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.     

TOF‐SIMS analysis of polycyclic aromatic hydrocarbons in Allan Hills 84001

Abstract— The presence of polycyclic aromatic hydrocarbons (PAHs) in the Martian meteorite Allan Hills 84001 (ALH 84001) was considered to be a major sign of ancient biogenic activity on planet Mars (McKay et al. 1996). An asserted spatial association of PAHs with carbonates, carriers of so‐called nanofossils, was crucial for their suggested connection to early life forms. Although both observations can be explained individually without employing living organisms, a lateral correlation of PAHs and carbonates would suggest a genetic link between PAHs and the microstructures, favoring a biogenic explanation. On the other hand, without such a correlation, a biogenic or even a Martian origin of the PAHs cannot be inferred. Here we show that there is no correlation of PAHs and carbonates in ALH 84001. Furthermore, a general trend of high PAH concentrations at locations where terrestrial lead is present obviously suggests a terrestrial origin for PAHs in ALH 84001.     

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.     

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.     

Bulk and stable isotopic compositions of carbonate minerals in Martian meteorite Allan Hills 84001: No proof of high formation temperature

Abstract— Understanding the origin of carbonate minerals in the Martian meteorite Allan Hills (ALH) 84001 is crucial to evaluating the hypothesis that they contain traces of ancient Martian life. Using arguments based on chemical equilibria among carbonates and fluids, an origin at >650 °C (inimical to life) has been proposed. However, the bulk and stable isotopic compositions of the carbonate minerals are open to multiple interpretations and so lend no particular support to a high-temperature origin. Other methods (possibly less direct) will have to be used to determine the formation temperature of the carbonates in ALH 84001.     

A petrographic history of martian meteorite ALH84001: Two shocks and an ancient age

Abstract— ALH84001 is an igneous meteorite, an orthopyroxenite of martian origin. It contains petrographic evidence of two shock metamorphic events, separated by thermal and chemical events. The evidence for two shock events suggests that ALH84001 is ancient and perhaps a sample of the martian highlands. From petrography and mineral chemistry, the history of ALH84001 must include: crystallization from magma, a first shock (impact) metamorphism, thermal metamorphism, low-temperature chemical alteration, and a second shock (impact) metamorphism. Originally, ALH84001 was igneous, an orthopyroxene-chromite cumulate. In the first shock event, the igneous rock was cut by melt-breccia or cataclastic veinlets, now bands of equigranular fine-grained pyroxene and other minerals (crush zones). Intact fragments of the cumulate were fractured and strained (now converted to polygonized zones). The subsequent thermal metamorphism (possibly related to the first shock) annealed the melt-breccia or cataclastic veinlets to their present granoblastic texture and permitted chemical homogenization of all mineral species present. The temperature of metamorphism was at least 875 °C, based on mineral thermometers. Next, Mg-Fe-Ca carbonates and pyrite replaced plagioclase in both clasts and granular bands, producing ellipsoidal carbonate globules with sub-micron scale compositional stratigraphy, repeated identically in all globules. The second shock event produced microfault offsets of carbonate stratigraphy and other mineral contacts, radial fractures around chromite and maskelynite, and strain birefringence in pyroxene. Maskelynite could not have been preserved from the first shock event, because it would have crystallized back to plagioclase. The martian source area for ALH84001 must permit this complex, multiple impact history. Very few craters on young igneous surfaces are on or near earlier impact features. It is more likely that ALH84001 was ejected from an old igneous unit (Hesperian or Noachian age), pocked by numerous impact craters over its long exposure at the martian surface.     

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.     

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.     

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.     

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.     

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.     

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.     

Recognition of minor constituents in reflectance spectra of Allan Hills 84001 chips and the importance for remote sensing on Mars

Abstract— Reflectance spectra of splits 92 and 271 from the Martian meteorite Allan Hills (ALH) 84001 are presented and analyzed in this paper. Although the visible and infrared spectra of both chips show that the dominant mineralogy is low-Ca pyroxene, the focus here is on identification of the minor constituents. Infrared spectra measured at multiple spots along the surface of chips 92 and 271 show subtle spectroscopic variations due to changes in the low-Ca pyroxene texture and composition and to the presence of secondary minerals. Absorption bands observed near 0.93 and 1.95 μm are characteristic of low-Ca pyroxene. Strong mid-infrared reststrahlen bands are observed near 9 and 19.5 μm in all surface spectra, and additional bands near 7, 10.5, 11.4, 17.8, 20.5 and 23 μm are variable depending on the low-Ca pyroxene texture and the presence of secondary minerals. Selected spectra exhibit carbonate features near 4, 6.4–7.1 and 11.3 μm. Detailed analysis of these carbonate features indicates the presence of Mg-Fe carbonate, which is consistent with petrographic studies. Many of these spectra with strong carbonate features exhibit a magnetite feature near 17.9 μm and a shoulder near 20.5 μm that cannot be uniquely ascribed to one mineral. Spectroscopic identification of the minor carbonate and magnetite minerals in this probable piece of Mars indicates that detection of small amounts of these minerals of possible biological significance will be possible using infrared hyperspectral analyses of the Martian surface. Also of importance for remote sensing on Mars is the result that Mg, Fe and Mg-Fe carbonates in a low-Ca pyroxene matrix should be distinguishable from one another in the spectral region measured by the thermal emmitance spectrometer (TES).     

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.     

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.     

Petrographic and geochemical evidence for multiphase formation of carbonates in the Martian orthopyroxenite Allan Hills 84001

Martian meteorites can provide valuable information about past environmental conditions on Mars. Allan Hills 84001 formed more than 4 Gyr ago, and owing to its age and long exposure to the Martian environment, and this meteorite has features that may record early processes. These features include a highly fractured texture, gases trapped during one or more impact events or during formation of the rock, and spherical Fe‐Mg‐Ca carbonates. In this study, we have concentrated on providing new insights into the context of these carbonates using a range of techniques to explore whether they record multiple precipitation and shock events. The petrographic features and compositional properties of these carbonates indicate that at least two pulses of Mg‐ and Fe‐rich solutions saturated the rock. Those two generations of carbonates can be distinguished by a very sharp change in compositions, from being rich in Mg and poor in Fe and Mn, to being poor in Mg and rich in Fe and Mn. Between these two generations of carbonate is evidence for fracturing and local corrosion.     

Spectroscopic analysis of Martian meteorite Allan Hills 84001 powder and applications for spectral identification of minerals and other soil components on Mars

Abstract— Spectroscopic measurement and analysis of Martian meteorites provide important information about the mineralogy of Mars, as well as necessary ground-truths for deconvolving remote sensing spectra of the Martian surface rocks. The spectroscopic properties of particulate ALH 84001 from 0.3 to 25 μm correctly identify low-Ca pyroxene as the dominant mineralogy. Absorption bands due to electronic transitions of ferrous iron are observed at 0.94 and 1.97 μm that are typical for low-Ca pyroxene. A strong, broad water band is observed near 3 μm that is characteristic of the water band typically associated with pyroxenes. Weaker features near 4.8, 5.2 and 6.2 μm are characteristic of particulate low-Ca pyroxene and can be distinguished readily from the features due to high-Ca pyroxene and other silicate minerals. The reflectance minimum occurs near 8.6 μm for the ALH 84001 powder, which is more consistent with high-Ca pyroxene and augite than low-Ca pyroxene. The dominant mid-infrared (IR) spectral features for the ALH 84001 powder are observed near 9 and 19.5 μm; however, there are multiple features in this region. These mid-IR features are generally characteristic of low-Ca pyroxene but cannot be explained by low-Ca pyroxene alone. Spectral features from 2.5–5 μm are typically associated with water, organics and carbonates and have been studied in spectra of the ALH 84001, split 92 powder and ALH 84001, splits 92 and 271 chip surfaces. Weak features have been identified near 3.5 and 4 μm that are assigned to organic material and carbonates. Another feature is observed at 4.27 μm in many surface spots and in the powder but has not yet been uniquely identified. Spectroscopic identification of minor organic and carbonate components in this probable piece of Mars suggests that detection of small amounts of organics and carbonates in the Martian surface regolith would also be possible using visible-infrared hyperspectral analyses. Laboratory spectroscopic analysis of Martian meteorites provides a unique opportunity to identify the spectral features of minerals and other components while they are embedded in their natural medium.     

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.     

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.     

Isotopic composition of trapped and cosmogenic noble gases in several Martian meteorites

Abstract— Isotopic abundances of the noble gases were measured in the following Martian meteorites: two shock glass inclusions from Elephant Moraine (EET) 79001, shock vein glass from Shergotty and Yamato (Y) 793605, and whole-rock samples of Allan Hills (ALH) 84001 and Queen Alexandra Range (QUE) 94201. These glass samples, when combined with literature data on a separate single glass inclusion from EET 79001 and a glass vein from Zagami, permit examination in greater detail of the isotopic composition of Ne, Ar, Kr, and Xe trapped from the Martian atmosphere. The isotopic composition of Martian Ne, if actually present in these glasses, remains poorly defined. The ⁴⁰Ar/³⁶Ar ratio of trapped Martian atmospheric Ar is probably considerably lower than the nominal ratio of 3000 measured by Viking, and data on impact glasses suggest a value of ～1900. The atmospheric ³⁶Ar/³⁸Ar ratio is ≤4.0. Martian atmospheric Kr may be enriched in lighter isotopes by ～0.5%/amu compared to both solar-wind Kr and to the Martian composition previously reported. The isotopic composition of Xe in these glasses agrees with that previously reported in the literature. The Martian atmospheric ³⁶Ar/¹³²Xe and ⁸⁴Kr/¹³²Xe elemental ratios are higher than those reported by Viking by factors of ～2.5–1.6 (depending on the ⁴⁰Ar/³⁶Ar ratio adopted) and ～1.8, respectively, and are discussed in a separate paper. Cosmogenic gases indicate space exposure ages of 2.7 ± 0.6 Ma for QUE 94201 and Shergotty and 14 ± 1 Ma for ALH 84001. Small amounts of ²¹Ne produced by energetic solar protons may be present in QUE 94201 but are not present in ALH 84001 or Y-793605. The space exposure age for Y-793605 is 4.9 ± 0.6 Ma and appears to be distinctly older than the ages for basaltic shergottites. However, uncertainties in cosmogenic production rates still makes somewhat uncertain the number of Martian impact events required to produce the exposure ages of Martian meteorites.