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PubMed1975

Search for amino acids in Apollo returned lunar soil.

The lunar samples from Apollo flights 11 through 17 provided the students of chemical evolution with an opportunity of examining extraterrestrial materials for evidence of early prebiological chemistry in the solar system. Our search was directed to water-extractable compounds with emphasis on amino acids. Gas chromatography, ion-exchange chromatography and gas chromatography combined with mass spectrometry were used for the analysis. It is our conclusion that amino acids are not present in the lunar regolith above the background levels of our investigations.

Amino Acids↗
PubMed1975

High pH ammonia toxicity, and the search for life on the Jovian planets.

Jovian plants have enviroments apparently suitable for the evolution of life, but nevertheless, present severe challenges to organisms. One such challenge arises from the presence of ammonia. Ammonia is an efficient biocide, its effect being dependent on pH as well as on concentration. The effects of pH and ammonia concentration were studied separately, where possible, on a variety of organisms, including some isolated from natural enviornments of high pH and/or ammonia concentration. Escherichia coli and Bacillus subtilis are both extremely sensitive to ammonia. An aerobic organism (growth up to pH 11.4) from an alkaline spring is more resistant, but exhibits a toxic response to ammonia at a pH much lower than its maximum for growth. The greatest ammonia resistance has been found in an unidentified organism growing at near neutral pH. Even in this case, however, survival at ammonia concentrations reasonably expected on the Jovian planets is measured in hours. This is, nevertheless, two to three orders of magnitude longer than for E. coli. Our data support the tentative conclusion that contamination of the Jovian planets with terrestrial organisms that can grow is unlikely. However, the range of toxic response noted, coupled with the observation that terrestrial life has not been exposed to high ammonia concentrations for millions of years, suggests that adaptation to greater ammonia tolerance may be possible.

Ammonia↗
PubMed1978

The Viking biological investigations: review and status.

The three experimental approaches incorporated into the Viking biology instrument have yielded results that are most readily explained as nonbiological phenomena. The predominant view among investigators trying to simulate the Mars results is that the surface material of Mars contains strongly oxidizing compounds which would account for many of the more intense reactions seen on Mars. Other mechanisms are also currently being proposed and studied.

Chemical Phenomena↗
PubMed1979

Solar-driven chemical energy source for a Martian biota.

Microorganisms deep in the Martian soil could derive energy indirectly from the sun via chemical reactions involving atmospheric products of the solar ultraviolet flux. The Viking discovery of a chemically uniform regolith which, though poor in organics, is rich in sulfur-containing compounds suggests reaction sequences in which sulfur is recycled through reduced and oxidized states by biologically catalyzed reactions with photochemically-produced atmospheric constituents. One candidate reaction, reduction of soil ssufate minerals by molecular hydrogen, is already exploited on earth by bacteria of the ubiquitous and tenacious Desulfovibrio genus.

Desulfovibrio↗
PubMed1979

Some comments on interpretations of Viking biological experiments.

Data from Viking experiments are analyzed from a biological viewpoint. The lack of organic matter in Martian soil could be due to the specificity of regions with optimal landing conditions. All data of labeled release experiments may be explained by assuming the existence of psychrophilic organisms, cultivated at temperatures above optimal ones, and other factors of a biological origin. The biological interpretation does not contradict the results of other life search experiments.

Carbon Dioxide↗
PubMed1975

The temperature dependences of some types of gaseous ionic reactions of astrochemical interest.

The rate constants of ion-molecule reactions which are of potential significance in astrochemical systems are found to exhibit significant, and in many cases, negative temperature dependences. The rate constants of fast ion-polar molecule reactions (e.g., XH+ + B leads to BH+ + X) may increase by a factor of 5-10 between 1000 and 10D. Slow reactions that proceed via reaction complexes (e.g., H- transfer and association reactions) often exhibit temperature dependences of the form k = AT-n, n = 1-5. Both transition state theory considerations and the coupled-oscillator RRK-type model are seen to be able to account qualitatively for the behavior of slow ion-molecule reactions.

Chemical Phenomena↗
PubMed1975

Fluorescence detection of organic molecules in the Jovian atmosphere.

A search for fluorescent emission due to the presence of possible organic molecules in the Jovian atmosphere is described. We first consider natural Jovian fluorescent emission excited by precipitating auroral particles. Due to our lack of knowledge of the Jovian precipitation particle energies and fluxes we next consider fluorescent emission excited by a laser system aboard a Jupiter spacecraft. Laser-induced fluorescence is routinely used to monitor trace constituents and pollutants in the terrestrial atmosphere. Several spacecraft laser systems are currently under development. Our calculations indicate that laser-induced fluorescent detection is approximately two orders of magnitude more sensitive than rocket ultraviolet measurements of possible Jovian absorption features at 2600 A that have been attributed to the presence of adenine or benzene.

Atmosphere↗
PubMed1975

Problems of component discrimination in space radiation dosimetry.

Resolving the LET spectrum of environmental radiation in space for assessing dose equivalents creates special problems due to superposition effects. Three components of the radiation field in space, trapped protons, tissue disintegration stars, and neutrons, contribute the bulk of the total dose equivalent. While lack of discrimination of neutron recoil and trapped primary protons does not interfere with correct determination of the combined dose equivalent as such, the simultaneous bursts of several low-energy protons and alpha particles from tissue disintegration stars completely defy LET-resolution with conventional instrumentation. So far, the tissue star dose has been determined only semiquantitatively from nuclear emulsion data. The neutron spectrum in space shows a markedly higher relative fluence in the region beyond 5 MeV than the fission neutron spectrum. Therefore, its LET spectrum centers less heavily on LET values near the proton Bragg Peak. This would call for assigning a QF value of less than 10 to the neutron dose in space. Still more serious shortcomings exist with regard to LET interpretation of heavy primaries.

Cosmic Radiation↗
PubMed1979

The Martian atmosphere: some unanswered questions.

The study of the Martian atmosphere and its significance for the possible origin of life on Mars is still very incomplete. Further investigations are needed to define the total volatile inventory, the early history of the atmosphere, and the relationship of the atmosphere to the question of indigenous life. In addition, studies of Venus, comets, and the Jupiter system will add significantly to our abilities to understand the early history of Mars.

Carbon↗
PubMed1979

Chemical and physical microenvironments at the Viking landing sites.

Physical and chemical considerations permit the division of the near-surface regolith on Mars into at least six zones of distinct microenvironments. The zones are euphotic, duricrust/peds, tempofrost, permafrost, endolithic, and interfacial/transitional. Microenvironments vary significantly in temperature extremes, mean temperature, salt content, relative pressure of water vapor, UV and visible light irradiance, and exposure to ionizing radiation events (100 Mrad) and oxidative molecular species. From what is known of the chemistry of the atmosphere and regolith fines (soil), limits upon the aqueous chemistry of soil pastes may be estimated. Heat of wetting could reach 45 cal/g dry soil; initial pH is indeterminate between 1 and 10; ionic strength and salinity are predicted to be extremely high; freezing point depression is inadequate to provide quantities of liquid water except in special cases. The prospects for biotic survival are grim by terrestrial standards, but the extremes of biological resiliency are inaccessible to evaluation. Second-generation in situ experiments which will better define Martian microenvironments are clearly possible. Antarctic dry valleys are approximations to Martian conditions, but deviate significantly by at least half-a-dozen criteria.

Chemical Phenomena↗
PubMed1979

Martian channels and the search for extraterrestrial life.

The origin of the channels on Mars has been a subject of intense interest since they were first recognized on early Mariner 9 images (Driscoll, 1972; Masursky, 1973). Their presence on the planet, and their striking resemblance to terrestrial flood channels related to glacial outbursts or to dendritic river systems has suggested to most investigators (Baker, 1974, 1977; Nummedal, 1978; Carr, 1979; Masursky et al., 1977) that they were formed by running water. Because life as we know it is dependent on water, the discovery by the 'Mariner cameras', of watercut channels and volcanoes as a source for water, and water ice in the residual north polar cap by Viking, has reaffirmed the choice of Mars as the best target for the search for extraterrestrial life.

Extraterrestrial Environment↗
PubMed1979

Solar radiation incident on the Martian surface.

Calculations indicate that the maximum daily solar radiation reaching the Martian surface is about 325 cal/cm2 during southern hemisphere summer at latitude of about 40 degrees S. In the ultraviolet region of the spectrum, the radiation reaching the surface at wavelengths greater than 2800 A is within 10% of the radiation incident on the atmosphere. There is significant extinction of radiation in the spectral region near 2500 A in mid and high latitudes due to adsorption of radiation by ozone; radiation reaching the surface may be reduced to one one-thousandth of that incident on the atmosphere during winter. Virtually no radiation of wavelengths less than 1900 A reaches the surface because of absorption by the large column abundance of carbon dioxide. Daily and latitudinal distributions of radiation are presented for wavelengths of 3000, 2500 and 2000 A.

Extraterrestrial Environment↗
PubMed1979

The implications and limitations of the findings of the Viking organic analysis experiment.

The gas chromatograph mass spectrometer instrument of the Viking mission has demonstrated the absence of organic compounds in the immediate surface layer of the two landing sites. The demonstration of the successful operation of the instrument (comparison of ground-based test data with those obtained during interplanetary flight and the data from the surface of the planet) and its limitations (e.g., the detection of highly cross-linked polymers or polymeric carbon suboxide) are reviewed. The measurements for bound water are based on indirect data, the detectability of evolved carbon dioxide and ammonia is poor, and oxygen, liberated from the soil samples, can not be detected.

Chemistry, Organic↗
PubMed1979

Mars ultraviolet simulation facility.

A facility was established for long-duration ultraviolet (UV) radiation exposure of natural and synthetic materials in order to test hypotheses concerning Martian soil chemistry observed by the Viking Mars landers. The system utilized a 2500 watt xenon lamp as the radiation source, with the beam passing through a heat-dissipating water filter before impinging upon an exposure chamber containing the samples to be irradiated. The chamber was designed to allow for continuous tumbling of the samples, maintenance of temperatures below 0 degrees C during exposure, and monitoring of beam intensity. The facility also provided for sample preparation under a variety of atmospheric conditions, in addition to the Mars nominal. As many as 33 sealed sample ampules have been irradiated in a single exposure. Over 100 samples have been irradiated for approximately 100 to 700 h. The facility has performed well in providing continuous UV irradiation of multiple samples for long periods of time under simulated Mars atmospheric and thermal conditions.

Chemical Phenomena↗
PubMed1979

Heterogeneous phase reactions of Martian volatiles with putative regolith minerals.

The chemical reactivity of several minerals thought to be present in Martian fines is tested with respect to gases known in the Martian atmosphere. In these experiments, liquid water is excluded from the system, environmental temperatures are maintained below 0 degrees C, and the solar illumination spectrum is stimulated in the visible and UV using a Xenon arc lamp. Reactions are detected by mass spectrometric analysis of the gas phase over solid samples. No reactions were detected for Mars nominal gas over sulfates, nitrates, chloride, nontronite clay, or magnetitie. Oxidation was not observed for basaltic glass, nontronite, and magnetite. However, experiments incorporating SO2 gas--an expected product of volcanism and intrusive volatile release--gave positive results. Displacement of CO2 by SO2 occurred in all four carbonates tested. These reactions are catalyzed by irradiation with the solar simulator. A calcium nitrate hydrate released NO2 in the presence of SO2. These results have implications for cycling of atmospheric CO2, H2O, and N2 through the regolith.

Atmosphere↗
PubMed1979

Frost-weathering on Mars: experimental evidence for peroxide formation.

A laboratory study of the interaction of H2O frost with samples of the minerals olivine (Mg,Fe)2SiO4 and pyroxene (Mg,Fe)SiO3 at -11 degrees C to -22 degrees C revealed that an acidic oxidant was produced. Exposure of the frost-treated minerals to liquie H2O produced a sudden drop in pH and resulted in the production of copious O2(g) (as much as approximately 10(20) molecules g-1). Exposure of frost-treated samples to 5 ml of 0.1M HCOONa solution resulted in the rapid oxidation of up to 43% of the formate to CO2(g). These reactions were qualitatively similar to the chemical activity observed during the active cycles of the Viking lander Gas Exchange and Labeled Release Biology experiments. Attempts to identify the oxidant by chemical indicators were inconclusive, but they tentatively suggested that chemisorbed hydrogen peroxide may have formed. The formation of chemisorbed peroxide could be explained as a byproduct of the chemical reduction of the mineral. The following model was proposed. H+ was incorporated into the mineral from surface frost. This would have left behind a residual of excess OH-(ads) (relative to surface H+). Electrons were then stripped from the surface OH-(ads) (due to the large repulsive potential between neighboring OH-(ads)) and incorporated into the crystal to restore charge balance and produce a chemical reduction of the mineral. The resultant surface hydroxyl radicals could then have combined to form the more stable chemisorbed hydrogen peroxide species. While the chemisorbed peroxide should be relatively stable at low temperatures, it should tend to decay to O(ads)+ H2O(g) at higher temperatures with an activation energy of greater than or approximately 34 kcal mole-1. This is consistent with the long-term storage and sterilization behavior of the Viking soil oxidants. It is possible that as little as 0.1--1% frost-weathered material in the martian soil could have produced the unusual chemical activity that occurred during the Viking Gas Exchange and Labeled Release experiments.

Chemical Phenomena↗
PubMed1979

Smectite clays in Mars soil: evidence for their presence and role in Viking biology experimental results.

Various chemical, physical and geological observations indicate that smectite clays are probably the major components of the Martian soil. Satisfactory ground-based chemical simulation of the Viking biology experimental results was obtained with the smectite clays nontronite and montmorillonite when they contained iron and hydrogen as adsorbed ions. Radioactive gas was released from the medium solution used in the Viking Labeled Release (LR) experiment when interacted with the clays, at rates and quantities similar to those measured by Viking on Mars. Heating of the active clay (mixed with soluble salts) to 160 degrees C in CO2 atmosphere reduced the decomposition activity considerably, again, as was observed on Mars. The decomposition reaction in LR experiment is postulated to be iron-catalyzed formate decomposition on the clay surface. The main features of the Viking Pyrolytic Release (PR) experiment were also simulated recently (Hubbard, 1979) which the iron clays, including a relatively low '1st peak' and significant '2nd peak'. The accumulated observations on various Martian soil properties and the results of simulation experiments, thus indicate that smectite clays are major and active components of the Martian soil. It now appears that many of the results of the Viking biology experiments can be explained on the basis of their surface activity in catalysis and adsorption.

Chemical Phenomena↗