Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

The stoichiometry and stability of arsenic gaseous complexes were determined in the system As-H₂O ± NaCl ± HCl ± H₂S 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 (H₃AsO₃) between an aqueous solution (pure H₂O) and its saturated vapor (K = mAs_vapor /mAs_liquid) were found to be independent of As^(III) solution concentrations (up to ∼1 to 2 mol As/kg) and equal to 0.012 ± 0.003, 0.063 ± 0.023, and 0.145 ± 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 H₂S (up to ∼0.5 mol/kg of vapor). XAFS spectroscopic measurements carried out on As^(III)-H₂O (±NaCl) solutions up to 500°C demonstrate that the As(OH)₃ complex dominates As speciation both in dense H₂O-NaCl fluids and low-density supercritical vapor. Vapor-liquid partition coefficients for As^(III) measured in the H₂O-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 (>2 mol As/kg) or As₂O₃ solid is consistent with the formation, in the vapor phase, of both As₄O₆ and As(OH)₃. Arsenic^(V) (arsenic acid, H₃AsO₄) 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 H₂O-vapor phase. These processes should be taken into account to accurately model element fractionation and chemical equilibria during magma degassing and fluid boiling.     

Turbulence in the ocean: Development of investigations, evolution of ideas, and prospects

We present an analytic survey of a series of works devoted to the direct methods for the investigation of turbulence in natural basins originated under the guidance of A. G. Kolesnikov in the 50s. We describe the principal results of the early stage which formed the basis for future investigations. The main scientific directions of the latest period are also considered from the viewpoint of the development of Kolesnikov's ideas: investigation of the processes of generation and energy supply of small-scale turbulence, relationship between turbulence and the fine vertical structure and internal waves, and the mechanisms of vertical turbulent exchange in the ocean. A model of vertical exchange under the conditions of intermittent “source” turbulence is distinguished. We also discuss the directions of development and prospects of the investigation of turbulence. Translated by Peter V. Malyshev and Dmitry V. Malyshev     

Preliminary results of the alignment and Hartmann tests of the AZT-22 telescope

The AZT-22 telescope installed in Turkey (Antalia) was aligned and tested on stars by the Hartmann method. The rms normal deviation of an equivalent optical system is 0.040±0.016 µm. The circle of confusion is 0.40±0.04 arcsec in diameter at a 50% energy level.     

Convection of salt fingers in theC-SALT region

We study possible mechanisms of mixing in the northwest part of the Tropical Atlantic (C-SALT) and show that homogeneous layers in the staircase structure can be observed across the entire frontal zone of the North Equatorial Countercurrent. In the central region of the frontal zone, one may observe horizontal motions of the upper parts of quasihomogeneous layers with respect to their lower parts and an essential role in the exchange processes is played by turbulence. The peripheral regions of the frontal zone are characterized by the presence of horizontal advection and isopycnic mixing. Far from the frontal interface, the principal contribution to the exchange processes is made by double diffusion. We demonstrate that, for the analysis of the vertical buoyancy fluxes caused by salt fingers, one can use both the Stern relation and the “law of 4/3”. Translated by Peter V. Malyshev and Dmitry V. Malyshev.     

Antimony(III) complexing with O-bearing organic ligands in aqueous solution: An X-ray absorption fine structure spectroscopy and solubility study

The stability and structure of aqueous complexes formed by trivalent antimony (Sb^III) with carboxylic acids (acetic, adipic, malonic, lactic, oxalic, tartaric, and citric acid), phenols (catechol), and amino acids (glycine) having O- and N-functional groups (carboxyl, alcoholic hydroxyl, phenolic hydroxyl and amine) typical of natural organic matter, were determined at 20 and 60 °C from solubility and X-ray absorption fine structure (XAFS) spectroscopy measurements. In organic-free aqueous solutions and in the presence of acetic, adipic, malonic acids and glycine, both spectroscopic and solubility data are consistent with the dominant formation of Sb^III hydroxide species, , at strongly acid, acid-to-neutral and basic pH, respectively, demonstrating negligible complexing with mono-functional organic ligands (acetic) or those having non adjacent carboxylic groups (adipic, malonic). In contrast, in the presence of poly-functional carboxylic and hydroxy-carboxylic acids and catechol, Sb^III forms stable 1:1 and 1:2 complexes with the studied organic ligands over a wide pH range typical of natural waters (3 < pH < 9). XAFS spectroscopy measurements show that in these species the central Sb^III atom has a distorted pseudo-trigonal pyramidal geometry composed of the lone pair of 5s² electrons of Sb and four oxygen atoms from two adjacent functional groups of the ligand (OC-OH and/or COH), forming a five-membered bidendate chelate cycle. Stability constants for these species, generated from Sb₂O₃ (rhomb.) solubility experiments, were used to model Sb complexing with natural humic acids possessing the same functional groups as those investigated in this study. Our predictions show that in an aqueous solution of pH between 2 and 10, containing 1 μg/L of Sb and 5 mg/L of dissolved organic carbon (DOC), up to 35% of total dissolved Sb binds to aqueous organic matter via carboxylic and hydroxy-carboxylic groups. This amount of complexed Sb for typical natural DOC concentrations is in agreement with that estimated from dialysis experiments performed with commercial humic acid in our work and those available in the literature for a range of standardized IHSS humic acids. Our results imply that a significant part of Sb is likely to be bound with humic acids via hydroxy-carboxylic moieties, in the form of bidendate complexes. However, following the strong chemical affinity of Sb^III for reduced sulfur, some undefined fraction of Sb^III might also be bound to the minor thiol-bearing moieties of humic acids; further studies are required to check this hypothesis.     

Space- and Time-Dependent Probabilities for Earthquake Fault Systems from Numerical Simulations: Feasibility Study and First Results

In weather forecasting, current and past observational data are routinely assimilated into numerical simulations to produce ensemble forecasts of future events in a process termed “model steering”. Here we describe a similar approach that is motivated by analyses of previous forecasts of the Working Group on California Earthquake Probabilities (WGCEP). Our approach is adapted to the problem of earthquake forecasting using topologically realistic numerical simulations for the strike-slip fault system in California. By systematically comparing simulation data to observed paleoseismic data, a series of spatial probability density functions (PDFs) can be computed that describe the probable locations of future large earthquakes. We develop this approach and show examples of PDFs associated with magnitude M > 6.5 and M > 7.0 earthquakes in California.     

Origin of the Permian-Triassic komatiites,northwestern Vietnam

Abstract Rare examples of Phanerozoic komatiites are found in the Song Da zone, NW Vietnam. These komatiites were erupted through continental crust and may belong to the SE extension of the Permo-Triassic Emeishan volcanic province located in SW China. They provide a good opportunity to study the source characteristics of starting plume magmas in a continental flood basalt province. Erupted on late-Permian carbonate rocks, the komatiitic rocks are interbedded with low-Ti olivine basalts. Basaltic komatiites display pyroxene spinifex textures, while more magnesian rocks (MgO up to 32 wt.%) are porphyritic, containing a single, cognate population of euhedral to elongated olivine phenocrysts with Fo up to 93.0%. This suggests a highly magnesian parental magma with 22–23 wt.% MgO. In terms of major and minor elements, the komatiites are similar to the ca. 89 Ma old Gorgona Island komatiites of Colombia. The Song Da komatiites are also strongly light-rare-earth-element- (LREE) depleted (Ce_N/Yb_N 0.30–0.62) and have unfractionated heavy rare earth element (HREE) patterns. The komatiites have high Os concentrations (up to 7.0 ppb), low but variable Re/Os ratios, and define an isochron with an age of 270±21 Ma, and an initial ¹⁸⁸Os/¹⁸⁷Os ratio of 0.12506± 0.00041 (_Os=+0.02±0.40). The Os isotopic systematics of the komatiites show no effects of crustal contamination. In contrast, their initial _Nd values range from +3 to +8, reflecting varying but generally small degrees of contamination with Proterozoic sialic basement material. Associated low-Ti basalts have low initial _Nd values (–0.8 to –7.5), high initial _Os values (15), flat or LREE-enriched REE patterns, and Nb-Ta depletion. These characteristics are also attributed to variable extents of crustal contamination.Editorial responsibility: T.L. Grove     

Heat and mass transport by weakly non-linear internal waves in the presence of turbulence

The method of asymptotic multiscale expansion is applied to determine the mean current velocity and density fields induced by a packet of internal waves. In the limiting case of a weakly non-linear plane wave, heat, salt, and impulse vertical transport is conditioned by the vertical component of the Stokes drift velocity, which is non-zero, when turbulent viscosity and diffusion are considered. As the wave period decreases, the wave fluxes of heat, salt, and impulse increase. In shallow waters, these fluxes become more vigorous and may be comparable to the respective turbulent flows or even to be more powerful. Translated by Vladimir A. Puchkin.     

Staircase and inversion structures of thermocline in the north-west Tropical Atlantic

The peculiarities of the vertical fine thermohaline structure of waters in the north-west Tropical Atlantic are considered on the data of STD surveys recorded in winter-spring 1984. The variability of the characteristics of staircase and inversion elements of stratification with depth is analysed over the horizontal as well as related to the mesoscale and large-scale dynamics of waters. The coefficients of horizontal turbulent exchange are estimated within the framework of Joyce's hypothesis on quasi-compensation of vertical and turbulent horizontal transport. The effects of double diffusion are considered to dominate in vertical transport.UDK 551.465.15Translated by Mikhail M. Trufanov.