The microbiology of spacecraft hardware: lessons learned from the planetary protection activities on the Beagle 2 spacecraft.

We consider the aseptic assembly of the Beagle 2 Mars probe and how the requirements of COSPAR planetary protection category IVa were achieved. Several areas for future investigation became apparent. An ESA mission is outlined in which a microbial bioburden is recovered after Earth orbit to assess viability following re-entry through the atmosphere.

A technique for the determination of 18O/16O and 17O/16O isotopic ratios in water from small liquid and solid samples.

We have developed a new technique in which a solid reagent, cobalt(III) fluoride, is used to prepare oxygen gas for isotope ratio measurement from water derived either from direct injection or from the pyrolysis of solid samples. The technique uses continuous flow, isotope ratio monitoring, gas chromatography/mass spectrometry (irmGC/MS) to measure the delta18O and delta17O of the oxygen gas. Water from appropriate samples is evolved by a procedure of stepped pyrolysis (0-1000 degrees C, typically in 50 degrees C increments) under a flowing stream of helium carrier gas. The method has considerable advantages over others used for water analysis in that it is quick; requires only small samples, typically 1-50 mg of whole rock samples (corresponding to approximately 0.2 micromol of H2O); and the reagent is easy and safe to handle. Reproducibility in isotope ratio measurement obtained from pyrolysis of samples of a terrestrial solid standard are delta18O +/- 0.54, delta17O +/- 0.33, and delta17O +/- 0.10/1000, 1sigma in all cases. The technique was developed primarily for the analysis of meteorites, and the efficiency of the method is illustrated herein by results from water standards, solid reference materials, and a sample of the Murchison CM2 meteorite.

Beagle 2: a proposed exobiology lander for ESA's 2003 Mars Express mission.

The aim of the proposed Beagle 2 small lander for ESA's 2003 Mars Express mission is to search for organic material on and below the surface of Mars and to study the inorganic chemistry and mineralogy of the landing site. The lander will have a total mass of 60kg including entry, descent, and landing system. Experiments will be deployed on the surface using a robotic arm. It will use a mechanical mole and grinder to obtain samples from below the surface, under rocks, and inside rocks. Sample analysis by a mass spectrometer will include isotopic analysis. An optical microscope, an X-ray spectrometer and a Mossbauer spectrometer will conduct in-situ rock studies.

Life on Mars: chemical arguments and clues from Martian meteorites.

Primitive terrestrial life-defined as a chemical system able to transfer its molecular information via self-replication and to evolve-probably originated from the evolution of reduced organic molecules in liquid water. Several sources have been proposed for the prebiotic organic molecules: terrestrial primitive atmosphere (methane or carbon dioxide), deep-sea hydrothermal systems, and extraterrestrial meteoritic and cometary dust grains. The study of carbonaceous chondrites, which contain up to 5% by weight of organic matter, has allowed close examination of the delivery of extraterrestrial organic material. Eight proteinaceous amino acids have been identified in the Murchison meteorite among more than 70 amino acids. Engel reported that L-alanine was surprisingly more abundant than D-alanine in the Murchison meteorite. Cronin also found excesses of L-enantiomers for nonprotein amino acids. A large collection of micrometeorites has been recently extracted from Antarctic old blue ice. In the 50- to 100-micron size range, carbonaceous micrometeorites represent 80% of the samples and contain 2% of carbon, on average. They might have brought more carbon than that involved in the present surficial biomass. The early histories of Mars and Earth clearly show similarities. Liquid water was once stable on the surface of Mars, attesting the presence of an atmosphere capable of deccelerating C-rich micrometeorites. Therefore, primitive life may have developed on Mars as well and fossilized microorganisms may still be present in the near subsurface. The Viking missions to Mars in 1976 did not find evidence of either contemporary or past life, but the mass spectrometer on the lander aeroshell determined the atmospheric composition, which has allowed a family of meteorites to be identified as Martian. Although these samples are essentially volcanic in origin, it has been recognized that some of them contain carbonate inclusions and even veins that have a carbon isotopic composition indicative of an origin from Martian atmospheric carbon dioxide. The oxygen isotopic composition of these carbonate deposits allows calculation of the temperature regime existing during formation from a fluid that dissolved the carbon dioxide. As the composition of the fluid is unknown, only a temperature range can be estimated, but this falls between 0 degree and 90 degrees C, which would seem entirely appropriate for life processes. It was such carbonate veins that were found to host putative microfossils. Irrespective of the existence of features that could be considered to be fossils, carbonate-rich portions of Martian meteorites tend to have material, at more than 1000 ppm, that combusts at a low temperature; i.e., it is an organic form of carbon. Unfortunately, this organic matter does not have a diagnostic isotopic signature so it cannot be unambiguously said to be indigenous to the samples. However, many circumstantial arguments can be made to the effect that it is cogenetic with the carbonate and hence Martian. If it could be proved that the organic matter was preterrestrial, then the isotopic fractionation between it and the carbon is in the right sense for a biological origin.

C, N, and noble gas isotopes in grain size separates of presolar diamonds from Efremovka.

Nanometer-size presolar diamonds from the Efremovka CV3 chondrite were physically separated into several grain size fractions by ultracentrifugation. The coarsest size fraction is the most enriched in carbon-12; the others have broadly similar carbon isotopic compositions. Measurement of noble gases shows that their concentration decreases with decreasing grain size. This effect is attributed to ion implantation. Such an episode could occur in the envelope of a supernova that produced the diamonds, or in interstellar space; in either case, ions with energies above a certain threshold pass completely through the smaller diamond grains without being captured. Concentrations of nitrogen show only minor variations with grain size, indicating a different mechanism of incorporation into the diamonds.

The origin of chondritic macromolecular organic matter: a carbon and nitrogen isotope study.

The N and C abundances and isotopic compositions of acid-insoluble carbonaceous material in thirteen primitive chondrites (five unequilibrated ordinary chondrites, three CM chondrites, three enstatite chondrites, a CI chondrite and a CR chondrite) have been measured by stepped combustion. While the range of C isotopic compositions observed is only delta 13C = 30%, the N isotopes range from delta 15N approximately -40 to 260%. After correction for metamorphism, presolar nanodiamonds appear to have made up a fairly constant 3-4 wt% of the insoluble C in all the chondrites studied. The apparently similar initial presolar nanodiamond to organic C ratios, and the correlations of elemental and isotopic compositions with metamorphic indicators in the ordinary and enstatite chondrites, suggest that the chondrites all accreted similar organic material. This original material probably most closely resembles that now found in Renazzo and Semarkona. These two meteorites have almost M-shaped N isotope release profiles that can be explained most simply by the super-position of two components, one with a composition between delta 15N = -20 and -40% and a narrow combustion interval, the other having a broader release profile and a composition of delta 15N approximately 260%. Although isotopically more subdued, the CI and the three CM chondrites all appear to show vestiges of this M-shaped profile. How and where the components in the acid-insoluble organics formed remains poorly constrained. The small variation in nanodiamond to organic C ratio between the chondrite groups limits the local synthesis of organic matter in the various chondrite formation regions to at most 30%. The most 15N-rich material probably formed in the interstellar medium, and the fraction of organic N in Renazzo in this material ranges from 40 to 70%. The isotopically light component may have formed in the solar system, but the limited range in nanodiamond to total organic C ratios in the chondrite groups is consistent with most of the organic material being, presolar.

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

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] approximately 0.34 ppm; delta 15N approximately +23%); although during stepped combustion, 15N-enriched N (delta 15N approximately +143%) is released in a narrow temperature interval between 700 degrees C and 800 degrees C (along with 13C-enriched C (delta 13C approximately +19%) and 40Ar). Cosmogenic species are found to be negligible at this temperature; thus, the isotopically heavy component is identified, in part, as Martian atmospheric gas trapped relatively recently in the history of ALH84001. The N and Ar data show that ALH84001 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 palaeoatmosphere 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: delta 15N > or = +200%, 40Ar/36Ar < or = 3000 and 36Ar/14N > or = 17 x 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.

Record of fluid-rock interactions on Mars from the meteorite ALH84001.

Allan Hills (ALH) 84001 is the most recently recognized member of a suite of meteorites--the SNCs--that almost certainly originated on Mars. Several factors distinguish ALH84001 from the other SNC meteorites. Preliminary studies suggest that it may be older than other martian meteorites. Moreover, it contains abundant, zoned domains of calcium-iron-magnesium carbonate that are indigenous to the sample and thus may hold important clues regarding near-surface processes on Mars and the evolution of the martian atmosphere. We report here analyses of the carbon and oxygen stable-isotope compositions of the carbonates that place constraints on their formation conditions. Our results imply the presence of at least two chemically distinct carbonates--one Ca,Fe-rich, the other Mg-rich--that are enriched in 13C relative to terrestrial carbonates (delta 13C approximately +41/1000), consistent with martian atmospheric CO2 as the carbon source. The oxygen isotope compositions of the carbonates indicate that they precipitated from a low-temperature fluid in the martian crust. Combined with textural and bulk geochemical considerations, the isotope data suggest that carbonate deposition took place in an open-system environment in which the ambient temperature fluctuated.

Terrestrial carbon and nitrogen isotopic ratios from cretaceous-tertiary boundary nanodiamonds.

One hypothesis for the origin of the nanometer-size diamonds found at the Cretaceous-Tertiary (K-T) boundary is that they are relict interstellar diamond grains carried by a postulated asteroid. The (13)C/(12)C and (15)N/(14)N ratios of the diamonds from two sites in North America, however, show that the diamonds are two component mixtures differing in carbon and nitrogen isotopic composition and nitrogen abundance. Samples from a site from Italy show no evidence for either diamond component. All the isotopic signatures obtained from the K-T boundary are material well distinguished from known meteoritic diamonds, particularly the fine-grain interstellar diamonds that are abundant in primitive chondrites. The K-T diamonds were most likely produced during the impact of the asteroid with Earth or in a plasma resulting from the associated fireball.

A new type of meteoritic diamond in the enstatite chondrite abee.

Diamonds with delta(13)C values of -2 per mil and less than 50 parts per million (by mass) nitrogen have been isolated from the Abee enstatite chondrite by the same procedure used for concentrating Cdelta, the putative interstellar diamond found ubiquitously in primitive meteorites and characterized by delta(13)C values of -32 to -38 per mil, nitrogen concentrations of 2,000 to 12,500 parts per million, and delta(15)N values of -340 per mil. Because the Abee diamonds have typical solar system isotopic compositions for carbon, nitrogen, and xenon, they are presumably nebular in origin rather than presolar. Their discovery in an unshocked meteorite eliminates the possibility of origins normally invoked to account for diamonds in ureilites and iron meteorites and suggests a low-pressure synthesis. The diamond crystals are approximately 100 nanometers in size, are of an unusual lath shape, and represent approximately 100 parts per million of Abee by mass.

Evidence for multiple sources of diamond from primitive chondrites.

Fine-grained diamonds, the most abundant form of circumstellar dust isolated from primitive meteorites, have elemental and isotopic characteristics that are dependent on the host meteorite type. Carbon isotopic compositions vary from -32 to -38 per mil, and nitrogen associated with the diamond changes in overall abundance by over a factor of four from 0.2 to 0.9 weight percent, between ordinary and CM2-type chondrites. Although the ratio of carbon to nitrogen evolves in a distinctive way during combustion of diamond separates, metamorphic degassing of nitrogen is not the main cause of the differences in nitrogen content. The data suggest that intrinsic differences must have been inherited by the diamonds at the time of their formation and that the diamonds were distributed heterogeneously in the solar nebula during condensation. However, the hypothesis that a distinct nitrogen carrier remains hidden within the diamond cannot be ruled out.

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.

Isotopic analysis of nesquehonite recovered from the surface of the LEW 85320 H5 ordinary chondrite shows that the delta 13C and delta 18O values of the two generations of bicarbonate (Antarctic and Texas) are different: delta 13C = +7.9% and +4.2%; delta 18O = +17.9% and 12.1% respectively. Carbon isotopic compositions are consistent with equilibrium formation from atmospheric carbon dioxide at -2 +/- 4 degrees C (Antarctic) and +16 +/- 4 degrees 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 delta 13C values have been identified in the SNC meteorites EETA 79001 and Nakhla, petrographic and temperature constraints argue against their simply being terrestrial weathering products.

Interstellar carbon in meteorites.

The Murchison and Allende chondrites contain up to 5 parts per million carbon that is enriched in carbon-13 by up to + 1100 per mil (the ratio of carbon-12 to carbon-13 is approximately 42, compared to 88 to 93 for terrestrial carbon). This "heavy" carbon is associated with neon-22 and with anomalous krypton and xenon showing the signature of the s-process (neutron capture on a slow time scale). It apparently represents interstellar grains ejected from late-type stars. A second anomalous xenon component ("CCFXe") is associated with a distinctive, light carbon (depleted in carbon-13 by 38 per mil), which, however, falls within the terrestrial range and hence may be of either local or exotic origin.

Organic analysis of the returned lunar sample.

Lunar fines have been examined for organic compounds by crushing, programmed heating, hydrofluoric acid etching, and solvent extraction. Products were examined by mass spectroscopy. A variety of small organic molecules, including methane and other hydrocarbons, accompanied the release of the rare gases when the sample was heated in a stepwise fashion to 900 degrees C under vacuum. Methane is more abundant (abundance on the order of 1 part per million) than argon in the matrix-entrapped gases liberated by hydrofluoric acid etching of lunar fines. Methane is also present in a dark portion of the gas-rich meteorite Kapoeta.