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

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

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

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

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Magnetic properties of Martian meteorites: Implications for an ancient Martian magnetic field

Abstract— The magnetic properties of samples of seven Martian meteorites (EET 79001, Zagami, Nakhla, Lafayette, Governador Valadares, Chassigny and ALH 84001) have been investigated. All possess a weak, very stable primary natural remanent magnetization (NRM), and some have less stable secondary components. In some cases, the latter are associated with magnetic contamination of the samples, imparted since their recovery, and with viscous magnetization, acquired during exposure of the meteorites to the geomagnetic field since they fell. The magnetic properties are carried by a small content (<1%) of titanomagnetite and, in ALH 84001, possibly by magnetite as well. The most likely source of the primary NRM is a thermoremanent magnetization acquired when the meteorite material last cooled from a high temperature in the presence of a magnetic field. Current evidence is that this was 1.3 Ga ago for the nakhlites and Chassigny and 180 Ma for shergottites: the time of the last relevant cooling of ALH 84001 is not presently known. Preliminary estimates of the strength of the magnetizing field are in the range 0.5–5 üT, which is at least an order of magnitude greater than the present field. It is tentatively concluded that the magnetic field was generated by a dynamo process in a Martian core with appropriate structure and properties.     

An abiotic origin for hydrocarbons in the Allan Hills 84001 martian meteorite through cooling of magmatic and impact‐generated gases

Abstract— Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO², and H² below approximately 250–300°C during rapid cooling of trapped magmatic or impact‐generated gases. Depending on temperature, bulk composition, and oxidation‐reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO² ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01–0.001 together with high CO/CO² ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO² ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine‐grain magnetite, formation of a CO‐rich local gas phase, reduction of water vapor to H², reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high‐temperature quenching of CO‐, H²‐rich impact gases could have led to magnetite‐catalyzed hydrocarbon synthesis     

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.     

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.