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 carbonates in the SNC meteorites Allan Hills 84001 and Nakhla

Abstract— We have measured the ¹³C/¹²C and ¹⁴C/¹²C ratios in CO₂ released by acid etching of the carbonate-bearing SNC meteorites Allan Hills 84001 and Nakhla. Most of the C released is strongly enriched in ¹³C. In 10 out of 12 samples, 15‰ <δ¹³C < 55‰. Terrestrial values of carbonateδ¹³C from weathering products are generally between ?10 and +10‰. Two leachate samples especially rich in ¹³C, ALH 84001,27 and Nakhla 25, have elemental Si/Mg ratios much lower than those of the bulk meteorites and ¹⁴C activities that are much lower than the values expected for terrestrial carbonates. The former observation indicates that these leachates consist primarily of carbonates and, less likely, phosphates. The latter observation implies that heavy C was introduced not by terrestrial weathering but by extraterrestrial processes. For ALH 84001,121 (sample 27) and Nakhla (BM 1913,26) δ¹³C = +41‰ and +35‰, respectively. The measured ¹⁸O/¹⁶O ratios in the leaches are similar: δ¹⁸O ～ 15 ± 5‰, contrasting with 4.2‰ in the bulk silicates. We infer that the C in the carbonates retains an extraterrestrial isotopic signature, but probably not O, due to its ease of isotopic exchange (Cole and Ohmoto, 1986).     

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.     

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.     

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.     

A nitrogen and argon stable isotope study of Allan Hills 84001: Implications for the evolution of the Martian atmosphere

Abstract— The abundances and isotopic compositions of N and Ar have been measured by stepped combustion of the Allan Hills 84001 (ALH 84001) Martian orthopyroxenite. Material described as shocked is N-poor ([N] ～ 0.34 ppm; δ¹⁵N ～ +23%); although during stepped combustion, ¹⁵N-enriched N (δ¹⁵N ～ +143%) is released in a narrow temperature interval between 700 °C and 800 °C (along with ¹³C-enriched C (δ¹³C ～ +19%) and ⁴⁰Ar). Cosmogenic species are found to be negligible at this temperature; thus, the iso-topically heavy component is identified, in part, as Martian atmospheric gas trapped relatively recently in the history of ALH 84001. The N and Ar data show that ALH 84001 contains species from the Martian lithosphere, a component interpreted as ancient trapped atmosphere (in addition to the modern atmospheric species), and excess ⁴⁰Ar from K decay. Deconvolution of radiogenic ⁴⁰Ar from other Ar components, on the basis of end-member ³⁶Ar/¹⁴N and ⁴⁰Ar/³⁶Ar ratios, has enabled calculation of a K-Ar age for ALH 84001 as 3.5–4.6 Ga, depending on assumed K abundance. If the component believed to be Martian palaeoatmos-phere was introduced to ALH 84001 at the time the K-Ar age was set, then the composition of the atmosphere at this time is constrained to: δ¹⁵N ≥ +200%, ⁴⁰Ar/³⁶Ar ≤ 300 and ³⁶Ar/¹⁴N ≥ 17 × 10^?5. In terms of the petrogenetic history of the meteorite, ALH 84001 crystallised soon after differentiation of the planet, may have been shocked and thermally metamorphosed in an early period of bombardment, and then subjected to a second event. This later process did not reset the K-Ar system but perhaps was responsible for introducing (recent) atmospheric gases into ALH 84001; and it might mark the time at which ALH 84001 suffered fluid alteration resulting in the formation of the plagioclase and carbonate mineral assemblages.     

Nannobacterial alteration of pyroxenes in martian meteorite Allan Hills 84001

Abstract— In martian meteorite Allan Hills (ALH) 84001, this scanning electron microscope study was focused on the ferromagnesian minerals, which are extensively covered with nanometer‐size bodies mainly 30–100 nm in diameter. These bodies range from spheres to ovoids to caterpillar shapes and resemble, both in size and shape, nannobacteria that attack weathered rocks on Earth and that can be cultured. Dense colonies alternate with clean, smooth cleavage surfaces, possibly formed later. Statistical study shows that the distribution of presumed nannobacteria is very clustered. In addition to the small bodies, there are a few occurrences of ellipsoidal 200–400 nm objects, that are within the lower size range of “normal” earthly bacteria. We conclude that the nanobodies so abundant in ALH 84001 are indeed nannobacteria, confirming the initial assertion of McKay et al. (1996). However, whether these bodies originated on Mars or are Antarctic contamination remains a valid question.     

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.     

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.     

Exposure of Allan Hills 84001 and other achondrites on the Antarctic ice

Abstract— The enrichment of F on Antarctic meteorites is the result of their exposure to the atmosphere, and its measurement allows a subdivision of the terrestrial age into a duration of exposure on the ice and the time a meteorite was enclosed by the ice. In many cases, the periods of surface exposure are only small fractions of the terrestrial ages of meteorites collected in Antarctica. The enrichment of F on the surfaces of Antarctic achondrites was investigated by means of nuclear reaction analysis (NRA): scanning proton beams with an energy of 2.7 and 3.4 MeV were used to induce the reactions ¹⁹F(p,αγ)¹⁶O and ¹⁹F(p, p'γ)¹⁹F, respectively. Gamma signals proportional to the F content were measured. The following Antarctic achondrites were investigated: Martian meteorite ALH 84001; diogenite ALHA77256; the eucrites ALHA81011 and ALHA78132; and in addition, the H5 chondrite ALHA79025. For ALH 84001, our data indicate a period of exposure on the ice of <500 years. Thus, this specimen was enclosed in the ice >95% of its terrestrial age of 13 000 years.     

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.     

Investigations into an unknown organism on the martian meteorite Allan Hills 84001

Abstract— Examination of fracture surfaces near the fusion crust of the martian meteorite Allan Hills (ALH) 84001 have been conducted using scanning electron microscopy (SEM) and atomic force microscopy (AFM) and has revealed structures strongly resembling mycelium. These structures were compared with similar structures found in Antarctic cryptoendolithic communities. On morphology alone, we conclude that these features are not only terrestrial in origin but probably belong to a member of the Actinomycetales, which we consider was introduced during the Antarctic residency of this meteorite. If true, this is the first documented account of terrestrial microbial activity within a meteorite from the Antarctic blue ice fields. These structures, however, do not bear any resemblance to those postulated to be martian biota, although they are a probable source of the organic contaminants previously reported in this meteorite.     

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.     

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.     

Cation diffusion in calcite: Determining closure temperatures and the thermal history for the Allan Hills 84001 meteorite

Abstract— The presence of zoned Fe, Mg, Ca, and Mn in the carbonate phases associated with the cracks and inclusions of the Allan Hills (ALH) 84001 meteorite provides evidence for constraining the thermal history of the meteorite. Using self- and tracer-diffusion coefficients obtained from laboratory experiments on natural calcite, cooling rates are calculated for various temperatures and diffusion distances to assist in the evaluation of the compositional zoning associated with the carbonate phases in ALH 84001. The closure temperature model provides the average temperature below which compositional zoning will be preserved for a given cooling rate, that is, the temperature at which diffusion will be ineffective in homogenizing the phase. The validity of various theories for the formation of the carbonate globules may be examined, therefore, in view of the diffusion-limited kinetic constraints. Experiments using a thin film-mineral diffusion couple and ion microprobe for depth profiling analysis were performed for the temperature range of 550–800 °C to determine self- and tracer-diffusion coefficients for Ca and Mg and in calcite. The resulting activation energies for Ca (E_a(Ca) = 271 ± 80 kJ/mol) and for Mg (E_a(Mg) = 284 ± 74 kJ/mol) were used then to calculate a series of cooling rate, grain size, and closure temperature curves. The data indicate, for example, that by the diffusion of Mg in calcite, a 10 μm compositional zone would be completely homogenized at a temperature of 300 °C for cooling rates <100 K/Ma. These data provide no constraint on formation models that propose a low-temperature fluid precipitation mechanism; however, they indicate that the carbonate globules were not exposed to a high-temperature environment for long time scales following formation.     

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.     

Argon-39-argon-40 “ages” and trapped argon in Martian shergottites,Chassigny, and Allan Hills 84001

Abstract— Argon-isotopic abundances were measured in neutron-irradiated samples of Martian meteorites Chassigny, Allan Hills (ALH) 84001, ALH 77005, Elephant Moraine (EET) 79001, Yamato (Y) 793605, Shergotty, Zagami, and Queen Alexandra Range (QUE) 94201, and in unirradiated samples of ALH 77005. Chassigny gives a ³⁹Ar-⁴⁰Ar age of 1.32 ± 0.07 Ga, which is similar to radiometric ages of the nakhlites. Argon-39-Argon-40 data for ALH 84001 indicate ages between 3.9 and 4.3 Ga. A more precise definition of this age requires detailed characterization of the multiple trapped Ar components in ALH 84001 and of ³⁹Ar recoil distribution. All six shergottite samples show apparent ³⁹Ar-⁴⁰Ar ages substantially older than the ～165–200 Ma range in ages given by other isotope dating techniques. Shergottites appear to contain ubiquitous Ar components acquired from the Martian atmosphere, the Martian mantle, and commonly terrestrial atmospheric contamination. Zagami feldspar also suggests inherited radiogenic ⁴⁰Ar. These data analyses indicate that the recent Martian atmospheric component trapped in shergottites has a ⁴⁰Ar/³⁶Ar ratio possibly as low as ～1750 and no greater than ～1900. These ratios are less than the value of 3000 ± 500 reported by Viking. The ⁴⁰Ar/³⁶Ar ratio for the Martian mantle component is probably <500 but is poorly constrained. The correlation between trapped ⁴⁰Ar/³⁶Ar and ¹²⁹Xe/¹³²Xe ratios in shergottite impact glasses and unirradiated samples of ALH 77005 shows considerable scatter and suggests that the ³⁶Ar/¹³²Xe ratio in the Martian components may vary. Resolution of Martian atmospheric ⁴⁰Ar/³⁶Ar ratio at different time periods (i.e., at ～4.0 and 0.2 Ga) is also difficult without an understanding of the composition of various trapped components.     

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.