The Molecular Record of Metabolic Activity in the Subsurface of the Río Tinto Mars Analog.

In the subsurface, the interplay between microbial communities and the surrounding mineral substrate, potentially used as an energy source, results in different mineralized structures. The molecular composition of such structures can record and preserve information about the metabolic pathways that have produced them. To characterize the molecular composition of the subsurface biosphere, we have analyzed some core samples by time-of-flight secondary ion mass spectrometry (ToF-SIMS) that were collected in the borehole BH8 during the operations of the Mars Analog and Technology Experiment (MARTE) project. The molecular analysis at a micron-scale mapped the occurrence of several inorganic complexes bearing PO3-, SOx(2 to 4)-, NOx(2,3)-, FeOx(1,2)-, SiO2-, and Cl-. Their distribution correlates with organic molecules that were tentatively assigned to saturated and monounsaturated fatty acids, polyunsaturated fatty acids, saccharides, phospholipids, sphingolipids, and potential peptide fragments. SOx- appear to be mineralizing some microstructures larger than 25 microns, which have branched morphologies, and that source SO3-bearing adducts. PO3-rich compounds occur in two different groups of microstructures which size, morphology, and composition are different. While a group of >40-micron sized circular micronodules lacks organic compounds, an ovoidal microstructure is associated with m/z of other lipids. The NO2-/NO3- and Cl- ions occur as small microstructure clusters (<20 microns), but their distribution is dissimilar to the mineralized microstructures bearing PO3-, and SO3-. However, they have a higher density in areas with more significant enrichment in iron oxides that are traced by different Fe-bearing anions like FeO2-. The distribution of the organic and inorganic negative ions, which we suggest, resulted from the preservation of at least three microbial consortia (PO4--, and NO2--/NO3--mineralizers PO4-lipid bearing microstructures), would have resulted from different metabolic and preservation pathways.

Coupled Si and O isotope measurements of meteoritic material by laser fluorination isotope ratio mass spectrometry.

We present a procedure for the determination of the isotopic ratios of silicon and oxygen from the same aliquot of anhydrous silicate material. The sample is placed in a bromine pentafluoride atmosphere as it is heated with a CO2 laser system releasing silicon tetrafluoride and oxygen gasses. The oxygen gas is then purified to remove other reaction by-products through several liquid nitrogen traps before being captured onto a molecular sieve and transferred to an isotope ratio mass spectrometer. The silicon tetrafluoride gas is then purified using a supplementary line by repeatedly freezing to -196°C with liquid nitrogen and then thawing with an ethanol slurry at -110°C through a series of metal and Pyrex traps. The purified gas is then condensed into a Pyrex sample tube before it is transferred to an isotope ratio mass spectrometer for silicon isotope ratio measurements. This system has silicon yields of greater than 90% for pure quartz, olivine, and garnet standards and has a reproducibility of ±0.1‰ (2σ) for pure quartz for both oxygen and silicon isotope measurements. Meteoritic samples were also successfully analyzed to demonstrate this system's ability to measure the isotopic ratio composition of bulk powders with precision. This unique technique allows for the fluorination of planetary material without the need for wet chemistry. Though designed to analyze small aliquots of meteoritic material (1.5 to 3 mg), this approach can also be used to investigate refractory terrestrial samples where traditional fluorination is not suitable.

Evidence for methane in Martian meteorites.

The putative occurrence of methane in the Martian atmosphere has had a major influence on the exploration of Mars, especially by the implication of active biology. The occurrence has not been borne out by measurements of atmosphere by the MSL rover Curiosity but, as on Earth, methane on Mars is most likely in the subsurface of the crust. Serpentinization of olivine-bearing rocks, to yield hydrogen that may further react with carbon-bearing species, has been widely invoked as a source of methane on Mars, but this possibility has not hitherto been tested. Here we show that some Martian meteorites, representing basic igneous rocks, liberate a methane-rich volatile component on crushing. The occurrence of methane in Martian rock samples adds strong weight to models whereby any life on Mars is/was likely to be resident in a subsurface habitat, where methane could be a source of energy and carbon for microbial activity.

Weathering of post-impact hydrothermal deposits from the Haughton impact structure: implications for microbial colonization and biosignature preservation.

Meteorite impacts are among the very few processes common to all planetary bodies with solid surfaces. Among the effects of impact on water-bearing targets is the formation of post-impact hydrothermal systems and associated mineral deposits. The Haughton impact structure (Devon Island, Nunavut, Canada, 75.2 °N, 89.5 °W) hosts a variety of hydrothermal mineral deposits that preserve assemblages of primary hydrothermal minerals commonly associated with secondary oxidative/hydrous weathering products. Hydrothermal mineral deposits at Haughton include intra-breccia calcite-marcasite vugs, small intra-breccia calcite or quartz vugs, intra-breccia gypsum megacryst vugs, hydrothermal pipe structures and associated surface "gossans," banded Fe-oxyhydroxide deposits, and calcite and quartz veins and coatings in shattered target rocks. Of particular importance are sulfide-rich deposits and their associated assemblage of weathering products. Hydrothermal mineral assemblages were characterized structurally, texturally, and geochemically with X-ray diffraction, micro X-ray diffraction, optical and electron microscopy, and inductively coupled plasma atomic emission spectroscopy. Primary sulfides (marcasite and pyrite) are commonly associated with alteration minerals, including jarosite (K,Na,H(3)O)Fe(3)(SO(4))(2)(OH)(6), rozenite FeSO(4)·4(H(2)O), copiapite (Fe,Mg)Fe(4)(SO(4))(6)(OH)(2)·20(H(2)O), fibroferrite Fe(SO(4))(OH)·5(H(2)O), melanterite FeSO(4)·7(H(2)O), szomolnokite FeSO(4)·H(2)O, goethite α-FeO(OH), lepidocrocite γ-FeO(OH) and ferrihydrite Fe(2)O(3)·0.5(H(2)O). These alteration assemblages are consistent with geochemical conditions that were locally very different from the predominantly circumneutral, carbonate-buffered environment at Haughton. Mineral assemblages associated with primary hydrothermal activity, and the weathering products of such deposits, provide constraints on possible microbial activity in the post-impact environment. The initial period of active hydrothermal circulation produced primary mineral assemblages, including Fe sulfides, and was succeeded by a period dominated by oxidation and low-temperature hydration of primary minerals by surface waters. Active hydrothermal circulation can enable the rapid delivery of nutrients to microbes. Nutrient availability following the cessation of hydrothermal circulation is likely more restricted; therefore, the biological importance of chemical energy from hydrothermal mineral deposits increases with time. Weathering of primary hydrothermal deposits and dissolution and reprecipitation of mobile weathering products also create many potential habitats for endolithic microbes. They also provide a mechanism that may preserve biological materials, potentially over geological timescales.

Drilling to gabbro in intact ocean crust.

Sampling an intact sequence of oceanic crust through lavas, dikes, and gabbros is necessary to advance the understanding of the formation and evolution of crust formed at mid-ocean ridges, but it has been an elusive goal of scientific ocean drilling for decades. Recent drilling in the eastern Pacific Ocean in Hole 1256D reached gabbro within seismic layer 2, 1157 meters into crust formed at a superfast spreading rate. The gabbros are the crystallized melt lenses that formed beneath a mid-ocean ridge. The depth at which gabbro was reached confirms predictions extrapolated from seismic experiments at modern mid-ocean ridges: Melt lenses occur at shallower depths at faster spreading rates. The gabbros intrude metamorphosed sheeted dikes and have compositions similar to the overlying lavas, precluding formation of the cumulate lower oceanic crust from melt lenses so far penetrated by Hole 1256D.

Early life recorded in archean pillow lavas.

Pillow lava rims from the Mesoarchean Barberton Greenstone Belt in South Africa contain micrometer-scale mineralized tubes that provide evidence of submarine microbial activity during the early history of Earth. The tubes formed during microbial etching of glass along fractures, as seen in pillow lavas from recent oceanic crust. The margins of the tubes contain organic carbon, and many of the pillow rims exhibit isotopically light bulk-rock carbonate delta13C values, supporting their biogenic origin. Overlapping metamorphic and magmatic dates from the pillow lavas suggest that microbial life colonized these subaqueous volcanic rocks soon after their eruption almost 3.5 billion years ago.