A search for amino acids and nucleobases in the Martian meteorite Roberts Massif 04262 using liquid chromatography‐mass spectrometry

The investigation into whether Mars contains signatures of past or present life is of great interest to science and society. Amino acids and nucleobases are compounds that are essential for all known life on Earth and are excellent target molecules in the search for potential Martian biomarkers or prebiotic chemistry. Martian meteorites represent the only samples from Mars that can be studied directly in the laboratory on Earth. Here, we analyzed the amino acid and nucleobase content of the shergottite Roberts Massif (RBT) 04262 using liquid chromatography‐mass spectrometry. We did not detect any nucleobases above our detection limit in formic acid extracts; however, we did measure a suite of protein and nonprotein amino acids in hot‐water extracts with high relative abundances of β‐alanine and γ‐amino‐n‐butyric acid. The presence of only low (to absent) levels of several proteinogenic amino acids and a lack of nucleobases suggest that this meteorite fragment is fairly uncontaminated with respect to these common biological compounds. The distribution of straight‐chained amine‐terminal n‐ω‐amino acids in RBT 04262 resembled those previously measured in thermally altered carbonaceous meteorites (Burton et al. 2012; Chan et al. 2012). A carbon isotope ratio of ?24‰ ± 6‰ for β‐alanine in RBT 04262 is in the range of reduced organic carbon previously measured in Martian meteorites (Steele et al. 2012). The presence of n‐ω‐amino acids may be due to a high temperature Fischer‐Tropsch‐type synthesis during igneous processing on Mars or impact ejection of the meteorites from Mars, but more experimental data are needed to support these hypotheses.     

Mass‐dependent fractionation of nickel isotopes in meteoritic metal

Abstract— We measured nickel isotopes via multicollector inductively coupled plasma mass spectrometry (MC‐ICPMS) in the bulk metal from 36 meteorites, including chondrites, pallasites, and irons (magmatic and non‐magmatic). The Ni isotopes in these meteorites are mass fractionated; the fractionation spans an overall range of ～0.4‰ amu^?1. The ranges of Ni isotopic compositions (relative to the SRM 986 Ni isotopic standard) in metal from iron meteorites (～0.0 to ～0.3‰ amu^?1) and chondrites (～0.0 to ～0.2‰ amu^?1) are similar, whereas the range in pallasite metal (～–0.1 to 0.0‰ amu^?1) appears distinct. The fractionation of Ni isotopes within a suite of fourteen IIIAB irons (～0.0 to ～0.3‰ amu^?1) spans the entire range measured in all magmatic irons. However, the degree of Ni isotopic fractionation in these samples does not correlate with their Ni content, suggesting that core crystallization did not fractionate Ni isotopes in a systematic way. We also measured the Ni and Fe isotopes in adjacent kamacite and taenite from the Toluca IAB iron meteorite. Nickel isotopes show clearly resolvable fractionation between these two phases; kamacite is heavier relative to taenite by ～0.4‰ amu^?1. In contrast, the Fe isotopes do not show a resolvable fractionation between kamacite and taenite. The observed isotopic compositions of kamacite and taenite can be understood in terms of kinetic fractionation due to diffusion of Ni during cooling of the Fe‐Ni alloy and the development of the Widmanstätten pattern.     

Helium loss from Martian meteorites mainly induced by shock metamorphism: Evidence from new data and a literature compilation

Abstract— Noble gas data from Martian meteorites have provided key constraints about their origin and evolution, and their parent body. These meteorites have witnessed varying shock metamorphic overprinting (at least 5 to 14 GPa for the nakhlites and up to 45–55 GPa (e.g., the lherzolitic shergottite Allan Hills [ALH] A77005), solar heating, cosmic‐ray exposure, and weathering both on Mars and Earth. Influences on the helium budgets of Martian meteorites were evaluated by using a new data set and literature data. Concentrations of ³He, ⁴He, U, and Th are measured and shock pressures for same sample aliquots of 13 Martian meteorites were determined to asses a possible relationship between shock pressure and helium concentration. Partitioning of ⁴He into cosmogenic and radiogenic components was performed using the lowest ⁴He/³He ratio we measured on mineral separates (⁴He/³He = 4.1, pyroxene of ALHA77005). Our study revealed significant losses of radiogenic ⁴He. Systematics of cosmogenic ³He and neon led to the conclusion that solar radiation heating during transfer from Mars to Earth and terrestrial weathering can be ruled out as major causes of the observed losses of radiogenic helium in bulk meteorites. For bulk rock we observed a correlation of shock pressure and radiogenic ⁴He loss, ranging between ?20% for Chassigny and other moderately shocked Martian meteorites up to total loss for meteorites shocked above 40 GPa. A steep increase of loss occurs around 30 GPa, the pressure at which plagioclase transforms to maskelynite. This correlation suggests significant ⁴He loss induced by shock metamorphism. Noble gas loss in rocks is seen as diffusion due to (1) the temperature increase during shock loading (shock temperature) and (2) the remaining waste heat after adiabatic unloading (post shock temperature). Modeling of ⁴He diffusion in the main U, Th carrier phase apatite showed that post‐shock temperatures of ?300 °C are necessary to explain observed losses. This temperature corresponds to the post‐shock temperature calculated for bulk rocks shocked at about 40 GPa. From our investigation, data survey, and modeling, we conclude that the shock event during launch of the meteorites is the principal cause for ⁴He loss.     

Potassium isotopic compositions of enstatite meteorites

Enstatite chondrites and aubrites are meteorites that show the closest similarities to the Earth in many isotope systems that undergo mass‐independent and mass‐dependent isotopic fractionations. Due to the analytical challenges to obtain high‐precision K isotopic compositions in the past, potential differences in K isotopic compositions between enstatite meteorites and the Earth remained uncertain. We report the first high‐precision K isotopic compositions of eight enstatite chondrites and four aubrites and find that there is a significant variation of K isotopic compositions among enstatite meteorites (from ?2.34‰ to ?0.18‰). However, K isotopic compositions of nearly all enstatite meteorites scatter around the bulk silicate earth (BSE) value. The average K isotopic composition of the eight enstatite chondrites (?0.47 ± 0.57‰) is indistinguishable from the BSE value (?0.48 ± 0.03‰), thus further corroborating the isotopic similarity between Earth's building blocks and enstatite meteorite precursors. We found no correlation of K isotopic compositions with the chemical groups, petrological types, shock degrees, and terrestrial weathering conditions; however, the variation of K isotopes among enstatite meteorite can be attributed to the parent‐body processing. Our sample of the main‐group aubrite MIL 13004 is exceptional and has an extremely light K isotopic composition (δ⁴¹K = ?2.34 ± 0.12‰). We attribute this unique K isotopic feature to the presence of abundant djerfisherite inclusions in our sample because this K‐bearing sulfide mineral is predicted to be enriched in ³⁹K during equilibrium exchange with silicates.     

Hydrogen isotopic composition of the Martian mantle inferred from the newest Martian meteorite fall,Tissint

The hydrogen isotopic composition of planetary reservoirs can provide key constraints on the origin and history of water on planets. The sources of water and the hydrological evolution of Mars may be inferred from the hydrogen isotopic compositions of mineral phases in Martian meteorites, which are currently the only samples of Mars available for Earth‐based laboratory investigations. Previous studies have shown that δD values in minerals in the Martian meteorites span a large range of ?250 to +6000‰. The highest hydrogen isotope ratios likely represent a Martian atmospheric component: either interaction with a reservoir in equilibrium with the Martian atmosphere (such as crustal water), or direct incorporation of the Martian atmosphere due to shock processes. The lowest δD values may represent those of the Martian mantle, but it has also been suggested that these values may represent terrestrial contamination in Martian meteorites. Here we report the hydrogen isotopic compositions and water contents of a variety of phases (merrillites, maskelynites, olivines, and an olivine‐hosted melt inclusion) in Tissint, the latest Martian meteorite fall that was minimally exposed to the terrestrial environment. We compared traditional sample preparation techniques with anhydrous sample preparation methods, to evaluate their effects on hydrogen isotopes, and find that for severely shocked meteorites like Tissint, the traditional sample preparation techniques increase water content and alter the D/H ratios toward more terrestrial‐like values. In the anhydrously prepared Tissint sample, we see a large range of δD values, most likely resulting from a combination of processes including magmatic degassing, secondary alteration by crustal fluids, shock‐related fractionation, and implantation of Martian atmosphere. Based on these data, our best estimate of the δD value for the Martian depleted mantle is ?116 ± 94‰, which is the lowest value measured in a phase in the anhydrously prepared section of Tissint. This value is similar to that of the terrestrial upper mantle, suggesting that water on Mars and Earth was derived from similar sources. The water contents of phases in Tissint are highly variable, and have been affected by secondary processes. Considering the H₂O abundances reported here in the driest phases (most likely representing primary igneous compositions) and appropriate partition coefficients, we estimate the H₂O content of the Tissint parent magma to be ≤0.2 wt%.     

Ejection ages from krypton‐81‐krypton‐83 dating and pre‐atmospheric sizes of martian meteorites

Abstract— Cosmic‐ray exposure (CRE) ages and Mars ejection times were calculated from the radionuclide ⁸¹Kr and stable Kr isotopes for seven martian meteorites. The following ⁸¹Kr‐Kr CRE ages were obtained: Los Angeles = 3.35 ± 0.70 Ma; Queen Alexandra Range 94201 = 2.22 ± 0.35 Ma; Shergotty = 3.05 ± 0.50 Ma; Zagami = 2.98 ± 0.30 Ma; Nakhla = 10.8 ± 0.8 Ma; Chassigny = 10.6 ± 2.0 Ma; and Allan Hills 84001 = 15.4 ± 5.0 Ma. Comparison of these ages with previously obtained CRE ages from the stable noble gas nuclei ³He, ²¹Ne, and ³⁸Ar shows excellent agreement. This indicates that the method for the production rate calculation for the stable nuclei is reliable. In all martian meteorites we observe effects induced by secondary cosmic‐ray produced epithermal neutrons. Epithermal neutron fluxes, φ_n (30–300 eV), are calculated based on the reaction ⁷⁹Br(n, γβ)⁸⁰Kr. We show that the neutron capture effects were induced in free space during Mars‐Earth transfer of the meteoroids and that they are not due to a pre‐exposure on Mars before ejection of the meteoritic material. Neutron fluxes and slowing down densities experienced by the meteoroids are calculated and pre‐atmospheric sizes are estimated. We obtain minimum radii in the range of 22–25 cm and minimum masses of 150–220 kg. These results are in good agreement with the mean sizes reported for model calculations using current semiempirical data.     

The chlorine isotope composition of Martian meteorites 2. Implications for the early solar system and the formation of Mars

We determined the chlorine isotope composition of 16 Martian meteorites using gas source mass spectrometry on bulk samples and in situ secondary ion microprobe analysis on apatite grains. Measured δ³⁷Cl values range from ?3.8 to +8.6‰. The olivine‐phyric shergottites are the isotopically lightest samples, with δ³⁷Cl mostly ranging from ?4 to ?2‰. Samples with evidence for a crustal component have positive δ³⁷Cl values, with an extreme value of 8.6‰. Most of the basaltic shergottites have intermediate δ³⁷Cl values of ?1 to 0‰, except for Shergotty, which is similar to the olivine‐phyric shergottites. We interpret these data as due to mixing of a two‐component system. The first component is the mantle value of ?4 to ?3‰. This most likely represents the original bulk Martian Cl isotope value. The other endmember is a ³⁷Cl‐enriched crustal component. We speculate that preferential loss of ³⁵Cl to space has resulted in a high δ³⁷Cl value for the Martian surface, similar to what is seen in other volatile systems. The basaltic shergottites are a mixture of the other two endmembers. The low δ³⁷Cl value of primitive Mars is different from Earth and most chondrites, both of which are close to 0‰. We are not aware of any parent‐body process that could lower the δ³⁷Cl value of the Martian mantle to ?4 to ?3‰. Instead, we propose that this low δ³⁷Cl value represents the primordial bulk composition of Mars inherited during accretion. The higher δ³⁷Cl values seen in many chondrites are explained by later incorporation of ³⁷Cl‐enriched HCl‐hydrate.     

A propensity for n‐ω‐amino acids in thermally altered Antarctic meteorites

Abstract– Asteroids and their fragments have impacted the Earth for the last 4.5 Gyr. Carbonaceous meteorites are known to contain a wealth of indigenous organic molecules, including amino acids, which suggests that these meteorites could have been an important source of prebiotic organic material during the origins of life on Earth and possibly elsewhere. We report the detection of extraterrestrial amino acids in thermally altered type 3 CV and CO carbonaceous chondrites and ureilites recovered from Antarctica. The amino acid concentrations of the thirteen Antarctic meteorites ranged from 300 to 3200 parts‐per‐billion (ppb), generally much less abundant than in amino acid‐rich CI, CM, and CR carbonaceous chondrites that experienced much lower temperature aqueous alteration on their parent bodies. In contrast to low‐temperature aqueously altered meteorites that show complete structural diversity in amino acids formed predominantly by Strecker–cyanohydrin synthesis, the thermally altered meteorites studied here are dominated by small, straight‐chain, amine terminal (n‐ω‐amino) amino acids that are not consistent with Strecker formation. The carbon isotopic ratios of two extraterrestrial n‐ω‐amino acids measured in one of the CV chondrites (δ¹³C approximately ?25‰) are consistent with ¹³C‐depletions observed previously in hydrocarbons produced by Fischer‐Tropsch type reactions. The predominance of n‐ω‐amino acid isomers in thermally altered meteorites hints at cosmochemical mechanisms for the preferential formation and preservation of a small subset of the possible amino acids.     

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).     

Precursors of Mars: Constraints from nitrogen and oxygen isotopic compositions of martian meteorites

Abstract— We present an approach to assess the nature of materials involved in the accretion of Mars by the planet's nitrogen (δ¹⁵N) and oxygen (Δ¹⁷O) isotopic compositions as derived from data on martian meteorites. δ¹⁵N for Mars has been derived from nitrogen and xenon systematics, while Δ¹⁷O has been taken from the literature data. These signatures indicate that Mars has most probably accreted from enstatite and ordinary chondritic materials in a ratio of 74:26 and may not have a significant contribution from the carbonaceous (CI, CM, or CV) chondrites. This is consistent with the chromium isotopic (?⁵³Cr) signatures of martian meteorites and the bulk planet Fe/Si ratio for Mars as suggested by the moment of inertia factor (I/MR²) obtained from the Mars Pathfinder data. Further, a simple homogeneous accretion from the above two types of materials is found to be consistent with the planet's moment of inertia factor and the bulk composition of the mantle. But, it requires a core with 6.7 wt% Si, which is consistent with the new results from the high pressure and temperature melting experiments and chemical data on the opaque minerals in enstatite chondrites.     

The formation of weathering products on the LEW 85320 ordinary chondrite: Evidence from carbon and oxygen stable isotope compositions and implications for carbonates in SNC meteorites

Abstract— Isotopic analysis of nesquehonite recovered from the surface of the LEW 85320 H5 ordinary chondrite shows that the δ¹³C and δ¹⁸O values of the two generations of bicarbonate (Antarctic and Texas) are different: δ¹³C = +7.9‰ and +4.2‰; δ¹⁸O = +17.9‰ and + 12.1‰ respectively. Carbon isotopic compositions are consistent with equilibrium formation from atmospheric carbon dioxide at ?2 ± 4 °C (Antarctic) and +16 ± 4 °C (Texas). Oxygen isotopic data imply that the water required for nesquehonite precipitation was derived from atmospheric water vapour or glacial meltwater which had locally exchanged with silicates, either in the meteorite or in underlying bedrock. Although carbonates with similar δ¹³C values have been identified in the SNC meteorites EETA 79001 and Nakhla, petrographic and temperature constraints argue against their simply being terrestrial weathering products.     

Noble gases in planetary atmospheres: Implications for the origin and evolution of atmospheres

The radiogenic and primordial noble gas content of the atmospheres of Venus, Earth, and Mars are compared with one another and with the noble gas content of other extraterrestial samples, especially meteorites. The fourfold depletion of ⁴⁰Ar for Venus relative to the Earth is attributed to the outgassing rates and associated tectonics and volcanic styles for the two planets diverging significantly within the first billion or so years of their history, with the outgassing rate for Venus becoming much less than that for the Earth at subsequent times. This early divergence in the tectonic style of the two planets may be due to a corresponding early onset of the runaway greenhouse on Venus. The 16-fold depletion of ⁴⁰Ar for Mars relative to the Earth may be due to a combination of a mild K depletion for Mars, a smaller fraction of its interior being outgassed, and to an early reduction in its outgassing rate. Venus has lost virtually all of its primordial He and some of its radiogenic He. The escape flux of He may have been quite substantial in Venus' early history, but much diminished at later times, with this time variation being perhaps strongly influenced by massive losses of H₂ resulting from efficient H₂O loss processes.Key trends in the primordial noble gas content of terrestial planetary atmospheres include (1) a several orders of magnitude decrease in ²⁰Ne and ³⁶Ar from Venus to Earth to Mars; (2) a nearly constant ²⁰Ne/³⁶Ar ratio which is comparable to that found in the more primitive carbonaceous chondrites and which is two orders of magnitude smaller than the solar ratio; (3) a sizable fractionation of Ar, Kr, and Xe from their solar ratios, although the degree of fractionation, especially for ³⁶Ar/¹³²Xe, seems to decrease systematically from carbonaceous chondrites to Mars to Earth to Venus; and (4) large differences in Ne and Xe isotopic ratios among Earth, meteorites, and the Sun. Explaining trends (2), (2) and (4), and (1) pose the biggest problems for the solar-wind implantation, primitive atmosphere, and late veneer hypotheses, respectively. It is suggested that the grain-accretion hypothesis can explain all four trends, although the assumptions needed to achieve this agreement are far from proven. In particular, trends (1), (2), (3), and (4) are attributed to large pressure but small temperature differences in various regions of the inner solar system at the times of noble gas incorporation by host phases; similar proportions of the host phases that incorporated most of the He and Ne on the one hand (X) and Ar, Kr, and Xe on the other hand (Q); a decrease in the degree of fractionation with increasing noble-gas partial pressure; and the presence of interstellar carriers containing isotopically anomalous noble gases.Our analysis also suggests that primordial noble gases were incorporated throughout the interior of the outer terrestial planets, i.e., homogeneous accretion is favored over inhomogeneous accretion. In accord with meteorite data, we propose that carbonaceous materials were key hosts for the primordial noble gases incorporated into planets and that they provided a major source of the planets' CO₂ and N₂.     

Large‐ion lithophile element fractionation during the early differentiation of Mars and the composition of the martian primitive mantle

Abstract— Basaltic shergottites display a systematic decrease in K/Th, K/U, and K/La ratios with increasing K content. These trends are interpreted as mixing lines between relatively young martian magmas derived from highly depleted mantle sources and an ancient large‐ion lithophile (LIL) element‐enriched crustal component. One implication of this is that a substantial fractionation of these ratios occurs during the early crustal differentiation on Mars. Isotopic evidence from SNC meteorites and compositional data from Pathfinder and orbital gamma ray spectroscopy suggest that in excess of 50% of the LIL element complement of Mars resides in the crustal reservoir. If so, the primitive mantle of Mars is significantly more volatile‐depleted (i.e., lower K/Th, K/U, K/La) than previously thought but probably (though not necessarily) still less volatile‐depleted than the primitive mantle of the Earth. The La/Th ratios of virtually all SNC meteorites are subchondritic, including those with the most severe LREE‐depletion. Extrapolation of the basaltic shergottite trend suggests that both the depleted mantle end member and the enriched crustal end member have subchondritic La/Th ratios. This is in contrast with the Earth where basalts from LIL element‐depleted sources such as MORB have superchondritic La/Th ratios, complementary to the subchondritic ratios of the continental crust. Accordingly, assuming that the refractory elements are in chondritic proportions for the Mars primitive mantle, an additional major geochemical reservoir must exist on Mars that may not yet have been sampled.     

Nitrogen components in IAB/IIICD iron meteorites

Abstract— Isotopic variations have been reported for many elements in iron meteorites, with distinct N signatures found in the metal and graphite of IAB irons. In this study, a dozen IAB/IIICD iron meteorites (see Table 1 for new classifications) were analyzed by stepwise pyrolysis to resolve nitrogen components. Although isotopic heterogeneity has been presumed to be lost in thermally processed parent objects, the high‐resolution nitrogen isotopic data indicate otherwise. At least one reservoir has a light nitrogen signature, δ¹⁵N = ?(74 ± 2)‰, at 900 °C to 1000 °C, with a possible second, even lighter, reservoir in Copiapo (δ¹⁵N ≤ ?82‰). These releases are consistent with metal nitride decomposition or low‐temperature metal phase changes. Heavier nitrogen reservoirs are observed in steps ≤700 °C and at 1200 °C to 1400 °C. The latter release has a δ¹⁵N signature with a limit of ≥?16‰. Xenon isotopic signatures are sensitive indicators for the presence of inclusions because of the very low abundances of Xe in metal. The combined high‐temperature release shows ¹³¹Xe and ¹²⁹Xe excesses to be consistent with shifts expected for Te(n,γ) reaction in troilite by epithermal neutrons, but there are also possible alterations in the isotopic ratios likely due to extinct ¹²⁹I and cosmic‐ray spallation. The IAB/IIICD iron data imply that at least one light N component survived the formation processes of iron parent objects which only partially exchanged nitrogen between phases. Preservation of separate N reservoirs conflicts with neither the model of impact‐heating effects for these meteorites nor reported age differences between metal and silicates.     

The origin of water on Mars

This paper considers the origin of water on Mars, in the context of a dynamical model that accounts for most of the Earth's water as a product of collisions between the growing Earth and planet-sized “embryos” from the asteroid belt. Mars' history is found to be different; to explain the present mass of Mars requires that it suffer essentially no giant collisions and the bulk of its growth is through addition of smaller bodies. Asteroids and comets from beyond 2.5 AU provide the source of Mars' water, which totals 6-27% of the Earth's present ocean (1 Earth ocean≡1.5×10²¹ kg), equivalent to 600-2700-m depth on the martian surface. The D/H ratio of this material is 1.2-1.6 times Standard Mean Ocean Water, the smaller value obtaining for the larger amount of water accreted. The upper half of the range of total water accreted, while many times less than that acquired by the Earth, is consistent with geological data on Mars, and the D/H value is that derived for martian magmatic water from SNC meteorites. Both together are consistent with published interpretations of the high D/H in present-day martian atmospheric water in terms of water loss through atmospheric escape.     

Methane emissions from Earth’s degassing: Implications for Mars

The presence of methane on Mars is of great interest, since one possibility for its origin is that it derives from living microbes. However, CH₄ in the martian atmosphere also could be attributable to geologic emissions released through pathways similar to those occurring on Earth. Using recent data on methane degassing of the Earth, we have estimated the relative terrestrial contributions of fossil geologic methane vs. modern methane from living methanogens, and have examined the significance that various geologic sources might have for Mars.Geologic degassing includes microbial methane (produced by ancient methanogens), thermogenic methane (from maturation of sedimentary organic matter), and subordinately geothermal and volcanic methane (mainly produced abiogenically). Our analysis suggests that ～80% of the “natural” emission to the terrestrial atmosphere originates from modern microbial activity and ～20% originates from geologic degassing, for a total CH₄ emission of ～28.0×10⁷ tonnes year^?1.Estimates of methane emission on Mars range from 12.6×10¹ to 57.0×10⁴ tonnes year^?1 and are 3–6 orders of magnitude lower than that estimated for Earth. Nevertheless, the recently detected martian, Northern-Summer-2003 CH₄ plume could be compared with methane expulsion from large mud volcanoes or from the integrated emission of a few hundred gas seeps, such as many of those located in Europe, USA, Mid-East or Asia. Methane could also be released by diffuse microseepage from martian soil, even if macro-seeps or mud volcanoes were lacking or inactive. We calculated that a weak microseepage spread over a few tens of km², as frequently occurs on Earth, may be sufficient to generate the lower estimate of methane emission in the martian atmosphere.At least 65% of Earth’s degassing is provided by kerogen thermogenesis. A similar process may exist on Mars, where kerogen might include abiogenic organics (delivered by meteorites and comets) and remnants of possible, past martian life. The remainder of terrestrial degassed methane is attributed to fossil microbial gas (～25%) and geothermal-volcanic emissions (～10%). Global abiogenic emissions from serpentinization are negligible on Earth, but, on Mars, individual seeps from serpentinization could be significant. Gas discharge from clathrate-permafrost destabilization should also be considered.Finally, we have shown examples of potential degassing pathways on Mars, including mud volcano-like structures, fault and fracture systems, and major volcanic edifices. All these types of structures could provide avenues for extensive gas expulsion, as on Earth. Future investigations of martian methane should be focused on such potential pathways.     

Natural transfer of viable microbes in space.

The possibility and probability of natural transfer of viable microbes from Mars to Earth and Earth to Mars traveling in meteoroids during the first 0.5 Ga and the following 4 Ga are investigated, including: --radiation protection against the galactic cosmic ray nuclei and the solar rays, dose rates as a function of the meteorite's radial column mass (radius x density), combined with dose rates generated by natural radioactivity within the meteorite; and survival curves for some bacterial species using NASA's HZETRN transport code --other factors affecting microbe survival: vacuum; central meteorite temperatures at launch, orbiting, and arrival; pressure and acceleration at launch; spontaneous DNA decay; metal ion migration --mean sizes and numbers of unshocked meteorites ejected and percentage falling on Earth, using current semiempirical results --viable flight times for the microbe species Bacillus subtilis and Deinococcus radiodurans R1 --the approximate fraction of microbes (with properties like the two species studied) viably arriving on Earth out of those ejected from Mars during the period 4 Ga BP to the present time, and during the 700 Ma from 4.5 to 3.8 Ga. Similarly, from Earth to Mars. The conclusion is that if microbes existed or exist on Mars, viable transfer to Earth is not only possible but also highly probable, due to microbes' impressive resistance to the dangers of space transfer and to the dense traffic of billions of martian meteorites which have fallen on Earth since the dawn of our planetary system. Earth-to-Mars transfer is also possible but at a much lower frequency.     

The Cu isotopic composition of iron meteorites

Abstract– High‐precision Cu isotopic compositions have been measured for the metal phase of 29 iron meteorites from various groups and for four terrestrial standards. The data are reported as the δ⁶⁵Cu permil deviation of the ⁶⁵Cu/⁶³Cu ratio relative to the NIST SRM 976 standard. Terrestrial mantle rocks have a very narrow range of variations and scatter around zero. In contrast, iron meteorites show δ⁶⁵Cu approximately 2.3‰ variations. Different groups of iron meteorites have distinct δ⁶⁵Cu values. Nonmagmatic IAB‐IIICD iron meteorites have similar δ⁶⁵Cu (0.03 ± 0.08 and 0.12 ± 0.10, respectively), close to terrestrial values (approximately 0). The other group of nonmagmatic irons, IIE, is isotopically distinct (?0.69 ± 0.15). IVB is the iron meteorite group with the strongest elemental depletion in Cu and samples in this group are enriched in the lighter isotope (δ⁶⁵Cu down to ?2.26‰). Evaporation should have produced an enrichment in ⁶⁵Cu over ⁶³Cu (δ⁶⁵Cu >0) and can therefore be ruled out as a mechanism for volatile loss in IVB meteorites. In silicate‐bearing iron meteorites, Δ¹⁷O correlates with δ⁶⁵Cu. This correlation between nonmass‐dependent and mass‐dependent parameters suggests that the Cu isotopic composition of iron meteorites has not been modified by planetary differentiation to a large extent. Therefore, Cu isotopic ratios can be used to confirm genetic links. Cu isotopes thus confirm genetic relationships between groups of iron meteorites (e.g., IAB and IIICD; IIIE and IIIAB); and between iron meteorites and chondrites (e.g., IIE and H chondrites). Several genetic connections between iron meteorites groups are confirmed by Cu isotopes, (e.g., IAB and IIICD; IIIE and IIIAB); and between iron meteorites and chondrites (e.g., IIE and H chondrites).     

Exposure history of lunar meteorites Queen Alexandra Range 93069 and 94269

Abstract— Cosmic-ray produced ¹⁴C (t_1/2 = 5730 years), ³⁶Cl (3.01 × 10⁵ years), ²⁶Al (7.05 × 10⁵ years), and ¹⁰Be (1.5 × 10⁶ years) in the recently discovered lunar meteorites Queen Alexandra Range 93069 (QUE 93069) and 94269 (QUE 94269) were measured by accelerator mass spectrometry. The abundance pattern of these four cosmogenic radionuclides and of noble gases indicates QUE 93069 and QUE 94269 were a paired fall and were exposed to cosmic rays near the surface of the Moon for at least several hundred million years before ejection. After the meteorite was launched from the Moon, where it had resided at a depth of 65–80 g/cm², it experienced a short transition time, ～20–50 ka, before colliding with the Earth. The terrestrial age of the meteorite is 5–10 ka. Comparison of the cosmogenic nuclide concentrations in QUE 93069/94269 and MAC 88104/88105 clearly shows that these meteorites were not ejected by a common event from the Moon.     

The chlorine isotope composition of iron meteorites: Evidence for the Cl isotope composition of the solar nebula and implications for extensive devolatilization during planet formation

The bulk chlorine concentrations and isotopic compositions of a suite of non‐carbonaceous (NC) and carbonaceous (CC) iron meteorites were measured using gas source mass spectrometry. The δ³⁷Cl values of magmatic irons range from ?7.2 to 18.0‰ versus standard mean ocean chloride and are unrelated to their chlorine concentrations, which range from 0.3 to 161 ppm. Nonmagmatic IAB irons are comparatively Cl‐rich containing >161 ppm with δ³⁷Cl values ranging from ?6.1 to ?3.2‰. The anomalously high and low δ³⁷Cl values are inconsistent with a terrestrial source, and as Cl contents in magmatic irons are largely consistent with derivation from a chondrite‐like silicate complement, we suggest that Cl is indigenous to iron meteorites. Two NC irons, Cape York and Gibeon, have high cooling rates with anomalously high δ³⁷Cl values of 13.4 and 18.0‰. We interpret these high isotopic compositions to result from Cl degassing during the disruption of their parent bodies, consistent with their low volatile contents (Ga, Ge, Ag). As no relevant mechanisms in iron meteorite parent bodies are expected to decrease δ³⁷Cl values, whereas volatilization is known to increase δ³⁷Cl values by the preferential loss of light isotopes, we interpret the low isotope values of <?5‰ and down to ?7.2‰ to most closely represent the primordial isotopic composition of Cl in the solar nebula. Similar conclusions have been derived from low δ³⁷Cl values down to ?6, and ?3.8‰ measured in Martian and Vestan meteorites, respectively. These low δ³⁷Cl values are in contrast to those of chondrites which average around 0‰ previously explained by the incorporation of isotopically heavy HCl clathrate into chondrite parent bodies. The poor retention of low δ³⁷Cl values in many differentiated planetary materials suggest that extensive devolatilization occurred during planet formation, which can explain Earth's high δ³⁷Cl value by the loss of approximately 60% of the initial Cl content.