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Desmarais, D. J.

Publications and source records attributed to Desmarais, D. J..

Exopaleontology and the search for a fossil record on Mars

Although present Martian surface conditions appear unfavorable for life as we know it, there is compelling geological evidence that the climate of early Mars was much more Earth-like, with a denser atmosphere and abundant surface water. The fact that life developed on the Earth within the first billion years of its history makes it quite plausible that life may have also developed on Mars. If life did develop on Mars, it is likely to have left behind a fossil record. This has led to the development of a new subdiscipline of paleontology, herein termed 'exopaleontology', which deals with the exploration for fossils on other planets. The most important factor enhancing microbial fossilization is the rapid entombment of microorganisms by fine-grained, stable mineral phases, such as silica, phosphate, or carbonate. The oldest body fossils on Earth are preserved in this way, occurring as permineralized cells in fine-grained siliceous sediments (cherts) associated with ancient volcanic terranes in Australia and South Africa. Modern terrestrial environments where minerals may precipitate in the presence of microorganisms include subaerial thermal springs and shallow hydrothermal systems, sub-lacustrine springs and evaporitic alkaline lakes, zones of mineralization within soils where 'hardpans' (e.g. calcretes, silcretes) form, and high latitude frozen soils or ground ice.

Farmer, Jack D.↗

Isotopic composition of Murchison organic compounds: Intramolecular carbon isotope fractionation of acetic acid. Simulation studies of cosmochemical organic syntheses

Recently, in our laboratories, samples of Murchison acetic acid were decarboxylated successfully and the carbon isotopic composition was measured for the methane released by this procedure. These analyses showed significant differences in C-13/C-12 ratios for the methyl and carboxyl carbons of the acetic acid molecule, strongly suggesting that more than one carbon source may be involved in the synthesis of the Murchison organic compounds. On the basis of this finding, laboratory model systems simulating cosmochemical synthesis are being studied, especially those processes capable of involving two or more starting carbon sources.

Yuen, G. U.↗

The biogeochemistry of microbial mats, stromatolites and the ancient biosphere

Stromatolites offer an unparalleled geologic record of early life, because they constitute the oldest and most abundant recognizable remains of microbial ecosystems. Microbial mats are living homologs of stromatolites; thus, the physiology of the microbiota as well as the processes which create those features of mats (e.g., biomarker organic compounds, elemental and stable isotopic compositions) which are preserved in the ancient record. Observations of the carbon isotopic composition (delta C-13) of stromatolites and microbial mats were made and are consistent with the hypothesis that atmospheric CO2 concentrations have declined by at least one to two orders of magnitude during the past 2.5 Ga. Whereas delta C-13 values of carbonate carbon average about 0 permil during both the early and mid-Proterozoic, the delta C-13 values of stromatolitic organic matter increase from an average of -35 between 2.0 and 2.6 Ga ago to an average of about -28 about 1.0 Ga ago. Modern microbial mats in hypersaline environments have delta C-13 values typically in the range of -5 to -9, relative to an inorganic bicarbonate source at 0 permil. Both microbial mats and pur cultures of cyanobacteria grown in waters in near equilibrium with current atmospheric CO2 levels exhibit minimal discrimination against C-13. In contrast, hot spring cyanobacterial mats or cyanobacterial cultures grown under higher CO2 levels exhibit substantially greater discrimination. If care is taken to compare modern mats with stromatolites from comparable environments, it might be possible to estimate ancient levels of atmospheric CO2. In modern microbial mats, a tight coupling exists between photosynthetic organic carbon production and subsequent carbon oxidation, mostly by sulfate reduction. The rate of one process fuels a high rate of the other, with much of the sulfate reduction occurring within the same depth interval as oxygenic photosynthesis. Other aspects of this study are presented.

Desmarais, D. J.↗

Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

Yuen, G. U.↗

Organic S13C values vary slightly with salinity in microbial mats at Guerrero Negro, Baja California Sur, Mexico: Implications for stromatolite S13C values

Stromatolites, layered sedimentary rock structures produced by communities of microorganisms, constitute the most abundant early evidence of life on Earth. Microbial mats, which are found most frequently in hypersaline marine or hot spring environments, serve as useful modern analogs of stromatolitic communities. Biochemical studies of mats were conducted to assist in the interpretations of stromatolites. The data suggest that salinity effects are insufficient by themselves to cause the C-13 differences observed betwwen Precambrain stromatolites and modern microbial mats.

Desmarais, D. J.↗

The carbon isotope biogeochemistry of the individual hydrocarbons in bat guano and the ecology of insectivorous bats in the region of Carlsbad, New Mexico

The structures and C-13 contents of individual alkanes extracted from bat guano found in the Carlsbad region of New Mexico can be related to both the photosynthetic pathways of the local plants and the feeding habits of the insects that support the bats. Carbon isotopic analyses of the 62 most important plant species in the Pecos River Valley, the most significant feeding area for the Carlsbad bats, reveal the presence of 29 species with C3 photosynthesis and 33 species, mostly grasses, with C4 photosynthesis. Although the abundances of nonagricultural C3 and C4 plants are similar, alfalfa and cotton, both C3 plants, constitute over 95 per cent of the crop biomass. The molecular composition of the bat guano hydrocarbons is fully consistent with an insect origin. Two isotopically distinct groups of insect branched alkanes were discerned. These two groups of alkanes derived from two chemotaxonomically distinct populations of insects possessing distinctly different feeding habits. It is likely that one population grazes predominantly on crops whereas the other population prefers native vegetation. This and other isotopic evidence supports the notion that crop pests constitute a major percentage of the bats' diet.

Desmarais, D. J.↗

Light element geochemistry of the Apollo 12 site

Analytical techniques of improved sensitivity have revealed details of the concentrations and isotopic compositions of light elements for a comprehensive suite of samples from the Apollo 12 regolith. These samples show a wide spread in maturity, although maximum contents observed for solar wind elements are less than observed at other sites, possibly reflecting relative recency of craters at the Apollo 12 site. Isotopic composition of nitrogen is consistent with the idea that N-15/N-14 in the solar wind has increased with time, at least a major part of this increase having occurred in the past 3.1 Gyr. Sulfur isotope systematics support a model in which sulfur is both added to the regolith, by meteoritic influx, and lost, by an isotopically selective process. Most soils from this site are heavily contaminated with terrestrial carbon.

Kerridge, J. F.↗

Evolution of carbon isotopes, agglutinates, and the lunar regolith

Apollo 17 light-mantle soils and Apollo 15 Apennine Front soils are compared with respect to isotopic enrichment of C-13 and the maturity of the site. Analyses of soil-size fractions indicate that while the carbon concentration on particle surfaces remains relatively constant with increasing soil maturity, total surface-correlated carbon increases due to increasing total soil surface area. The role of agglutinates in the incorporation of surface-correlated carbon into aggregate grains is examined; agglutinates contain a major percentage of the carbon found in mature soil, and the volume-correlated carbon component in agglutinates apparently continues to increase after the surface-correlated carbon concentrations have reached a constant value. Constraints that may limit the carbon concentration in lunar soils to a value not greater than 300 micrograms/g are considered.

Desmarais, D. J.↗

The distribution in lunar soil of hydrogen released by pyrolysis

The hydrogen contents of various Apollo 15 rocks and Apollo 15 and 16 soil particle types and sieve fractions have been determined by the pyrolysis method. The Apollo 15 crystalline rocks analyzed release very little hydrogen (approximately 6 micromoles H/g sample). The mineral, glass, and light-colored breccia fragments in the soils contain approximately 5, 30, and 10 micromoles H/g sample, respectively. The dark breccias and glassy agglutinates examined have much higher hydrogen contents (60 and 110 micromoles H/g sample). For soil particle diameters less than 105 microns, hydrogen content increases linearly with particle surface area per particle mass. The calculated grain surface average concentrations of hydrogen in the Apollo 15 and 16 soils fall short of experimentally determined saturation values by a factor of 20. The volume-correlated component of hydrogen in a soil increases with the maturity of the soil.

Desmarais, D. J.↗

Techniques for the analysis of gases sequentially released from lunar samples

Description of two methods for the analysis of light gases that are sequentially evolved from 2 to 10 mg of lunar sample. A hydrofluoric acid hydrolysis of lunar material is achieved by repeated exposure of the sample to hydrogen fluoride. In the second technique, gases are evolved from lunar samples by the stepwise heating of these samples to 1400 C. The gases evolved by either hydrolysis or pyrolysis are analyzed in a gas chromatographic system using a helium ionization detector. The sensitivities of this detector for the gases, as analyzed, range from 20 picograms/sec for hydrogen to 0.2 picogram/sec for carbon dioxide.

Desmarais, D. J.↗

The distribution in lunar soil of carbon released by pyrolysis

The carbon contents of various lunar soil particle types and sieve fractions of Apollo 15 and 16 samples have been determined by the pyrolysis method. The mineral, glass, and high-grade breccia fragments in the soils examined contain relatively low amounts of carbon (approximately 8, 25, and 25 microg C/g sample respectively in 149-250 micron grains). Most low-grade breccias and all agglutinates examined have high carbon contents (approximately 52 and 80 microg C/g sample respectively), and agglutinate abundance is indicative of the carbon content and maturity of a soil. The distribution of carbon with respect to particle size in mature soils generally reveals a minimum in carbon content at about 100 micron particle diameter. At smaller particle diameters, carbon content is directly proportional to particle surface area and therefore increases with the ratio (surface area)/(particle mass). A model relating the cycle of comminution and aggregation of soil particles to the redistribution of surface implanted carbon is developed.

Desmarais, D. J.↗