Frost-weathering on Mars: Experimental evidence for peroxide formation

Summary 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°C to –22°C revealed that an acidic oxidant was produced. Exposure of the frost-treated minerals to liquid H₂O produced a sudden drop in pH and resulted in the production of copious O_2(g) (as much as ~ 10²⁰ 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 CO_2(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^c 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 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.This paper contains the material given in invited presentations at the COSPAR Meeting, Innsbruck, Austria, 5–7 June 1978 and at the Second Conference on Simulation of Mars Surface Properties, NASA Ames Research Center, 17–18 August 1978     

Classification and ecological characterization of coniferous forest phytogeocoenoses of Hokkaido,Japan

Coniferous forest phytogeocoenoses of Hokkaido Island, Japan, were studied to classify them based on vegetation characteristics, to analyse their soils, to correlate the vegetation and soil characteristics, and to provide some ecological interpretation for the phytogeocoenosis differentiation and establishment. Five forest types were distinguished based on the vegetation structure, each of which was comparable to plant association of Krajina (1960); 1. the moss type, 2. the Sasa kurilensis type, 3. the Sasa senanensis type, 4. the Carex sachalinensis type, and 5. the Dryopteris crassirhizoma type. Soil base status indicated by pH, electric conductivity, amount of calcium and magnesium, and base saturation showed a fair correlation with the forest types. The forest types were, therefore, arranged along a soil nutritional gradient. The moss type developed in the least fertile habitats whereas the Dryopteris crassirhizoma type in the most fertile habitats, and others were in between the two. It was suggested that in the island, where climate was humid with excess of soil water throughout a year, soil nutritional regime, more specifically availability of bivalent cations which tended to be removed by the excessive soil water, seemed to be a critical factor to differentiate and establish the forest types.This study was financially supported by the Science Research Grant of the (Monbusho) Japanese Goverment (Grant No. 60540422).     

Protein extraction and activity in reverse micelles of a nonionic detergent

We describe, for the first time, the ability of a polyoxyethylene sorbitan trioleate-isopropanol microemulsion in hexane to solubilize pure proteins. The dependences of cytochrome c extraction and buffer solubilization by the reverse micellar system on ionic strength of the aqueous phase, detergent concentration, and cosurfactant concentration result in increased extraction. In addition, subtilisin (a serine protease) is shown to be active in this microemulsion. Further the activity of the enzyme can be regulated by the water content of the micelles, enabling control of enzyme activity by "solvent engineering."     

Effect of hydration on the morphology of enzyme powder

We report the first direct images of the hydration of protein powders. Using an environmental scanning electron microscope (ESEM) we have taken a series of micrographs of a region of the enzyme (subtilisin) power whilst hydrating the sample. In addition, the sample has been viewed during exposure to toluene vapors. The ESEM is a remarkable new instrument that will have wide applicability in imaging of biological materials in their native environments.     

Intraspecific variation in the response of rice (Oryza sativa) to increased CO2– photosynthetic, biomass and reproductive characteristics

Two rice ( Oryza sativa L.) cultivars of contrasting morphologies, IR-36 and Fujiyama-5, were exposed to ambient (360 μl l⁻¹) and ambient plus 300 μl l⁻¹ CO₂ from time of emergence until ca 50% grain fill at the Duke University Phytotron, Durham, North Carolina. Exposure to increased CO₂ resulted in about a 50% increase in the photosynthetic rate for both cultivars and photosynthetic enhancement was still evident after 3 months of exposure to a high CO₂ environment. The photosynthetic response at 5% CO₂ and the response of CO₂ assimilation (A) to internal CO₂ (C_i) suggest a reallocation of biochemical resources from RuBP carboxylation to RuBP regeneration. Increases in total plant biomass at elevated CO₂ were approximately the same in both cultivars, although differences in allocation patterns were noted in root/shoot ratio. Differences in reproductive characteristics were also observed between cultivars at an elevated CO₂ environment with a significant increase in harvest index for IR-36 but not for Fujiyama-5. Changes in carbon allocation in reproduction between these two cultivars suggest that lines of rice could be identified that would maximize reproductive output in a future high CO₂ environment.     

Carbon isotope discrimination at vegetative stage as an indicator of yield and water use efficiency of spring wheat (Triticum turgidum L. var. durum)

A field experiment was conducted to investigate if carbon isotope (¹³C) discrimination () measured at the vegetative stage of spring wheat (Triticum turgidum L. var. durum) is related with the yield and water use efficiency (WUE) at ripening. A line source sprinkler irrigation system exposed the wheat genotypes to different watering regimes, from rainfed to full irrigation and thereby increased the range in yield and WUE attainable in the four genotypes studied. The results indicated that values measured at the late stem elongation stage 60 days after planting (DAP), showed strong positive correlation with total dry matter yield (r=0.732^***), and a highly significant negative correlation with WUE (r=–0.755^***) measured at ripening 105 DAP. The data suggest that the imprints of measured at vegetative growth stage persists throughout the entire growth period, until maturity. Subject to confirmation from additional studies in other crops and locations, early measurements of may prove a useful tool for rapid and early screening of cultivars, for high yield and high WUE.     

Active site conformation in myoglobin as determined by X-ray absorption spectroscopy

X-ray absorption fine structure experiments were performed to study structural and dynamic aspects of the active site of various forms of myoglobin. The structures determined for deoxyMb, MbCO, and MbO2 are consistent with the structure established by X-ray absorption fine structure experiment and X-ray crystallography. The first shell of ferrous MbNO determined contains 5 nitrogens located at 2.02 A and a short NO bond length of 1.76 A. This study focuses on the change of the XAFS Debye-Waller factor with temperature, which is a measure of thermal and static disorder. It was found that the changes of Debye-Waller factor with temperature for the Mb proteins, except deoxyMb, are consistent with a simple Einstein model, in which a single frequency was assumed for the bond stretching modes. In contrast, the temperature dependence of deoxyMb cannot be fitted to the Einstein model and a large disorder was found at low temperatures, which indicates the existence of conformational substates of the active site.     

Method for Lyophilizing Brain Proteolipid Preparation That Increases Subsequent Solubilization by Detergent

Abstract: A frozen mixture of solubilized brain proteolipid proteins in chloroform-methanol is not sublimable in a vacuum. However, when 7 to 10 volumes of benzene were added to a chloroform-methanol solution containing 5 mg of proteolipid protein per ml, the proteolipid proteins remained in solution for a while and the frozen mixture was easily sublimated at 2 mm Hg. Before the addition of benzene, higher concentrations of protein required the acidification of the medium to avoid precipitation of proteolipid proteins. In contrast to what happens when proteolipid proteins are obtained by the evaporation of the organic mixture at room temperature, the protein obtained by lyophilization was soluble in aqueous solutions of ionic and nonionic detergents. Sodium dodecyl sulfate at 0.6 to 0.7% concentration completely solubilized the proteolipid protein obtained by lyophilization. With the nonionic detergents Lubrol WX and Triton X-100, a solubilization between 50 and 65% was achieved. Sodium deoxycholate was practically ineffective. Triton X-100 showed selectivity in solubilizing certain proteins. The role of lipids in the solubilization of proteolipid proteins with detergents is discussed.