Magnetic studies on Shergotty and other SNC meteorites

Hysteresis measurements on three shergottite and two nakhlite meteorites indicate single domain grain size behavior for the highly shocked Shergotty, Zagami, and EETA 79001 meteorites, with more multidomain-like behavior for the unshocked Nakhla and Governador Valadares meteorites. High viscosity and initial susceptibility for Antarctic shergottite ALHA 77005 indicate the presence of superparamagnetic grains in this specimen. Thermomagnetic curves likewise reveal a range of oxidation states for the high ulvospinel titanomagnetite grains which dominate the magnetic properties of these first five meteorites. Thermomagnetic analysis indicate Shergotty and Zagami as the least initially oxidized, while EETA 79001 appears to be the most oxidized. Cooling of the meteorite samples from high temperature in air results in a substantial increase in magnetization due to the production of magnetite through oxidation exsolution of titanomagnetite. However, vacuum heating substantially suppresses this process, and in the case of EETA 79001 and Nakhla, results in a rehomogenization of the titanomagnetite grains.Remanence measurements on several subsamples of Shergotty and Zagami meteorites reveal a large variation in intensity that does not seem related to the abundance of remanence carriers. The other meteorites carry only weak remanence, suggesting weak magnetizing fields as the source of their magnetic signal. A paleointensity experiment on a weakly magnetized subsample of Shergotty reveals a low temperature component of magnetization acquired in a field of 2,000 gammas. Also present was a high temperature component reflecting a paleo-field strength of between 250 and 1,000 gammas, depending on the nature and degree of alteration that the sample may have undergone with heating. This is consistent with an earlier paleointensity estimate of 1,000 gammas for ALHA 77005. The weak field environment that these meteorites seem to reflect is consistent with either a Martian or asteroidal body origin, but inconsistent with a terrestrial origin.     

Polycyclic aromatic hydrocarbons (PAHs) in Antarctic Martian meteorites, carbonaceous chondrites, and polar ice

Recent analyses of the carbonate globules present in the Martian meteorite ALH84001 have detected polycyclic aromatic hydrocarbons (PAHs) at the ppm level (McKay et al., 1996). The distribution of PAHs observed in ALH84001 was interpreted as being inconsistent with a terrestrial origin and were claimed to be indigenous to the meteorite, perhaps derived from an ancient martian biota. We have examined PAHs in the Antarctic shergottite EETA79001, which is also considered to be from Mars, as well as several Antarctic carbonaceous chondrites. We have found that many of the same PAHs detected in the ALH84001 carbonate globules are present in Antarctic carbonaceous chondrites and in both the matrix and carbonate (druse) component of EETA79001. We also investigated PAHs in polar ice and found that carbonate is an effective scavenger of PAHs in ice meltwater. Moreover, the distribution of PAHs in the carbonate extract of Antarctic Allan Hills ice is remarkably similar to that found in both EETA79001 and ALH84001. The reported presence of L-amino acids of apparent terrestrial origin in the EETA79001 druse material (McDonald and Bada, 1995) suggests that this meteorite is contaminated with terrestrial organics probably derived from Antarctic ice meltwater that had percolated through the meteorite. Our data suggests that the PAHs observed in both ALH84001 and EETA79001 are derived from either the exogenous delivery of organics to Mars or extraterrestrial and terrestrial PAHs present in the ice meltwater or, more likely, from a mixture of these sources. It would appear that PAHs are not useful biomarkers in the search for extinct or extant life on Mars.     

The Shergotty Consortium and SNC meteorites: An overview

The Shergotty meteorite has a multi-phase (magmatic and shock) history. While the Shergotty picture is complex, consortium studies have advanced our knowledge and understanding of Shergotty and shergottites, nakhlites and Chassigny (SNC) meteorites. Martian origin for the SNC meteorites is strongly favored by several workers from the evidence of trapped noble gases and nitrogen compositions in glasses (lithology C) of the EETA 79001 meteorite, which compare well with the Martian atmosphere analysis made by the Viking Spacecraft. The parent body is about 2 to 4 times richer in volatiles (Cl, Br, Na, K, Rb, Zn, F, Pb, etc.) than the Earth. Consortium studies on Shergotty show very low thermoluminescence, no deformation of tracks, cosmic ray exposure age of about 2.5 million years (m.y.), a pre-atmospheric size of about 12 cm radius, and apparently one shock event at 30 GPa pressure that converted plagioclase to maskelynite. The crystallization age of Shergotty by the Sm-Nd method is 360 ± 16 m.y. The Rb-Sr age for Shergotty is reported as 166 m.y. and the Pb-U age as about 200 m.y. Interpretations of age-dating and exposure scenarios are controversial and may require further studies.At least two scenarios for the ejection of SNC meteorites are possible: 1) ejection as a large body (>6 m size) by a single impact on Mars and then multiple breakup in the asteroidal belt at about 11 m.y. for Chassigny and nakhlites, at 2.5 m.y. for Shergotty, Zagami and ALHA 77005, and at 0.6 m.y. for EETA 79001; and 2) ejection of small objects (<0.5 m size) by multiple impacts on the Martian terrain at 11, 2.5 and 0.6 m.y. with no breakup in space.     

Beryllium-10 contents of shergottites,nakhlites, and Chassigny

Accelerator mass spectrometry gives the following ¹⁰Be contents (dpm/kg) for the SNC meteorites: Shergotty, 13.0 ± 1.5 and 17.3 ± 2.7; Zagami, 18.6 ± 2.5 and 20.0 ± 3.2; ALHA 77005, 15 ± 3; EETA 79001A, 7.8 ± 1.1 and 6.3 ± 0.5; EETA 79001B, 8.5 ± 1.1; Nakhla, 19.7 ± 3.3; Lafayette, 18.1 ± 2.5; Governador Valadares, 25.6 ± 3.6; Chassigny, 20.5 ± 3.1. The ¹⁰Be contents of the NC meteorites indicate that significant accumulation of cosmogenic nuclides occurred in decimeter rather than planetary-size bodies. The agreement of the ³He, ²¹Ne, and ¹⁰Be exposure ages of the shergottites also supports small-body irradiation. A long terrestrial age for EETA 79001 appears unlikely.     

Exposure history of shergottites

The cosmogenic nuclides ³⁶Cl (t_1/2 = 3.0 × 10⁵ years). ²⁶Al (7.05 × 10⁵ years). ¹⁰Be (1.6 × 10⁶ years) and ⁵³Mn (3.7 × 10⁶ years) were measured in three shergottites, ALHA 77005, EETA 79001, and Shergotty by accelerator mass spectrometry and neutron activation. The cosmogenic nuclide data constrain the history and origin of shergottites. ALHA 77005 was ejected from its parent body about 2.7 My ago and was exposed to cosmic rays as a body of 5–6 cm radius. Solar cosmic ray produced ²⁶A1 and ⁵³Mn were first clearly observed in this meteorite. The exposure age of EETA 79001 was 0.6 My and the preatmospheric radius was about 15 cm. The exposure age of Shergotty was calculated to be 2.2 My and the preatmospheric size was about 10–15 cm in radius. The terrestrial age of ALHA 77005 was 0.2 My and that of EETA 79001 was less than 0.06 My. All cosmogenic nuclide data indicate that the three shergottites were never exposed to cosmic rays in their parent bodies, whether that parent body was Mars or an asteroid. All shergottites were ejected from greater than a 3 m depth in their parent bodies. The ejection of EETA 79001 was a different event from that of the other shergottites.     

Noble gas contents of shergottites and implications for the Martian origin of SNC meteorites

Isotopic concentrations of the noble gases have been measured in several different phases of Elephant Moraine A79001 and in whole rock samples of Zagami and Allan Hills A77005, three meteorites which belong to the rare group of SNC achondrites that may have originated from the planet Mars. Shocked phases of EETA79001 contain a trapped Ar, Kr, and Xe component characterized by ${}^{84}\text{Kr}{}^{132}\text{Xe}$ ～15, ${}^{40}\text{Ar}{}^{36}\text{Ar}\text{> 2000}$, ${}^{129}\text{Xe}{}^{132}\text{Xe ≥ 2}$, and ${}^4\text{He}{}^{40}\text{Ar}\text{≤ 0.1}$. These elemental and isotopic ratios are unlike those for any other noble gas component except analyses of the Martian atmosphere made by Viking spacecraft. The isotopic composition of the trapped Kr shows an approximate 1% per mass unit enrichment of lighter isotopes compared to terrestrial Kr, and the traped Xe may show either a fission component or a fractionated enrichment of heavier isotopes compared to terrestrial Xe. It is hypothesized that these gases represent a portion of the Martian atmosphere which was shock-implanted into EETA79001, and that they constitute direct evidence of a Martian origin for the shergottite meteorites. Cosmic ray-produced gases in the eight known SNC meteorites form three distinct groups with exposure ages of ～11 MY (Chassigny and the nakhlites), ～2.6 MY (Shergotty, Zagami, and ALHA77005), and ～0.5 MY (EETA79001). These ages suggest three distinct events and cannot have been produced by irradiation for a common time under greatly different shielding. Comparison of cosmogenic ${}^3\text{He}{}^{21}\text{Ne}$ measured in EETA79001 with two independent models for the production of this ratio as a function of shielding indicates that this meteorite was irradiated in space as a relatively small object. If the SNC meteorites were ejected from Mars ～ 180 My ago, the shock age of the shergottites, they must have been relatively large objects (>6 meters diameter) which experienced at least three space collisions to initiate cosmic ray exposure. Ejection from Mars by three events at the times of initiation of cosmic ray exposure would permit the ejected objects to have been much smaller (<1 meter diameter), but would require three such events on 1.3 Gy Martian terraine in the past ～10 MY and would not explain the common 180 MY shock age seen in all four shergottites.     

Ion microprobe measurements of O/O ratios of phosphate minerals in the Martian meteorites ALH84001 and Los Angeles

Oxygen isotope ratios of merrillite and chlorapatite in the Martian meteorites ALH84001 and Los Angeles have been measured by ion microprobe in multicollector mode. δ¹⁸O values of phosphate minerals measured in situ range from ∼3 to 6‰, and are similar to Martian meteorite whole-rock values, as well as the δ¹⁸O of igneous phosphate on Earth. These results suggest that the primary, abiotic, igneous phosphate reservoir on Mars is similar in oxygen isotopic composition to the basaltic phosphate reservoir on Earth. This is an important first step in the characterization of Martian phosphate reservoirs for the use of δ¹⁸O of phosphate minerals as a biomarker for life on Mars. Cumulative textural, major-element, and isotopic evidence presented here suggest a primary, igneous origin for the phosphates in Los Angeles and ALH84001; textural and chemical evidence suggests that phosphates in ALH84001 were subsequently shock-melted in a later event.     

Xenon and other noble gases in shergottites

We have determined the isotopic composition of the xenon component trapped in EETA 79001 lithologies B and C, which we refer to as SPB-xenon. SPB-xenon is isotopically distinct from known xenon reservoirs, but differs in regular fashion. Normalized to ¹³²Xe, the light isotope ratios are indistinguishable from air, the ¹²⁹Xe/¹³²Xe ratio is about 2.4, and ¹³⁴Xe and ¹³⁶Xe are enhanced relative to the terrestrial atmosphere or AVCC. The apparent heavy-isotope enrichments are not generated by in situ fission and there is no spectral evidence for the presence of ²⁴⁴Pu fission xenon. However, the xenon composition does match that of fractionated AVCC except at ¹²⁹Xe, and consequently may be derived from or related to that component. ALHA 77005, Shergotty and EETA 79001 lithology A also have enhanced ¹²⁹Xe/¹³²Xe ratios in most temperature steps, and are seemingly consistent with varying mixtures of SPB-xenon and terrestrial xenon.Our results for neon and argon in EETA 79001 confirm earlier results on the exposure ages. We have also verified that the trapped ³⁸Ar/³⁶Ar ratio in lithology C is apparently substantially different from the terrestrial or meteoritic value. Krypton in EETA 79001,C is more fractionated with respect to AVCC than is terrestrial krypton and in the opposite direction as xenon. EETA 79001,C contains excess ⁸⁰Kr (and perhaps ⁸²Kr and ¹²⁸Xe), presumably from neutron capture on bromine and iodine, but these neutron captures do not appear to have occurred by in situ processes.     

Thermoluminescence and the shock and reheating history of meteorites—III: The shergottites

The thermoluminescence (TL) sensitivities of the four shergottites are extremely low and display a 10-fold range (values are 0.15 to 1.8, where Dhajala = 1000), with the TL sensitivity decreasing with increasing peak temperature (from about 140 to 180°C) and peak width (from about 100 to 150°C). A mineral separation experiment indicates that the mineral producing the TL is associated with the maskelynite, presumably nanogram per gram quantities of crystalline feldspar are present in the maskelynite. Samples of Shergotty, Allan Hills A77005 and Elephant Moraine A79001 were annealed at 400–900°C for 24–98 h. For Shergotty, the peak increased in width and moved to higher temperatures in the glow-curve, while for Allan Hills A77005 and Elephant Moraine A79001, whose TL peaks were already broad and at high temperatures, remained unchanged. All samples showed a significant increase in TL sensitivity when annealed at >600–700°C. Apparently, the feldspar is present in varying proportions of high to low-temperature form and in amounts which vary from meteorite to meteorite. We conclude that the shergottites underwent post-shock recrystallization at a variety of cooling rates and that the order of increasing cooling rate was Shergotty, Allan Hills A77005, Zagami and Elephant Moraine A79001. The presence of a high-temperature phase implies peak post-shock cooling temperatures >600°C and that the size of the ejecta was <10 m. Current theories are well able to explain the ejection of such small objects from Mars.     

Chronology and petrogenesis of young achondrites,Shergotty, Zagami,and ALHA77005: late magmatism on a geologically active planet

A study was undertaken to determine the chronology, petrogenesis and relationships among the shergottites, Shergotty and Zagami and the unique achondrite ALHA77005. These meteorites are the product of a variety of complex processes.Petrogenesis: Chondrite-normalized abundance patterns of Shergotty and Zagami are very similar and show pronounced depletions of both the light REE (La-Nd) and heavy REE (Dy-Lu) relative to Sm-Gd. These characteristic depletions are even more pronounced for ALHA77005. The light REE depletion is qualitatively consistent with the presence of cumulus pyroxene and/or olivine in these meteorites, but trace element models show that the parental magmas of all three meteorites were probably also light REE depleted. Both trace element model calculations and combined Rb-Sr and Sm-Nd isotopic systematics show that the meteorites could not have been co-magmatic nor can ALHA77005 be representative of the source material of the shergottites. Light REE depletion of the parental magmas also implies light REE depletion of the source material. The Sm-Nd systematics of the shergottites require a time-averaged sub-chondritic (light REE enriched) Sm-Nd ratio since 4.6 AE ago. The Sm-Nd systematics of ALHA77005 permit a time-averaged super-chondritic (light REE depleted) Sm/Nd ratio if its crystallization age is less than T_ICE = 0.72 AE.Chronology. Rb-Sr internal isochrons for all three meteorites and a Sm-Nd internal isochron for Zagami are concordant at ~ 180 Myr. ³⁹Ar-⁴⁰Ar plateau ages of Shergotty and Zagami maskelynite are ~250–260 Myr. These ages apparently reflect resetting of these isotopic systems by shock metamorphism which converted the feldspar to maskelynite. The concordance of these ages suggests a single shock event during which the meteorites were in close physical proximity. The time of this event is most precisely given by the Rb-Sr age of 180 ± 4 Myr for Zagami.The crystallization ages of the meteorites were not precisely determined. Extreme upper limits are determined by Sm-Nd model ages relative to an eucrite initial ${}^{143}\text{Nd}{}^{144}\text{Nd = 0.505835}$ at 4.6 AE ago. These model ages for Shergotty, Zagami and ALHA77005 are 3600, 3500 and 2850 Myr, respectively. The Sm-Nd whole rock age of 1340 ± 60 Myr for the three meteorites gives the crystallization age if the Sm/Nd ratios of the precursor materials were always the same. We consider this 1340 Myr age as a “best estimate” upper limit. “Best estimate” lower limits for Shergotty and Zagami are taken from the average ³⁹Ar-⁴⁰Ar ages of 1200 and 900 Myr of pyroxene separates. The average ³⁹Ar-⁴⁰Ar age of a whole rock sample of ALHA77005 was 1600 Myr and can be partitioned between a low temperature (feldspar) phase and a high temperature (olivine + pyroxene + inclusions) “phase”. The average apparent ³⁹Ar-⁴⁰Ar age of the low temperature phase is ~1050 Myr, which is chosen as the “best estimate” lower limit to the age. The crystallization ages of Shergotty, Zagami and ALHA77005 probably lie within the ranges of 1200–1300, 900–1300 and 1000–1300 Myr, respectively. The Rb-Sr whole rock age of 4400 ± 400 Myr and single-stage BABI model ages of ~4800–5100 Myr are interpreted as reflecting differentiation of the parent body at ~4600 Myr ago.The complex geochemical and isotopic evolution recorded by these meteorites suggests a geologically active parent body capable of sustaining melting at two or more epochs in its history.     

Hf-W isotope systematics of chondrites, eucrites, and martian meteorites: Chronology of core formation and early mantle differentiation in Vesta and Mars

The timescale of accretion and differentiation of asteroids and the terrestrial planets can be constrained using the extinct ¹⁸²Hf-¹⁸²W isotope system. We present new Hf-W data for seven carbonaceous chondrites, five eucrites, and three shergottites. The W isotope data for the carbonaceous chondrites agree with the previously revised ¹⁸²W/¹⁸⁴W of chondrites, and the combined chondrite data yield an improved ?_W value for chondrites of −1.9 ± 0.1 relative to the terrestrial standard. New Hf-W data for the eucrites, in combination with published results, indicate that mantle differentiation in the eucrite parent body (Vesta) occurred at 4563.2 ± 1.4 Ma and suggest that core formation took place 0.9 ± 0.3 Myr before mantle differentiation. Core formation in asteroids within the first ∼5 Myr of the solar system is consistent with the timescales deduced from W isotope data of iron meteorites. New W isotope data for the three basaltic shergottites EETA 79001, DaG 476, and SAU 051, in combination with published ¹⁸²W and ¹⁴²Nd data for Martian meteorites reveal the preservation of three early formed mantle reservoirs in Mars. One reservoir (Shergottite group), represented by Zagami, ALH77005, Shergotty, EETA 79001, and possibly SAU 051, is characterized by chondritic ¹⁴²Nd abundances and elevated ?_W values of ∼0.4. The ¹⁸²W excess of this mantle reservoir results from core formation. Another mantle reservoir (NC group) is sampled by Nakhla, Lafayette, and Chassigny and shows coupled ¹⁴²Nd-¹⁸²W excesses of 0.5-1 and 2-3 ? units, respectively. Formation of this mantle reservoir occurred 10-20 Myr after CAI condensation. Since the end of core formation is constrained to 7-15 Myr, a time difference between early silicate mantle differentiation and core formation is not resolvable for Mars. A third early formed mantle reservoir (DaG group) is represented by DaG 476 (and possibly SAU 051) and shows elevated ¹⁴²Nd/¹⁴⁴Nd ratios of 0.5-0.7 ? units and ?_W values that are indistinguishable from the Shergottite group. The time of separation of this third reservoir can be constrained to 50-150 Myr after the start of the solar system. Preservation of these early formed mantle reservoirs indicates limited convective mixing in the Martian mantle as early as ∼15 Myr after CAI condensation and suggests that since this time no giant impact occurred on Mars that could have led to mantle homogenization. Given that core formation in planetesimals was completed within the first ∼5 Myr of the solar system, it is most likely that Mars and Earth accreted from pre-differentiated planetesimals. The metal cores of Mars and Earth, however, cannot have formed by simply combining cores from these pre-differentiated planetesimals. The ¹⁸²W/¹⁸⁴W ratios of the Martian and terrestrial mantles require late effective removal of radiogenic ¹⁸²W, strongly suggesting the existence of magma oceans on both planets. Large impacts were probably the main heat source that generated magma oceans and led to the formation metallic cores in the terrestrial planets. In contrast, decay of short-lived ²⁶Al and ⁶⁰Fe were important heat sources for melting and core formation in asteroids.     

Kinetic model of carbonate dissolution in Martian meteorite ALH84001

The magnetites and sulfides located in the rims of carbonate globules in the Martian meteorite ALH84001 have been claimed as evidence of past life on Mars. Here, we consider the possibility that the rims were formed by dissolution and reprecipitation of the primary carbonate by the action of water. To estimate the rate of these solution-precipitation reactions, a kinetic model of magnesite-siderite carbonate dissolution was applied and used to examine the physicochemical conditions under which these rims might have formed. The results indicate that the formation of the rims could have taken place in < 50 yr of exposure to small amounts of aqueous fluids at ambient temperatures. Plausible conditions pertaining to reactions under a hypothetical ancient Martian atmosphere (1 bar CO₂), the modern Martian atmosphere (8 mbar CO₂), and the present terrestrial atmosphere (0.35 mbar CO₂) were explored to constrain the site of the process. The results indicated that such reactions likely occurred under the latter two conditions. The possibility of Antarctic weathering must be entertained, which, if correct, would imply that the plausibly biogenic minerals (single-domain magnetite of characteristic morphology and sulfide) reported from the rims may be the products of terrestrial microbial activity. This model is discussed in terms of the available isotope data and found to be compatible with the formation of ALH84001 rims. Particularly, anticorrelated variations of radiocarbon with δ¹³C indicate that carbonate in ALH84001 was affected by solution-precipitation reactions immediately after its initial fall (∼13,000 yr ago) and then again during its recent exposure prior to collection.     

Siderophile elements in Martian meteorites and implications for core formation in Mars

Noble metals, Mo, W, and 24 other elements were determined in six SNC meteorites of presumably Martian origin. Based on element correlations, representative siderophile element concentrations for the silicate mantle of Mars were inferred. From a comparison with experimentally determined metal/silicate partition coefficients of the moderately siderophile elements: Fe, Ni, Co, W, Mo, and Ga, it is concluded that equilibrium between core forming metal and silicates in Mars has occurred at high temperatures (around 2200°C) and low pressures (<1 GPa). This suggests that metal segregation occurred concurrently with rapid accretion of Mars, which is consistent with the inference from excess ¹⁸²W in Martian meteorites (Lee and Halliday, 1997). Concentrations of Ir, Os, Ru, Pt, and Au in the analyzed Martian meteorites, except ALH84001, are at a level of approximately 10⁻²–10⁻³ × CI. The comparatively high abundances of noble metals in Martian meteorites require the addition of chondritic material after core formation. The similarity in Au/La and Pt/Ca ratios between ALH84001 and the other Martian meteorites suggests crystallization of ALH84001 after complete accretion of Mars.     

Noble gases and nitrogen in Martian meteorites Dar al Gani 476, Sayh al Uhaymir 005 and Lewis Cliff 88516: EFA and extra neon

Meteorite “finds” from the terrestrial hot deserts have become a major contributor to the inventory of Martian meteorites. In order to understand their nitrogen and noble gas components, we have carried out stepped heating experiments on samples from two Martian meteorites collected from hot deserts. We measured interior and surface bulk samples, glassy and non-glassy portions of Dar al Gani 476 and Sayh al Uhaymir 005. We have also analyzed noble gases released from the Antarctic shergottite Lewis Cliff 88516 by crushing and stepped heating. For the hot desert meteorites significant terrestrial Ar, Kr, Xe contamination is observed, with an elementally fractionated air (EFA) component dominating the low temperature releases. The extremely low Ar/Kr/Xe ratios of EFA may be the result of multiple episodes of trapping/loss during terrestrial alteration involving aqueous fluids. We suggest fractionation processes similar to those in hot deserts to have acted on Mars, with acidic weathering on the latter possibly even more effective in producing elementally fractionated components. Addition from fission xenon is apparent in DaG 476 and SaU 005. The Ar-Kr-Xe patterns for LEW 88516 show trends as typically observed in shergottites - including evidence for a crush-released component similar to that observed in EETA 79001. A trapped Ne component most prominent in the surface sample of DaG 476 may represent air contamination. It is accompanied by little trapped Ar (²⁰Ne/³⁶Ar > 50) and literature data suggest its presence also in some Antarctic finds. Data for LEW 88516 and literature data, on the other hand, suggest the presence of two trapped Ne components of Martian origin characterized by different ²⁰Ne/²²Ne, possibly related to the atmosphere and the interior. Caution is recommended in interpreting nitrogen and noble gas isotopic signatures of Martian meteorites from hot deserts in terms of extraterrestrial sources and processes. Nevertheless our results provide hope that vice-versa, via noble gases and nitrogen in meteorites and other relevant samples from terrestrial deserts, Martian secondary processes can be studied.     

Negative δO values in Allan Hills 84001 carbonate: Possible evidence for water precipitation on mars

The Martian meteorite ALH84001 contains ∼1% by weight of carbonate formed by secondary processes on the Martian surface or in the shallow subsurface. The major form of this carbonate is chemically and isotopically zoned rosettes which have been well documented elsewhere. This study concentrates upon carbonate regions ∼200 μm across which possess previously unobserved magnesium rich inner cores, interpreted here as rosette fragments, surrounded by a later stage cement containing rare Ca-rich carbonates (up to Ca₈₁Mg₀₇Fe₀₄Mn₀₇) intimately associated with feldspar. High spatial resolution ion probe analyses of Ca-rich carbonate surrounding rosette fragments have δ¹⁸O_V-SMOW values as low as −10‰. These values are not compatible with deposition from a global Martian atmosphere invoked to explain ALH84001 rosettes. The range of δ¹⁸O values are also incompatible with a fluid that has equilibrated with the Martian crust at high temperature or from remobilisation of carbonate of rosette isotopic composition. At Martian atmospheric temperatures, the small CO₂(gas)-CO₂(ice) fractionation makes meteoric CO₂ an unlikely source for −10‰ carbonates. In contrast, closed system Rayleigh fractionation of H₂O can generate δ¹⁸O_H2O −30‰, as observed at high latitudes on Earth. We suggest that atmospheric transport and precipitation of H₂O in a similar fashion to that on Earth provides a source of suitably ¹⁸O depleted water for generation of carbonate with δ¹⁸O_V-SMOW = −10‰.     

火星生命研究的进展与前景

关于火星是否存在或曾经存在生命的争论由来已久。有人以ALH84001火星陨石新鲜破裂面上的大量碳酸盐小球体和多环芳香烃（PAHs）为主要依据，推论火星至少在13～36亿 aBP前很可能有生命形态存在。然而，很多人认为ALH84001陨石的各种特性可以是非生物成因的。由于地球上的生物在超过115℃的温度下很难存活（火星可与之类比），争论的焦点逐渐集中在碳酸盐球体的形成温度上。也有研究者关注该陨石上有机物质的来源问题。对ALH84001陨石的综合学科研究提出了互相矛盾的证据。综述了自1996年以来在国外各种主要期刊上发表的关于 ALH84001陨石与火星生命的研究成果（也包括了一些对其他火星陨石的研究），认为目前尚不能断言火星生命存在与否。对火星继续深入探索以获取进一步的证据是十分必要的。以美国国家航空和宇航局（NASA）Odys sey宇宙飞船起始的火星探测计划将引发新一轮火星生命研究的热潮。     

Petrography and bulk chemistry of Martian orthopyroxenite ALH84001: implications for the origin of secondary carbonates

New petrologic and bulk geochemical data for the SNC-related (Martian) meteorite ALH84001 suggest a relatively simple igneous history overprinted by complex shock and hydrothermal processes. ALH84001 is an igneous orthopyroxene cumulate containing penetrative shock deformation textures and a few percent secondary extraterrestrial carbonates. Rare earth element (REE) patterns for several splits of the meteorite reveal substantial heterogeneity in REE abundances and significant fractionation of the REEs between crushed and uncrushed domains within the meteorite. Complex zoning in carbonates indicates nonequilibrium processes were involved in their formation, suggesting that CO2-rich fluids of variable composition infiltrated the rock while on Mars. We interpret petrographic textures to be consistent with an inorganic origin for the carbonate involving dissolution-replacement reactions between CO2-charged fluids and feldspathic glass in the meteorite. Carbonate formation clearly postdated processes that last redistributed the REE in the meteorite.     

Martian regolith in Elephant Moraine 79001 shock melts? Evidence from major element composition and sulfur speciation

Shock veins and melt pockets in Lithology A of Martian meteorite Elephant Moraine (EETA) 79001 have been investigated using electron microprobe (EM) analysis, petrography and X-ray Absorption Near Edge Structure (XANES) spectroscopy to determine elemental abundances and sulfur speciation (S²⁻ versus S⁶⁺). The results constrain the materials that melted to form the shock glasses and identify the source of their high sulfur abundances. The XANES spectra for EETA79001 glasses show a sharp peak at 2.471 keV characteristic of crystalline sulfides and a broad peak centered at 2.477 keV similar to that obtained for sulfide-saturated glass standards analyzed in this study. Sulfate peaks at 2.482 keV were not observed. Bulk compositions of EETA79001 shock melts were estimated by averaging defocused EM analyses. Vein and melt pocket glasses are enriched in Al, Ca, Na and S, and depleted in Fe, Mg and Cr compared to the whole rock. Petrographic observations show preferential melting and mobilization of plagioclase and pyrrhotite associated with melt pocket and vein margins, contributing to the enrichments. Estimates of shock melt bulk compositions obtained from glass analyses are biased towards Fe- and Mg- depletions because, in general, basaltic melts produced from groundmass minerals (plagioclase and clinopyroxene) will quench to a glass, whereas ultramafic melts produced from olivine and low-Ca pyroxene megacrysts crystallize during the quench. We also note that the bulk composition of the shock melt pocket cannot be determined from the average composition of the glass but must also include the crystals that grew from the melt - pyroxene (En_72-75Fs_20-21Wo_5-7) and olivine (Fo_75-80). Reconstruction of glass + crystal analyses gives a bulk composition for the melt pocket that approaches that of lithology A of the meteorite, reflecting bulk melting of everything except xenolith chromite.Our results show that EETA79001 shock veins and melt pockets represent local mineral melts formed by shock impedance contrasts, which can account for the observed compositional anomalies compared to the whole rock sample. The observation that melts produced during shock commonly deviate from the bulk composition of the host rock has been well documented from chondrites, rocks from terrestrial impact structures and other Martian meteorites. The bulk composition of shock melts reflects the proportions of minerals melted; large melt pockets encompass more minerals and approach the whole rock whereas small melt pockets and thin veins reflect local mineralogy. In the latter, the modal abundance of sulfide globules may reach up to 15 vol%. We conclude the shock melt pockets in EETA79001 lithology A contain no significant proportion of Martian regolith.     

Microscale carbon isotope variability in ALH84001 carbonates and a discussion of possible formation environments

The carbonates in martian meteorite ALH84001 preserve a record of aqueous processes on Mars at 3.9 Ga, and have been suggested to contain signatures of ancient martian life. The conditions of the carbonate formation environment are critical for understanding possible evidence for life on Mars, the history of water on Mars, and the evolution of the martian atmosphere. Despite numerous studies of petrographic relationships, microscale oxygen isotope compositions, microscale chemical compositions, and other minerals associated with the carbonates, formation models remain relatively unconstrained. Microscale carbon isotope analyses of ALH84001 carbonates reveal variable δ¹³C values ranging from +27 to +64‰. The isotopic compositions are correlated with chemical composition and extent of crystallization such that the Mg-poor, early-formed carbonates are relatively ¹³C depleted and the Mg-rich, later forming carbonates, are ¹³C enriched. These data are inconsistent with many of the previously proposed environments for carbonate formation, and a new set of hypotheses are proposed. Specifically, two new models that account for the data involve low temperature (<100°C) aqueous processes: (1) the carbonates formed during mixing of two fluids derived from separate chemical and isotopic reservoirs; or (2) the carbonates formed from high pH fluids that are exposed to a CO₂-rich atmosphere and precipitate carbonate, similar to high pH springs on Earth.