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.     

Siderophile trace elements in ALH84001, other SNC meteorites and eucrites: Evidence of heterogeneity,possibly time-linked,in the mantle of Mars

Abstract— We report neutron activation analyses, including radiochemical determination of trace siderophile elements (Au, Ge, Ir, Ni, Os and Re), for three SNC/martian meteorites, and Os and Re results for numerous eucrites. Ratios such as Ga/Al in the SNC orthopyroxenite ALH84001 confirm its martian affinity—its many distinctive characteristics, most notably its near-primordial age, notwithstanding. To the list of ALH84001's idiosyncrasies can now be added extraordinarily low concentrations of Au, Ni and, especially, Re (17 pg/g), for a martian meteorite. We consider several possible origins for the anomalously low Re content in ALH84001, including metasomatism or alteration. The pyroxene-cumulate nature of this rock probably does not account for its low Re content. Other SNC meteorites are also cumulates. An examination of Re-Nd variations among terrestrial basalts and komatiites suggests that Re is compatible with mantle minerals in general and only incompatible with olivine (however, olivine dominates the mantle residuum, especially during komatiite genesis). Our preferred model is that the ALH84001 parent melt formed in a mantle source region that was far more Re-depleted, and/or at a substantially lower oxygen fugacity, than the sources of the young SNC meteorites. Such a contrast is consistent with models that replenish siderophile elements in planetary mantles by gradual admixture of late-accreting matter and similarly derive most planetary water (which serves as an oxidant) very late in accretion. According to this model, ALH84001 formed before the siderophile-rich matter and water had been mixed well into the martian interior. Possibly the martian mantle never became generally as Re-rich and/or oxidized as the source region(s) of the younger SNCs.     

Nuclear tracks and light noble gases in Allan Hills 84001: Preatmospheric size,fall characteristics,cosmic-ray exposure duration and formation age

Abstract— Cosmic-ray produced nuclear tracks and noble gases have been studied in the martian orthopyroxenite Allan Hills 84001 to delineate its cosmic-ray exposure history, preatmospheric size, and fall characteristics. A K-Ar age of 3.9 Ga, cosmic-ray exposure duration of 16.7 Ma, and a preatmospheric radius of 10 cm have been deduced from the noble gas and track data. The track data suggest ALH 84001 to be a single fall that has suffered atmospheric mass ablation in excess of 85%, higher than the value deduced for the shergottites, ALHA 77005, EETA 79001, and Shergotty. The formation age, as well as the cosmic-ray exposure duration, determined in this work are in good agreement with values reported earlier and are distinctly different from other shergottite, nakhlite, and chassignite (SNC) meteorites analysed so far. The high cosmogenic ²²Ne/²¹Ne ratio of 1.22 most probably reflects an effect due to non-chondritic composition of ALH 84001 as the track data suggest high shielding (<5cm) for the analysed samples. There are signatures in the noble gas data that indicate the possible presence of trapped Ar and Ne of martian atmospheric origin in ALH 84001.     

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.     

Launch of martian meteorites in oblique impacts

A high-velocity oblique impact into the martian surface accelerates solid target material to escape velocity. A fraction of that material eventually falls as meteorites on Earth. For a long time they were called the SNC meteorites (Shergotty, Nakhla, and Chassigny). We study production of potential martian meteorites numerically within the frame of 3D hydrodynamic modeling. The ratio of the volume of escaping solid ejecta to projectile volume depends on the impact angle, impact velocity and the volatile content in the projectile and in the target. The size distribution of ejected fragments appears to be of crucial importance for the atmosphere-ejecta interaction in the case of a relatively small impact (with final crater size <3 km): 10-cm-sized particles are decelerated efficiently, while 30-50% of larger fragments could escape Mars. The results of numerical modeling are compared with shock metamorphic features in martian meteorites, their burial depth, and preatmospheric mass. Although it is impossible to accelerate ejected fragments to escape velocity without substantial compression (above 10 GPa), the maximum temperature increase in dunite (Chassigny) or ortopyroxenite (ALH84001) may be lower than 200 degree. This result is consistent with the observed chaotic magnetization of ALH84001. The probability of microbes' survival may be rather high even for the extreme conditions during the ejection process.     

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.     

Experimental hydrothermal alteration of a martian analog basalt: Implications for martian meteorites

Abstract— A number of martian meteorite samples contain secondary alteration minerals such as Ca‐Mg‐Fe carbonates, Fe oxides, and clay minerals. These mineral assemblages hint at hydrothermal processes occurring in the martian crust, but the alteration conditions are poorly constrained. This study presents the results of experiments that examined the alteration of a high‐Fe basalt by CO₂‐saturated aqueous fluids at 23 and 75 °C and by mixed H₂O‐CO₂ vapors at 200 and 400 °C and water‐rock ratios of 1:1 and 1:10. Results indicate that observable alteration of the basalt takes place after runs of only seven days. This alteration includes mobilization of silica into phases such as opal‐CT and quartz, as well as the formation of carbonates, oxides, and at some conditions, zeolites and hydrous silicates. The degree of alteration increases with run temperature and, in high‐temperature vapor experiments, with increasing water content of the vapor. The degree of alteration and the mineralogy observed in the martian meteorites suggests that none of these samples were exposed to aqueous fluids for long periods of time. Nakhla and Lafayette probably interacted with water for relatively brief periods of time; if so, silica may have been leached from the parent rocks by the altering fluids. Allan Hills 84001 shows possible evidence for very limited interaction with an aqueous fluid, but the overall slight degree of alteration described for this meteorite strongly suggests that it never interacted extensively or at high temperature with any water‐bearing fluid. Elephant Moraine A79001 may not have been altered by aqueous fluids at all. The results of this study best support models wherein the meteorite parent rocks were wetted intermittently or for brief periods of time rather than models that invoke long‐term reaction with large volumes of water. Our experiments studied alteration of a high‐Fe basalt by dilute, CO₂‐saturated, aqueous solutions at 23 and 75 °C and by mixed H₂O‐CO₂ vapors at 200 and 400 °C. The results suggest that alteration of the parent rock takes place even after very short reaction times of seven days. All experiments produced carbonate minerals, including calcite, and in some cases, magnesite, siderite, and ankerite. A free silica phase, either opal, quartz, or hydrated silica, formed in most experiments. More altered experiments also contained minerals such as zeolites and hydrous phyllosilicates. Clay minerals were not observed to form in any experiments. In aqueous fluids, higher temperature corresponded with a higher degree of alteration, whereas changing fluid composition had no observable effect. In high‐temperature vapors, the degree of alteration was controlled by temperature and the proportion of H₂O to CO₂, with water‐rock ratio also playing a role in transport of silica. Application of these results to martian meteorites that contain secondary alteration minerals suggests that none of the martian rocks underwent extensive interaction with aqueous fluids. Nakhla and Lafayette contain clay minerals, which suggests that they interacted with water to some extent, possibly at elevated temperatures. Although ALH84001 shows possible evidence of very limited interaction with aqueous fluids, EETA79001 does not. These results support models for the alteration of these meteorites that do not invoke long‐term interaction with water or reaction with large volumes of water. Except for some models for alteration of ALH84001, this conclusion agrees with most of the literature on alteration of martian meteorites.     

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.     

The rocks of Mars,from far and near

Abstract— The age, structure, composition, and petrogenesis of the martian lithosphere have been constrained by spacecraft imagery and remote sensing. How well do martian meteorites conform to expectations derived from this geologic context? Both data sets indicate a thick, extensive igneous crust formed very early in the planet's history. The composition of the ancient crust is predominantly basaltic, possibly andesitic in part, with sediments derived from volcanic rocks. Later plume eruptions produced igneous centers like Tharsis, the composition of which cannot be determined because of spectral obscuration by dust. Martian meteorites (except Allan Hills 84001) are inferred to have come from volcanic flows in Tharsis or Elysium, and thus are not petrologically representative of most of the martian surface. Remote‐sensing measurements cannot verify the fractional crystallization and assimilation that have been documented in meteorites, but subsurface magmatic processes are consistent with orbital imagery indicating thick crust and large, complex magma chambers beneath Tharsis volcanoes. Meteorite ejection ages are difficult to reconcile with plausible impact histories for Mars, and oversampling of young terrains suggests either that only coherent igneous rocks can survive the ejection process or that older surfaces cannot transmit the required shock waves. The mean density and moment of inertia calculated from spacecraft data are roughly consistent with the proportions and compositions of mantle and core estimated from martian meteorites. Thermal models predicting the absence of crustal recycling, and the chronology of the planetary magnetic field agree with conclusions from radiogenic isotopes and paleomagnetism in martian meteorites. However, lack of vigorous mantle convection, as inferred from meteorite geochemistry, seems inconsistent with their derivation from the Tharsis or Elysium plumes. Geological and meteoritic data provide conflicting information on the planet's volatile inventory and degassing history, but are apparently being reconciled in favor of a periodically wet Mars. Spacecraft measurements suggesting that rocks have been chemically weathered and have interacted with recycled saline groundwater are confirmed by weathering products and stable isotope fractionations in martian meteorites.     

Martian atmospheric and indigenous components of xenon and nitrogen in the Shergotty,Nakhla, and Chassigny group meteorites

Abstract— In a study of the isotopic signatures of trapped Xe in shock-produced glass of shergottites and in ALH 84001, we observe three components: (1) modern Martian atmospheric Xe that is isotopically mass fractionated relative to solar Xe, favoring the heavy isotopes, (2) solar-like Xe, as previously observed in Chassigny, and (3) an isotopically fractionated (possibly ancient) component with little or no radiogenic ¹²⁹Xe_rad. In situ-produced fission and spallation components are observed predominantly in the high-temperature steps. Heavy N signatures in ALH 84001, EET 79001 and Zagami reveal Martian atmospheric components. The low-temperature release of ALH 84001 shows evidence for the presence of a light N component (δ¹⁵N ≤ -21%), which is consistent with the component observed in the other Shergotty, Nakhla and Chassigny (SNC) group meteorites. The highest observed ¹²⁹Xe/¹³⁰Xe ratio of 15.60 in Zagami and EET 79001 is used here to represent the present Martian atmospheric component, and the isotopic composition of this component is compared with other solar system Xe signatures. The ¹²⁹Xe/¹³⁰Xe ratios in ALH 84001 are lower but appear to reflect varying mixing ratios with other components. The consistently high ¹²⁹Xe/¹³⁰Xe ratios in rocks of different radiometric ages suggest that Martian atmospheric Xe evolved early on. As already concluded in earlier work, only a small fission component is observed in the Martian atmospheric component. Assuming that a chondritic ²⁴⁴Pu/¹²⁹I initial ratio applies to Mars, this implies that either Pu-derived fission Xe is retained in the solid planet (in fact, in situ-produced fission Xe is observed in ALH 84001) or may reflect a very particular degassing history of the planet.     

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.     

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.     

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.     

Searching for the source regions of martian meteorites using MGS TES: Integrating martian meteorites into the global distribution of igneous materials on Mars

Abstract— The objective of this study was to identify and map possible source regions for all 5 known martian meteorite lithologies (basalt, lherzolite, clinopyroxenite, orthopyroxenite, and dunite) using data from the Mars Global Surveyor Thermal Emission Spectrometer (MGS TES). We deconvolved the TES data set using laboratory spectra of 6 martian meteorites (Los Angeles, Zagami, ALH A77005, Nakhla, ALH 84001, and Chassigny) as end members, along with atmospheric and surface spectra previously derived from TES data. Global maps (16 pixels/degree) of the distribution of each meteorite end member show that meteorite‐like compositions are not present at or above TES detectability limits over most of the planet's dust‐free regions. However, we have confidently identified local‐scale (100s‐1000s km²) concentrations of olivine‐ and orthopyroxene‐bearing materials similar to ALH A77005, Chassigny, and ALH 84001 in Nili Fossae, in and near Ganges Chasma, in the Argyre and Hellas basin rims, and in Eos Chasma. Nakhla‐like materials are identified near the detection limit throughout the eastern Valles Marineris region and portions of Syrtis Major. Basaltic shergottites were not detected in any spatially coherent areas at the scale of this study. Martian meteorite‐like lithologies represent only a minor portion of the dust‐free surface and, thus, are not representative of the bulk composition of the ancient crust. Meteorite‐like spectral signatures identified above TES detectability limits in more spatially restricted areas (<tens of km) are targets of ongoing analysis.     

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.     

Ion microprobe U‐Th‐Pb dating of phosphates in martian meteorite ALH 84001

Abstract— Phosphates in martian meteorites are important carriers of trace elements, although, they are volumetrically minor minerals. PO₄ also has potential as a biomarker for life on Mars. Here, we report measurements of the U‐Th‐Pb systematics of phosphates in the martian meteorite ALH 84001 using the Sensitive High Resolution Ion MicroProbe (SHRIMP) installed at Hiroshima University, Japan. Eleven analyses of whitlockites and 1 analysis of apatite resulted in a total Pb/U isochron age of 4018 ± 81 Ma in the ²³⁸U/²⁰⁶Pb‐²⁰⁷Pb/²⁰⁶Pb‐²⁰⁴Pb/²⁰⁶ Pb 3‐D space, and a ²³²Th‐²⁰⁸Pb age of 3971 ± 860 Ma. These ages are consistent within a 95% confidence limit. This result is in agreement with the previously published Ar‐Ar shock age of 4.0 ± 0.1 Ga from maskelynite and other results of 3.8–4.3 Ga but are significantly different from the Sm‐Nd age of 4.50 ± 0.13 Ga based on the whole rock and pyroxene. Taking into account recent studies on textural and chemical evidence of phosphate, our result suggests that the shock metamorphic event defines the phosphate formation age of 4018 ± 81 Ma, and that since then, ALH 84001 has not experienced a long duration thermal metamorphism, which would reset the U‐Pb system in phosphates.     

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).     

Martian “microfossils” in lunar meteorites?

Abstract— One of the five lines of evidence used by McKay et al. (1996) for relic life in the Martian meteorite Allan Hills (ALH) 84001 was the presence of objects thought to be microfossils. These ovoid and elongated forms are similar to structures found in terrestrial rocks and described as “nanobacteria” (Folk, 1993; McBride et al, 1994). Using the same procedures and apparatus as McKay et al. (1996), we have found structures on internal fracture surfaces of lunar meteorites that cannot be distinguished from the objects described on similar surfaces in ALH 84001. The lunar surface is currently a sterile environment and probably always has been. However, the lunar and Martian meteorites share a common terrestrial history, which includes many thousands of years of exposure to Antarctic weathering. Although we do not know the origin of these ovoid and elongated forms, we suggest that their presence on lunar meteorites indicates that the objects described by McKay et al. (1996) are not of Martian biological origin.     

Ferric iron in SNC meteorites as determined by Mössbauer spectroscopy: Implications for martian landers and martian oxygen fugacity

Abstract— Mössbauer spectra of martian meteorites are currently of great interest due to the Mössbauer spectrometers on the Athena mission MER rovers as well as the European Space Agency Mars Express mission, with its Beagle 2 payload. Also, considerable current effort is being made to understand the oxygen fugacity of martian magmas because of the effect of fO₂ on mineral chemistry and crystallization processes. For these 2 reasons, the present study was conceived to acquire room temperature Mössbauer spectra of mineral separates and whole rock samples of 10 SNC meteorites. The results suggest that mineral identification using remote application of this technique will be most useful when the phases present have distinctive parameters arising from Fe in very different coordination polyhedra; for example, pyroxene coexisting with olivine can be discriminated easily, but opx versus cpx cannot. The MER goal of using Mössbauer spectroscopy to quantify the relative amounts of individual mineral species present will be difficult to satisfy if silicates are present because the lack of constraints on wt% FeO contents of individual silicate phases present will make modal calculations impossible. The remote Mössbauer spectroscopy will be most advantageous if the rocks analyzed are predominantly oxides with known stoichiometries, though these phases are not present in the SNCs. As for the detection of martian oxygen fugacity, no evidence exists in the SNC samples studied of a relationship between Fe³⁺ content and fO₂ as calculated by independent methods. Possibly, all of the Fe³⁺ observed in olivine is the result of dehydrogenation rather than oxidation, and this process may also be the source of all the Fe³⁺ observed in pyroxene. The observed Fe³⁺ in pyroxene also likely records an equilibrium between pyroxene and melt at such low fO₂ that little or no Fe³⁺ would be expected.