All cells contain much more potassium, phosphate, and transition metals than modern (or reconstructed primeval) oceans, lakes, or rivers. Cells maintain ion gradients by using sophisticated, energydependent membrane enzymes (membrane pumps) that are embedded in elaborate ion-tight membranes. The first cells could possess neither ion-tight membranes nor membrane pumps, so the concentrations of small inorganic molecules and ions within protocells and in their environment would equilibrate. Hence, the ion composition of modern cells might reflect the inorganic ion composition of the habitats of protocells. We attempted to reconstruct the "hatcheries" of the first cells by combining geochemical analysis with phylogenomic scrutiny of the inorganic ion requirements of universal components of modern cells. These ubiquitous, and by inference primordial, proteins and functional systems show affinity to and functional requirement for K + , Zn 2+ , Mn 2+, and phosphate. Thus, protocells must have evolved in habitats with a high K + /Na + ratio and relatively high concentrations of Zn, Mn, and phosphorous compounds. Geochemical reconstruction shows that the ionic composition conducive to the origin of cells could not have existed in marine settings but is compatible with emissions of vapor-dominated zones of inland geothermal systems. Under the anoxic, CO 2 -dominated primordial atmosphere, the chemistry of basins at geothermal fields would resemble the internal milieu of modern cells. The precellular stages of evolution might have transpired in shallow ponds of condensed and cooled geothermal vapor that were lined with porous silicate minerals mixed with metal sulfides and enriched in K + , Zn 2+, and phosphorous compounds.
The stoichiometry and stability of arsenic gaseous complexes were determined in the system AsH 2 O Ϯ NaCl Ϯ HCl Ϯ H 2 S at temperatures up to 500°C and pressures up to 600 bar, from both measurements of As (III) and As (V) vapor-liquid and vapor-solid partitioning, and X-ray absorption fine structure (XAFS) spectroscopic study of As (III)-bearing aqueous fluids. Vapor-aqueous solution partitioning for As (III) was measured from 250 to 450°C at the saturated vapor pressure of the system (P sat) with a special titanium reactor that allows in situ sampling of the vapor phase. The values of partition coefficients for arsenious acid (H 3 AsO 3) between an aqueous solution (pure H 2 O) and its saturated vapor (K ϭ mAs vapor /mAs liquid) were found to be independent of As (III) solution concentrations (up to ϳ1 to 2 mol As/kg) and equal to 0.012 Ϯ 0.003, 0.063 Ϯ 0.023, and 0.145 Ϯ 0.020 at 250, 300, and 350°C, respectively. These results are interpreted by the formation, in the vapor phase, of As(OH) 3 (gas), similar to the aqueous As hydroxide complex dominant in the liquid phase. Arsenic chloride or sulfide gaseous complexes were found to be negligible in the presence of HCl or H 2 S (up to ϳ0.5 mol/kg of vapor). XAFS spectroscopic measurements carried out on As (III)-H 2 O(ϮNaCl) solutions up to 500°C demonstrate that the As(OH) 3 complex dominates As speciation both in dense H 2 O-NaCl fluids and low-density supercritical vapor. Vapor-liquid partition coefficients for As (III) measured in the H 2 O-NaCl system up to 450°C are consistent with the As speciation derived from these spectroscopic measurements and can be described by a simple relationship as a function of the vapor-to-liquid density ratio and temperature. Arsenic (III) partitioning between vapor and As-concentrated solutions (Ͼ2 mol As/kg) or As 2 O 3 solid is consistent with the formation, in the vapor phase, of both As 4 O 6 and As(OH) 3. Arsenic (V) (arsenic acid, H 3 AsO 4) vapor-liquid partitioning at 350°C for dilute aqueous solution was interpreted by the formation of AsO(OH) 3 in the vapor phase. The results obtained were combined with the corresponding properties for the aqueous As(III) hydroxide species to generate As(OH) 3 (gas) thermodynamic parameters. Equilibrium calculations carried out by using these data indicate that As(OH) 3 (gas) is by far the most dominant As complex in both volcanic gases and boiling hydrothermal systems. This species is likely to be responsible for the preferential partition of arsenic into the vapor phase as observed in fluid inclusions from high-temperature (400 to 700°C) Au-Cu (-Sn,-W) magmatic-hydrothermal ore deposits. The results of this study imply that hydrolysis and hydration could be also important for other metals and metalloids in the H 2 O-vapor phase. These processes should be taken into account to accurately model element fractionation and chemical equilibria during magma degassing and fluid boiling.
Macrobioerosion is a common process in marine ecosystems. Many types of rock-boring organisms break down hard substrates, particularly carbonate rocks and calcareous structures such as dead corals and shells. In paleontology, the presence of rocks with boreholes and fossil macroboring assemblage members is one of the primary diagnostic features of shallow marine paleo-environments. Here we describe a silicate rock-boring organism and an associated community in submerged siltstone rock outcrops in Kaladan River, Myanmar. The rock-boring mussel Lignopholas fluminalis is a close relative of the marine piddocks, and its borings belong to the ichnospecies Gastrochaenolites anauchen. The neotectonic uplift of the area leading to gradual decrease of the sea level with subsequent shift from estuarine to freshwater environment was the most likely driver for the origin of this community. Our findings highlight that rocks with macroborings are not an exclusive indicator of marine paleo-ecosystems, but may also reflect freshwater habitats.
Geological activity on icy planets and planetoids includes cryovolcanism. Until recently, most research on terrestrial permafrost has been engineering-oriented, and many related phenomena have received too little attention. Although fast processes in the Earth’s cryosphere were known before, they have never been attributed to cryovolcanism. The discovery of a couple of tens of meters wide crater in the Yamal Peninsula aroused numerous hypotheses of its origin, including a meteorite impact or migration of deep gas as a result of global warming. However, the origin of the Yamal crater can be explained in terms of cryospheric processes. Thus, the Yamal crater appears to result from collapse of a large pingo, which formed within a thaw lake when it shoaled and dried out allowing a large talik (that is layer or body of unfrozen ground in a permafrost area) below it to freeze back. The pingo collapsed under cryogenic hydrostatic pressure built up in the closed system of the freezing talik. This happened before the freezing completed, when a core of wet ground remained unfrozen and stored a huge amount of carbon dioxide dissolved in pore water. This eventually reached gas-phase saturation, and the resulting overpressure came to exceed the lithospheric confining stress and the strength of the overlying ice. As the pingo exploded, the demarcation of the crater followed the cylindrical shape of the remnant talik core.
Abstract-Dhofar (Dho) 225 and Dho 735 are carbonaceous chondrites found in a hot desert and having affinities to Belgica-like Antarctic chondrites (Belgica [B-] 7904 and Yamato [Y-] 86720). Texturally they resemble CM2 chondrites, but differ in mineralogy, bulk chemistry and oxygen isotopic compositions. The texture and main mineralogy of Dho 225 and Dho 735 are similar to the CM2 chondrites, but unlike CM2 chondrites they do not contain any (P, Cr)-sulfides, nor tochilinite 6Fe 0.9 S*5(Fe,Mg)(OH) 2 . H 2 O-contents of Dho 225 and Dho 735 (1.76 and 1.06 wt%) are lower than those of CM2 chondrites (2-18 wt%), but similar to those in the metamorphosed carbonaceous chondrites of the Belgica-like group. Bulk compositions of Dho 225 and Dho 735, as well as their matrices, have low Fe and S and low Fe ⁄ Si ratios relative to CM2 chondrites. X-ray powder diffraction patterns of the Dho 225 and Dho 735 matrices showed similarities to laboratory-heated Murchison CM2 chondrite and the transformation of serpentine to olivine. Dho 225 and 735's oxygen isotopic compositions are in the high 18 O range on the oxygen diagram, close to the Belgica-like meteorites. This differs from the oxygen isotopic compositions of typical CM2 chondrites. Experimental results showed that the oxygen isotopic compositions of Dho 225 and Dhofar 725, could not be derived from those of typical CM2 chondrites via dehydration caused by thermal metamorphism. Dho 225 and Dho 735 may represent a group of chondrites whose primary material was different from typical CM2 chondrites and the Belgica-like meteorites, but they formed in an oxygen reservoir similar to that of the Belgica-like meteorites.
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