Effect of Nontronite Smectite Clay on the Chemical Evolution of Several Organic Molecules under Simulated Martian Surface Ultraviolet Radiation Conditions

Most of the phyllosilicates detected at the surface of Mars today are probably remnants of ancient environments that sustained long-term bodies of liquid water at the surface or subsurface and were possibly favorable for the emergence of life. Consequently, phyllosilicates have become the main mineral target in the search for organics on Mars. But are phyllosilicates efficient at preserving organic molecules under current environmental conditions at the surface of Mars? We monitored the qualitative and quantitative evolutions of glycine, urea, and adenine in interaction with the Fe3+-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated martian surface ultraviolet light (190-400 nm), mean temperature (218 +/- 2 K), and pressure (6 +/- 1 mbar) in a laboratory simulation setup. We tested organic-rich samples that were representative of the evaporation of a small, warm pond of liquid water containing a high concentration of organics. For each molecule, we observed how the nontronite influences its quantum efficiency of photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine; their efficiencies of photodecomposition were reduced by a factor of 5 when mixed at a concentration of 2.6x10(-2) mol of molecules per gram of nontronite. Moreover, when the amount of nontronite in the sample of glycine was increased by a factor of 2, the gain of photoprotection was multiplied by a factor of 5. This indicates that the photoprotection provided by the nontronite is not a purely mechanical shielding effect but is also due to stabilizing interactions. No new evolution product was firmly identified, but the results obtained with urea suggest a particular reactivity in the presence of nontronite, leading to an increase of its dissociation rate. Key Words: Martian surface-Organic chemistry-Photochemistry-Astrochemistry-Nontronite-Phyllosilicates. Astrobiology 15, 221-237.

(Table 7) Fe**3+/Fe**2+ ratios in selected nontronite samples at DSDP Leg 70 Holes

Since its discovery in 1974 (Klitgord and Mudie, 1974), the Galapagos mounds hydrothermal field has received much attention. Sediment samples were taken during Leg 54 of the Deep Sea Drilling Project (DSDP) and by other expeditions to the area (e.g., Corliss et al., 1978). While a hydrothermal origin for the mounds sediments has been generally accepted, several different theories of origin for the mounds themselves have been proposed (e.g., Corliss et al., 1978; Natland et al., 1979; Williams et al., 1979). One of the aims of DSDP Leg 70 was to return to the mounds field and, using the new hydraulic piston cor er described elsewhere in this volume, to obtain more complete recovery of mounds sediments than had previously been possible. It was our hope that this would help in our understanding of the nature and origin of these deposits. In this chapter, we describe the results of chemical analysis of over 250 sediment samples taken during the course of Leg 70.

Coprolites from the Cretaceous Bearpaw Formation of Saskatchewan

Coprolites from the Beechy Member of the Cretaceous Bearpaw Formation, southern Saskatchewan, presumably deposited by one or more species of mosasaur or large fish/shark, were recovered and analyzed using SEM/EDS. The data reveal the presence of pseudomorphous coccoid bacteria, potential filamentous bacteria, bacterial endospores and filamentous fungi. No recorded fossil plant or bone material could be identified, either within the highly compressed coprolitic mat-flattened full coprolite bolus - of recovered marine sediment encased in a mixed mat of hematite-apatite primary minerals heavily coated with Ca-smectite and nontronite, or the full coprolite bolus. The presence of fossil bacteria with morphological characteristics similar to those of endospores in other environments suggests that only robust microbial forms such as these survive diagenesis, partly with some carbon still intact, the remainder replaced with silica and iron. The data support the view that coprolites can serve as a useful source of information on the ancient microbial world. © 2012 Elsevier Ltd.

The lateritic profile of Balkouin, Burkina Faso: geochemistry, mineralogy and genesis

This study reports on the geochemical and mineralogical characterization of a lateritic profile cropping out in the Balkouin area, Central Burkina Faso, aimed at obtaining a better understanding of the processes responsible for the formation of the laterite itself and the constraints to its development. The lateritic profile rests on a Paleoproterozoic basement mostly composed of granodioritic rocks related to the Eburnean magmatic cycle passing upwards to saprolite and consists of four main composite horizons (bottom to top): kaolinite and clay-rich horizons, mottled laterite and iron-rich duricrust. In order to achieve such a goal, a multi-disciplinary analytical approach was adopted, which includes inductively coupled plasma (ICP) atomic emission and mass spectrometries (ICP-AES and ICP-MS respectively), X-ray powder diffraction (XRPD), scanning electron microscopy with energy dispersive spectrometry (SEM-EDS) and micro-Raman spectroscopy.

The geochemical data, and particularly the immobile elements distribution and REE patterns, show that the Balkouin laterite is the product of an in situ lateritization process that involved a strong depletion of the more soluble elements (K, Mg, Ca, Na, Rb, Sr and Ba) and an enrichment in Fe; Si was also removed, particularly in the uppermost horizons. All along the profile the change in composition is coupled with important changes in mineralogy. In particular, the saprolite is characterized by occurrence of abundant albitic plagioclase, quartz and nontronite; kaolinite is apparently absent. The transition to the overlying lateritic profile marks the breakdown of plagioclase and nontronite, thus allowing kaolinite to become one of the major components upwards, together with goethite and quartz. The upper part of the profile is strongly enriched in hematite (+ kaolinite). Ti oxides (at least in part as anatase) and apatite are typical accessory phases, while free aluminum hydroxides are notably absent. Mass change calculations emphasize the extent of the mass loss, which exceeds 50 wt% (and often 70 wt%) for almost all horizons; only Fe was significantly concentrated in the residual system.

The geochemical and mineralogical features suggest that the lateritic profile is the product of a continuous process that gradually developed from the bedrock upwards, in agreement with the Schellmann classic genetic model. The laterite formation must have occurred at low pH (? 4.5) and high Eh (? 0.4) values, i.e., under acidic and oxidizing environments, which allowed strongly selective leaching conditions. The lack of gibbsite and bohemite is in agreement with the compositional data: the occurrence of quartz (± amorphous silica) all along the profile was an inhibiting factor for the formation of free aluminum hydroxides.