteration products, or shock melts that have undergone alkali volatilization. Carbonate was deposited around previously formed mixed‐feldspar glass clasts, suggesting that carbonate deposition occurred after the shock event that formed the granular bands (crushed zones) in this meteorite. SiO₂‐rich glasses appear to be silica remobilized during shock, with little addition of other material. A petrogenetic history of ALH 84001 consistent with the observations of feldspathic and silica glasses is (1) igneous crystallization and cumulate formation; (2) a pre‐carbonate shock event that formed the granular bands (crushed zones) and sheared chromites, and melted igneous plagioclase and sanidine to form mixed‐feldspar glasses; (3) carbonate and silica deposition in the granular bands (veining of plagioclase glasses by SiO₂ and deposition of carbonate around mixed‐feldspar and plagioclase glass clasts); (4) a post‐carbonate shock event that resulted in invasion of carbonate by feldspathic melts, shock faulting and decarbonation of carbonate, high‐temperature mobilization of silica melts, and minor dissolution of orthopyroxene by silica melts.     

Epitaxial growth of nanophase magnetite in Martian meteorite Allan Hills 84001: Implications for biogenic mineralization

Abstract— Crystallographic relationships between magnetite, sulfides, and carbonate rosettes in fracture zones of the Allan Hills (ALH) 84001 Martian meteorite have been studied using analytical electron microscopy. We have focused on those magnetite grains whose growth mechanisms can be rigorously established from their crystallographic properties. Individual magnetite nanocrystals on the surfaces of carbonates are epitaxially intergrown with one another in “stacks” of single-domain crystals. Other magnetite nanocrystals are epitaxially intergrown with the surfaces of the carbonate substrates. The observed magnetite/carbonate (hkl) Miller indices orientation relationships are (?, ?, 3)_m ‖ (1, ?, 0)_c and (1, ?, 1)_m ‖ (0,0, 3)_c with lattice mismatches of ～13% and ～11%, respectively. Epitaxy is a common mode of vapor-phase growth of refractory oxides like magnetite, as is the spiral growth about axial screw dislocations previously observed in other magnetite nanocrystals in ALH 84001. Epitaxy rules out intracellular precipitation of these magnetites by (Martian) organisms, provides further evidence of the high-temperature (>120 °C) inorganic origins of magnetite in ALH 84001, and indicates that the carbonates also have been exposed to elevated temperatures.     

Magnetite in ALH 84001: An origin by shock‐induced thermal decomposition of iron carbonate

Abstract— In martian orthopyroxenite ALH 84001, pockets of feldspathic glass frequently contain carbonate masses that have been disrupted and dispersed within feldspathic shock melt as a result of impact(s). Transmission electron microscope studies of carbonate fragments embedded within feldspathic glass show that the fragments contain myriad, nanometer‐sized magnetite particles with cuboid, irregular, and teardrop morphologies, frequently associated with voids. The fragments of carbonate must have been incorporated into the melt at temperatures of ?900°C, well above the upper thermal stability of siderite (FeCO₃), which decomposes to produce magnetite and CO₂ below ?450°C. These observations suggest that most, if not all, of the fine‐grained magnetite associated with Fe‐bearing carbonate in ALH 84001 could have been formed as result of the thermal decomposition of the siderite (FeCO₃) component of the carbonate and is not due to biological activity.     

Olivine in Martian meteorite Allan Hills 84001: Evidence for a high-temperature origin and implications for signs of life

Abstract— Olivine from Martian meteorite Allan Hills (ALH) 84001 occurs as clusters within orthopyroxene adjacent to fractures containing disrupted carbonate globules and feldspathic shock glass. The inclusions are irregular in shape and range in size from ～40 μm to submicrometer. Some of the inclusions are elongate and boudinage-like. The olivine grains are in sharp contact with the enclosing orthopyroxene and often contain small inclusions of chromite. The olivine exhibits a very limited range of composition from Fo₆₅ to Fo₆₆ (n = 25). The δ¹⁸O values of the olivine and orthopyroxene analyzed by ion microprobe range from +4.3 to +5.3‰ and are indistinguishable from each other within analytical uncertainty. The mineral chemistries, O-isotopic data, and textural relationships indicate that the olivine inclusions were produced at a temperature >800 °C. It is unlikely that the olivines formed during the same event that gave rise to the carbonates in ALH 84001, which have more elevated and variable δ¹⁸O values, and were probably formed from fluids that were not in isotopic equilibrium with the orthopyroxene or olivine. The reactions most likely instrumental in the formation of olivine could be either the dehydration of hydrous silicates that formed during carbonate precipitation or the reduction of orthopyroxene and spinel. If the olivine was formed by either reaction during a postcarbonate heating event, the implications are profound with regards to the interpretations of McKay et al. (1996). Due to the low diffusion rates in carbonates, this rapid, high-temperature event would have resulted in the preservation of the fine-scale carbonate zoning, while partially devolatilizing select carbonate compositions on a submicrometer scale (Brearley, 1998a). This may have resulted in the formation of the minute magnetite grains that McKay et al. (1996) attributed to biogenic activity.     

Experimental shock decomposition of siderite and the origin of magnetite in Martian meteorite ALH 84001

Abstract Shock recovery experiments to determine whether magnetite could be produced by the decomposition of iron‐carbonate were initiated. Naturally occurring siderite was first characterized by a variety of techniques to be sure that the starting material did not contain detectable magnetite. Samples were shocked in tungsten‐alloy holders (W = 90%, Ni = 6%, Cu = 4%) to further ensure that any iron phases in the shock products were contributed by the siderite rather than the sample holder. Each sample was shocked to a specific pressure between 30 to 49 GPa. Transformation of siderite to magnetite as characterized by TEM was found in the 49 GPa shock experiment. Compositions of most magnetites are >50% Fe⁺² in the octahedral site of the inverse spinel structure. Magnetites produced in shock experiments display the same range of sizes (?50–100 nm), compositions (100% magnetite to 80% magnetite‐20% magnesioferrite), and morphologies (equant, elongated, euhedral to subhedral) as magnetites synthesized by Golden et al. (2001) and as the magnetites in Martian meteorite Allan Hills (ALH) 84001. Fritz et al. (2005) previously concluded that ALH 84001 experienced ?32 GPa pressure and a resultant thermal pulse of ?100–110°C. However, ALH 84001 contains evidence of local temperature excursions high enough to melt feldspar, pyroxene, and a silica‐rich phase. This 49 GPa experiment demonstrates that magnetite can be produced by the shock decomposition of siderite as a result of local heating to > 470°C. Therefore, magnetite in the rims of carbonates in Martian meteorite ALH 84001 could be a product of shock devolatilization of siderite as well.     

Multi‐generational carbonate assemblages in martian meteorite Allan Hills 84001: Implications for nucleation,growth, and alteration

Abstract— The carbonate mineralogy of several complex carbonate‐rich regions in Allan Hills (ALH) 84001 has been examined. These regions contain familiar forms of carbonate, as well as textural forms previously unreported including carbonate rosettes, planiform “slab” carbonates, distinct “post‐slab” magnesites, and carbonates interstitial to feldspathic glass and orthopyroxene. Slab carbonates reveal portions of the carbonate growth sequence not seen in the rosettes and suggest that initial nucleating compositions were calcite‐rich. The kinetically controlled growth of rosettes and slab carbonates was followed by an alteration event that formed the magnesite‐siderite layers on the exterior surfaces of the carbonate. Post‐slab magnesite, intimately associated with silica glass, is compositionally similar to the magnesite in these exterior layers but represents a later generation of carbonate growth. Feldspathic glasses had little or no thermal effect on carbonates, as indicated by the lack of thermal decomposition or any compositional changes associated with glass/carbonate contacts.     

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.     

ALH84001, a cumulate orthopyroxenite member of the martian meteorite clan

Abstract— ALH84001, originally classified as a diogenite, is a coarse-grained, cataclastic, orthopyroxenite meteorite related to the martian (SNC) meteorites. The orthopyroxene is relatively uniform in composition, with a mean composition of Wo_3.3En_69.4Fs_27.3. Minor phases are euhedral to subhedral chromite and interstitial maskelynite, An_31.1Ab_63.2Or_5.7, with accessory augite, Wo_42.2En_45.1Fs_12.7, apatite, pyrite and carbonates, Cc_11.5Mg_58.0Sd_29.4Rd_1.1. The pyroxenes and chromites in ALH84001 are similar in composition to these phases in EETA79001 lithology A megacrysts but are more homogeneous. Maskelynite is similar in composition to feldspars in the nakhlites and Chassigny. Two generations of carbonates are present, early (pre-shock) strongly zoned carbonates and late (post-shock) carbonates. The high Ca content of both types of carbonates indicates that they were formed at moderately high temperature, possibly ～700 °C. ALH84001 has a slightly LREE-depleted pattern with La 0.67x and Lu 1.85x CI abundances and with a negative Eu anomaly (Eu/Sm 0.56x CI). The uniform pyroxene composition is unusual for martian meteorites, and suggests that ALH84001 cooled more slowly than did the shergottites, nakhlites or Chassigny. The nearly monomineralic composition, coarse-grain size, homogenous orthopyroxene and chromite compositions, the interstitial maskelynite and apatite, and the REE pattern suggest that ALH84001 is a cumulate orthopyroxenite containing minor trapped, intercumulus material.     

Thermal history of ALH 84001 meteorite by Fe2+‐Mg ordering in orthopyroxene

Abstract— A single orthopyroxene crystal from the Martian meteorite Allan Hills (ALH) 84001 was studied by X‐ray diffraction (XRD) and electron microprobe analysis (EMPA) to retrieve information about its thermal history. Both sets of data were used to measure the Fe²⁺‐Mg order degree between the M1 and M2 sites expressed by the distribution coefficient k_D. The 529 ± 30°C closure temperature (T_c) of the Fe²⁺‐Mg ordering process of ALH 84001 orthopyroxene (Fs₂₈) was calculated using Stimpfl (2005a, 2005b) ln k_D versus 1/T equation obtained for intermediate iron sample. At this T_c, the orthopyroxene cooling rate, calculated by Ganguly's (1982) numerical method, was 0.1 °C/day. This study puts new constraints on the last high‐temperature thermal episode recorded by orthopyroxene. With reference to the geological history (Treiman 1998), we ascribe this episode to the I3 event, and we interpret the T_c of 529 °C as a lower limit for this impact heating. Our data confirm that experimentally defined physical conditions for the formation of magnetite from decomposition of carbonates took place on the Martian surface during event I3.     

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.     

Comprehensive imaging and Raman spectroscopy of carbonate globules from Martian meteorite ALH 84001 and a terrestrial analogue from Svalbard

Abstract— We report a comprehensive imaging study including confocal microRaman spectroscopy, scanning electron microscopy (SEM), and 3‐D extended focal imaging light microscopy of carbonate globules throughout a depth profile of the Martian meteorite Allan Hills (ALH) 84001 and similar objects in mantle peridotite xenoliths from the Bockfjorden volcanic complex (BVC), Svalbard. Carbonate and iron oxide zoning in ALH 84001 is similar to that seen in BVC globules. Hematite appears to be present in all ALH 84001 carbonate‐bearing assemblages except within a magnesite outer rim found in some globules. Macromolecular carbon (MMC) was found in intimate association with magnetite in both ALH 84001 and BVC carbonates. The MMC synthesis mechanism appears similar to established reactions within the Fe‐C‐O system. By inference to a terrestrial analogue of mantle origin (BVC), these results appear to represent the first measurements of the products of an abiotic MMC synthesis mechanism in Martian samples. Furthermore, the ubiquitous but heterogeneous distribution of hematite throughout carbonate globules in ALH 84001 may be partly responsible for some of the wide range in measured oxygen isotopes reported in previous studies. Using BVC carbonates as a suitable analogue, we postulate that a low temperature hydrothermal model of ALH 84001 globule formation is most likely, although alteration (decarbonation) of a subset of globules possibly occurred during a later impact event.     

The history of Allan Hills 84001 revised: Multiple shock events

Abstract— The geologic history of Martian meteorite Allan Hills (ALH) 84001 is more complex than previously recognized, with evidence for four or five crater-forming impacts onto Mars. This history of repeated deformation and shock metamorphism appears to weaken some arguments that have been offered for and against the hypothesis of ancient Martian life in ALH 84001. Allan Hills 84001 formed originally from basaltic magma. Its first impact event (I1) is inferred from the deformation (D1) that produced the granular-textured bands (“crush zones”) that transect the original igneous fabric. Deformation D1 is characterized by intense shear and may represent excavation or rebound flow of rock beneath a large impact crater. An intense thermal metamorphism followed D1 and may be related to it. The next impact (I2) produced fractures, (Fr2) in which carbonate “pancakes” were deposited and produced feldspathic glass from some of the igneous feldspars and silica. After I2, carbonate pancakes and globules were deposited in Fr2 fractures and replaced feldspathic glass and possibly crystalline silicates. Next, feldspars, feldspathic glass, and possibly some carbonates were mobilized and melted in the third impact (I3). Microfaulting, intense fracturing, and shear are also associated with I3. In the fourth impact (I4), the rock was fractured and deformed without significant heating, which permitted remnant magnetization directions to vary across fracture surfaces. Finally, ALH 84001 was ejected from Mars in event I5, which could be identical to I4. This history of multiple impacts is consistent with the photogeology of the Martian highlands and may help resolve some apparent contradictions among recent results on ALH 84001. For example, the submicron rounded magnetite grains in the carbonate globules could be contemporaneous with carbonate deposition, whereas the elongate magnetite grains, epitaxial on carbonates, could be ascribed to vapor-phase deposition during I3.     

Alteration minerals,fluids, and gases on early Mars: Predictions from 1‐D flow geochemical modeling of mineral assemblages in meteorite ALH 84001

Clay minerals, although ubiquitous on the ancient terrains of Mars, have not been observed in Martian meteorite Allan Hills (ALH) 84001, which is an orthopyroxenite sample of the early Martian crust with a secondary carbonate assemblage. We used a low‐temperature (20 °C) one‐dimensional (1‐D) transport thermochemical model to investigate the possible aqueous alteration processes that produced the carbonate assemblage of ALH 84001 while avoiding the coprecipitation of clay minerals. We found that the carbonate in ALH 84001 could have been produced in a process, whereby a low‐temperature (~20 °C) fluid, initially equilibrated with the early Martian atmosphere, moved through surficial clay mineral and silica‐rich layers, percolated through the parent rock of the meteorite, and precipitated carbonates (thereby decreasing the partial pressure of CO₂) as it evaporated. This finding requires that before encountering the unweathered orthopyroxenite host of ALH 84001, the fluid permeated rock that became weathered during the process. We were able to predict the composition of the clay minerals formed during weathering, which included the dioctahedral smectite nontronite, kaolinite, and chlorite, all of which have been previously detected on Mars. We also calculated host rock replacement in local equilibrium conditions by the hydrated silicate talc, which is typically considered to be a higher temperature hydrothermal phase on Earth, but may have been a common constituent in the formation of Martian soils through pervasive aqueous alteration. Finally, goethite and magnetite were also found to precipitate in the secondary alteration assemblage, the latter associated with the generation of H₂. Apparently, despite the limited water–rock interaction that must have led to the formation of the carbonates ~ 3.9 Ga ago, in the vicinity of the ALH 84001 source rocks, clay formation would have been widespread.     

Hydrogen‐isotopic compositions in Allan Hills 84001 and the evolution of the martian atmosphere

Abstract— Hydrogen‐isotopic compositions of carbonate and maskelynite in Allan Hills (ALH) 84001 were measured by secondary ion mass spectrometry (SIMS). the δd values of both minerals show considerable deviation. The deviation seems to be caused by addition of varying amounts of terrestrial water in the case of carbonate. In the case of maskelynite, H is heterogeneously distributed and the deviation in δD values seems to be due to mixing of this indigenous heavy H with isotopically normal H present in the SIMS chamber. The indigenous δD value in ALH 84001 seems to be ～2000%‰. Carbonate rather than maskelynite seems to be the main carrier of H in ALH 84001. Because ALH 84001 is ～4 Ga old, the H‐isotopic composition suggests that a large fraction of the initial martian atmosphere had already escaped by 4 Ga.     

Hosts of hydrogen in Allan Hills 84001: Evidence for hydrous martian salts in the oldest martian meteorite?

Abstract— The martian meteorite, Allan Hills (ALH) 84001, contains D‐rich hydrogen of plausible martian origin (Leshin et al., 1996). The phase identity of the host(s) of this hydrogen are not well known and could include organic matter (McKay et al., 1996), phlogopite (Brearley, 2000), glass (Mittlefehldt, 1994) and/or other unidentified components of this rock. Previous ion microprobe studies indicate that much of the hydrogen in ALH 84001 as texturally associated with concretions of nominally anhydrous carbonates, glass and oxides (Boctor et al., 1998; Sugiura and Hoshino, 2000). We examined the physical and chemical properties of the host(s) of this hydrogen by stepped pyrolysis of variously pre‐treated subsamples. A continuous‐flow method of water reduction and mass spectrometry (Eiler and Kitchen, 2001) was used to permit detailed study of the small amounts of this hydrogen‐poor sample available for study. We find that the host(s) of D‐rich hydrogen released from ALH 84001 at relatively low temperatures (?500 °C) is soluble in orthophosphoric and dilute hydrochloric acids and undergoes near‐complete isotopic exchange with water within hours at temperatures of 200 to 300 °C. These characteristics are most consistent with the carrier phase(s) being a hydrous salt (e.g., carbonate, sulfate or halide); the thermal stability of this material is inconsistent with many examples of such minerals (e.g., gypsum) and instead suggests one or more relatively refractory hydrous carbonates (e.g., hydromagnesite). Hydrous salts (particularly hydrous carbonates) are common on the Earth only in evaporite, sabkha, and hydrocryogenic‐weathering environments; we suggest that much (if not all) of the “martian” hydrogen in ALH 84001 was introduced in analogous environments on or near the martian surface rather than through biological activity or hydrothermal alteration of silicates in the crust.     

The reaction of carbonates in contact with laser-generated,superheated silicate melts: Constraining impact metamorphism of carbonate-bearing target rocks

We simulated entrainment of carbonates (calcite, dolomite) in silicate impact melts by 1-bar laser melting of silicate–carbonate composite targets, using sandstone, basalt, calcite marble, limestone, dolomite marble, and iron meteorite as starting materials. We demonstrate that carbonate assimilation by silicate melts of variable composition is extremely fast (seconds to minutes), resulting in contamination of silicate melts with carbonate-derived CaO and MgO and release of CO₂ at the silicate melt–carbonate interface. We identify several processes, i.e., (1) decomposition of carbonates releases CO₂ and produces residual oxides (CaO, MgO); (2) incorporation of residual oxides from proximally dissociating carbonates into silicate melts; (3) rapid back-reactions between residual CaO and CO₂ produce idiomorphic calcite crystallites and porous carbonate quench products; (4) high-temperature reactions between Ca-contaminated silicate melts and carbonates yield typical skarn minerals and residual oxide melts; (5) mixing and mingling between Ca- or Ca,Mg-contaminated and Ca- or Ca,Mg-normal silicate melts; (6) precipitation of Ca- or Ca,Mg-rich silicates from contaminated silicate melts upon quenching. Our experiments reproduce many textural and compositional features of typical impact melts originating from silicate–carbonate targets. They reinforce hypotheses that thermal decomposition of carbonates, rapid back-reactions between decomposition products, and incorporation of residual oxides into silicate impact melts are prevailing processes during impact melting of mixed silicate–carbonate targets. However, by comparing our results with previous studies and thermodynamic considerations on the phase diagrams of calcite and quartz, we envisage that carbonate impact melts are readily produced during adiabatic decompression from high shock pressure, but subsequently decompose due to heat influx from coexisting silicate impact melts or hot breccia components. Under certain circumstances, postshock conditions may favor production and conservation of carbonate impact melts. We conclude that the response of mixed carbonate–silicate targets to impact might involve melting and decomposition of carbonates, the dominant response being governed by a complex variety of factors.     

The igneous crystallization history of an ancient Martian meteorite from rare earth element microdistributions

Abstract— Rare earth element (REE) and other selected trace and minor element concentrations were measured in individual grains of orthopyroxene, feldspathic glass (of plagioclase composition) and merrillite of the ALH 84001 Martian meteorite. Unlike in other Martian meteorites, phosphate is not the main REE carrier in ALH 84001. The REE pattern of ALH 84001 bulk rock is dependent on the modal abundances of three REE-bearing phases, namely, orthopyroxene, which contains most of the heavy rare earth elements (HREEs); feldspathic glass, which dominates the Eu abundances; and merrillite, which contains the majority of the light rare earth elements (LREEs). Variations in the REE abundances previously observed in different splits of ALH 84001 can easily be explained in terms of small variations in the modal abundances of these three minerals without the need to invoke extensive redistribution of LREEs. At least some orthopyroxenes (i.e., those away from contacts with feldspathic glass) in ALH 84001 appear to have preserved their original REE zonation from igneous fractionation. An estimate of the ALH 84001 parent magma composition from that of the unaltered orthopyroxene “core” (i.e., zoned orthopyroxene with the lowest REE abundances) indicates that it is LREE depleted. This implies that the Martian mantle was already partly depleted within ～100 Ma of solar system formation, which is consistent with rapid accretion and differentiation of Mars. Although equilibration and exchange of REEs between phases (in particular, transport of LREEs into the interstitial phases, feldspathic glass and merrillite) cannot be ruled out, our data suggest that the LREE enrichment in melts “in equilibrium” with these interstitial phases is most likely the result of late-stage infiltration of the cumulate pile by a LREE-enriched melt.     

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.     

High‐pressure polymorphs of magnesian orthopyroxene from a shock vein in the Yamato‐000047 lherzolitic shergottite

Abstract– We found a simple thin shock vein, less than or equal to about 60 μm in width and 1.8 mm in length, in the poikilitic area in the Yamato (Y‐) 000047 lherzolitic shergottite. The shock vein occurs only in magnesian Ca‐poor clinopyroxene, which may have transformed from orthopyroxene during the pressure increase at the shock event. The shock vein consists of (Mg_0.8,Fe_0.2)SiO₃ pyroxene polymorphs, such as columnar akimotoite, two kinds of pyroxene glasses, dendritic akimotoite, and framboidal pyroxene glass, in the order from the periphery to the center. The compositions and textures suggest that columnar akimotoite in the periphery of the shock vein crystallized from solid‐state phase transition of clinopyoroxene during the cooling of the vein, and the remains in the shock vein solidified from shock‐produced melt. The glass includes two kinds of massive glass in the vein and framboidal glass in the vein center. The framboidal glass is the most magnesian and may have been vitrified from perovskite crystallized from high‐pressure melt produced at high temperature ≥3000 °C and high‐pressure 23–40 GPa. Dendritic akimotoites in the vein center metastably crystallized from residual shock melt. The formation sequences of the constituent phases in the shock vein happen in the following order: columnar akimotoites, rim glass, center glass, framboidal glass, and dendritic akimotoites. The increase of the Raman intensity of 660–670 cm^?1 in the order of rim glass, center glass, and framboidal glass suggests that the formation of the pyroxene chain proceeds faster in the vein center than in the vein rim due to its slower cooling. The finding of the shock vein consisting merely of high‐pressure polymorphs of pyroxene, akimotoite, and framboidal glass (vitrified perovskite) is the first reported among all Martian meteorites.