Molecular and isotopic characteristics of gas hydrate-bound hydrocarbons in southern and central Lake Baikal

We investigated the molecular composition (methane, ethane, and propane) and stable isotope composition (methane and ethane) of hydrate-bound gas in sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved from eight gas seep sites, located in the southern and central Baikal basins. Empirical classification of the methane stable isotopes (δ¹³C and δD) for all the seep sites indicated the dominant microbial origin of methane via methyl-type fermentation; however, a mixture of thermogenic and microbial gases resulted in relatively high methane δ¹³C signatures at two sites where ethane δ¹³C indicated a typical thermogenic origin. At one of the sites in the southern Baikal basin, we found gas hydrates of enclathrated microbial ethane in which ¹³C and deuterium were both highly depleted (mean δ¹³C and δD of –61.6‰ V-PDB and –285.4‰ V-SMOW, respectively). To the best of our knowledge, this is the first report of C₂ δ¹³C–δD classification for hydrate-bound gas in either freshwater or marine environments.     

Conditions of pocket formation in the Oktyabrskaya tourmaline-rich gem pegmatite (the Malkhan field, Central Transbaikalia, Russia)

Coexisting melt (MI), fluid-melt (FMI) and fluid (FI) inclusions in quartz from the Oktaybrskaya pegmatite, central Transbaikalia, have been studied and the thermodynamic modeling of PVTX-properties of aqueous orthoboric-acid fluids has been carried out to define the conditions of pocket formation. At room temperature, FMI in early pocket quartz and in quartz from the coarse-grained quartz–oligoclase host pegmatite contain crystalline aggregates and an orthoboric-acid fluid. The portion of FMI in inclusion assemblages decreases and the volume of fluid in inclusions increases from the early to the late growth zones in the pocket quartz. No FMI have been found in the late growth zones. Significant variations of solid/fluid ratios in the neighboring FMI result from heterogeneous entrapment of coexisting melts and fluids by a host mineral. Raman spectroscopy, SEM EDS and EMPA indicate that the crystalline aggregates in FMI are dominated by mica minerals of the boron-rich muscovite–nanpingite CsAl₂[AlSi₃O₁₀](OH,F)₂ series as well as lepidolite. Topaz, quartz, potassium feldspar and several unidentified minerals occur in much lower amounts. Fluid isolations in FMI and FI have similar total salinity (4–8 wt.% NaCl eq.) and H₃BO₃ contents (12–16 wt.%). The melt inclusions in host-pegmatite quartz homogenize at 570–600 °C. The silicate crystalline aggregates in large inclusions in pocket quartz completely melt at 615 °C. However, even after those inclusions were significantly overheated at 650±10 °C and 2.5 kbar during 24 h they remained non-homogeneous and displayed two types: (i) glass+unmelted crystals and (ii) fluid+glass. The FMI glasses contain 1.94–2.73 wt.% F, 2.51 wt.% B₂O₃, 3.64–5.20 wt.% Cs₂O, 0.54 wt.% Li₂O, 0.57 wt.% Ta₂O₅, 0.10 wt.% Nb₂O₅, 0.12 wt.% BeO. The H₂O content of the glass could exceed 12 wt.%. Such compositions suggest that the residual melts of the latest magmatic stage were strongly enriched in H₂O, B, F, Cs and contained elevated concentrations of Li, Be, Ta, and Nb. FMI microthermometry showed that those melts could have crystallized at 615–550 °C.

Crystallization of quartz–feldspar pegmatite matrix leads to the formation of H₂O-, B- and F-enriched residual melts and associated fluids (prototypes of pockets). Fluids of different compositions and residual melts of different liquidus–solidus P–T-conditions would form pockets with various internal fluid pressures. During crystallization, those melts release more aqueous fluids resulting in a further increase of the fluid pressure in pockets. A significant overpressure and a possible pressure gradient between the neighboring pockets would induce fracturing of pockets and “fluid explosions”. The fracturing commonly results in the crushing of pocket walls, formation of new fractures connecting adjacent pockets, heterogenization and mixing of pocket fluids. Such newly formed fluids would interact with a primary pegmatite matrix along the fractures and cause autometasomatic alteration, recrystallization, leaching and formation of “primary–secondary” pockets.     

Error analysis of integrated water vapor measured by СIMEL photometer

Water vapor plays a key role in weather and climate forming, which leads to the need for continuous monitoring of its content in different parts of the Earth. Intercomparison and validation of different methods for integrated water vapor (IWV) measurements are essential for determining the real accuracies of these methods. CIMEL photometers measure IWV at hundreds of ground-based stations of the AERONET network. We analyze simultaneous IWV measurements performed by a CIMEL photometer, an RPG-HATPRO MW radiometer, and a FTIR Bruker 125-HR spectrometer at the Peterhof station of St. Petersburg State University. We show that the CIMEL photometer calibrated by the manufacturer significantly underestimates the IWV obtained by other devices. We may conclude from this intercomparison that it is necessary to perform an additional calibration of the CIMEL photometer, as well as a possible correction of the interpretation technique for CIMEL measurements at the Peterhof site.     

Study of the ice conditions in the Gulf of Ob

The results of theoretical studies of fracture lines in the ice floes of the Gulf of Ob as a function of the coefficient of internal sliding are presented in this paper. An estimate of the fractal dimensions of the emerging topological structures and the results of the calculation of stresses in the ice cover of the Gulf of Ob are presented as functions of different directions of external forcing caused by the joint action of winds and currents on the ice. The geographical locations of the zones of possible loads are shown, together with the estimates of the hummock sizes in the zones of the maximal compression of the ice floes in the Gulf of Ob.     

Spatio-temporal variations of density of the particles generating the optical emission of meteor plasma

The data of absolute spectrophotometry of meteors permit to determine number densities of particles of different elements.It is possible to solve mathematically the problem on space-time structure of the meteor with the model of a spherically symmetrical flare.The space distribution of radiating matter can be estimated by the integral equation of Abel type.Variation of density of particles in time can be found from the differential equations of kinetics.     

The 1.10- and 1.18-μm nightside windows of Venus observed by SPICAV-IR aboard Venus Express

Observations of the 1.10- and 1.18-μm nightside windows by the SPICAV-IR instrument aboard Venus Express were analyzed to characterize the various sources of gaseous opacity and determine the H₂O mole fraction in the lower atmosphere of Venus. We showed that the line profile model of Afanasenko and Rodin (Afanasenko, T.S., Rodin, A.V. [2007]. Astron. Lett. 33, 203–210) underestimates the CO₂ absorption in the high-wavelength wing of the 1.18-μm window and we derived an empirical lineshape that matches this wing well. An additional continuum opacity is required to reproduce the variation of the 1.10- and 1.18-μm radiances with surface elevation as observed by the VIRTIS-M instrument aboard Venus Express. A constant absorption coefficient of 0.7 ± 0.2 × 10⁻⁹ cm⁻¹ am⁻² best reproduces the observed variation. We compared spectra calculated with different CO₂ and H₂O line lists. We found that the CDSD line list lacks the 5ν₁ + ν₃ series of CO₂ bands, which provide significant opacity in Venus’ deep atmosphere, and we have constructed a composite line list that best reproduces the observations. We also showed for the first time that HDO brings significant absorption at 1140–1190 nm. Using the best representation of the atmospheric opacity we could reach, we retrieved a water vapor mole fraction of ppmv, pertaining to the altitude range 5–25 km. Combined with previous measurements in the 1.74- and 2.3-μm windows, this result provides strong evidence for a uniform H₂O profile below 40 km, in agreement with chemical models.     

Active Galactic Nuclei among Polar-Ring Galaxies

Astronomy Letters - Based on SDSS data, we consider the fraction of active galactic nuclei among polar-ring galaxies. We have found evidence for an excess of Seyfert galaxies and LINERS among...     

Land use contribution to the anthropogenic emission of greenhouse gases in Russia in 2000–2011

Presented is the assessment of the contribution that such major types of the land use in Russia as arable lands, forage lands, settlements, and peatery make to anthropogenic fluxes of carbon dioxide CO₂, methane CH₄, and nitrogen oxide N₂O, The assessment is based on the methods of computation monitoring carried out in the period from 2000 to 2011. The results of the study demonstrated that every year arable lands cause the emission of CO₂ and N₂O of about 117.0 and 74.9 million t CO₂ equiv, and peatery, 0.54 and 105.4 thousand t CO₂ equiv, respectively. The balance of soil carbon in hayfields and pastures is close to zero. The average emissions of CH₄ and N₂O from the manure of pasture animals amount to 0.2 and 5.0 million t CO₂ equiv/year, and those from grass fires, 276.1 and 372.5 thousand t CO₂ equiv/year, respectively. The carbon balance in permanent soils of settlements is also almost close to zero, and newly built-up lands are the source of CO₂ (9.5 million t/year). The natural overgrowing of fallow lands leads to the accumulation of the soil carbon (about 92.4 million t CO₂/year). It was revealed that the intensity of CO₂ emission is defined by the soil carbon balance and that of other gases, by the amount of nitrogen fertilizers, plant residues, and manure coming to the soil. The total emission from the land use is 106.9 million t CO₂ equiv/year that makes up 4.9% of the total anthropogenic emission of greenhouse gases in the Russian Federation.     

An X-ray absorption fine structure and nuclear magnetic resonance spectroscopy study of gallium-silica complexes in aqueous solution

The influence of aqueous silica on gallium(III) hydrolysis in dilute (2 × 10⁻⁴ ≤ m_Ga ≤ 5 × 10⁻³) and moderately concentrated (0.02 ≤ m_Ga ≤ 0.3) aqueous solutions was studied at ambient temperature, using high resolution X-ray absorption fine structure (XAFS) and nuclear magnetic resonance (NMR) spectroscopies, respectively. Results show that, in Si-free acidic solutions (pH < 3), Ga is hexa-coordinated with oxygens of H₂O molecules and/or OH groups in the first coordination sphere of the metal. With increasing pH, these hydroxyl groups are progressively replaced by bridging oxygens (-O-), and polymerized Ga-hydroxide complexes form via Ga-O-Ga chemical bonds. In the 2.5-3.5 pH range, both XAFS and NMR spectra are consistent with the dominant presence of the Ga₁₃ Keggin polycation, which has the same local structure as A1₁₃. Under basic pH (pH > 8), Ga exhibits a tetrahedral coordination, corresponding to Ga(OH)₄⁻ species, in agreement with previous NMR and potentiometric studies. Major changes in Ga hydrolysis have been detected in the presence of aqueous silica. Ga is tetra-coordinated, both in basic and acid (i.e., at pH > 2.7) Si-bearing solutions (0.01 ≤ m_Si ≤ 0.2), and forms stable gallium-silicate complexes. In these species, Ga binds via bridging oxygen to 2 ± 1 silicons, with an average Ga-Si distance of 3.16 ± 0.05 Å, and to 2 ± 1 silicons, with an average Ga-Si distance of 3.39 ± 0.03 Å. These two sets of Ga-Si distances imply the formation of two types of Ga-silicate aqueous complex, cyclic Ga-Si_2-3 species (formed by the substitution of Si in its tri-, tetra- or hexa-cyclic polymers by Ga atoms), and chainlike GaSi_2-4 species (similar to those found for A1), respectively. The increase in the number of Si neighbors (a measure of the complex concentration and stability), in alkaline media, with increasing SiO₂(aq) content and decreasing pH is similar to that for A1-Si complexes found in neutral to basic solutions. At very acid pH and moderate silica concentrations, the presence of another type of Ga-Si complex, in which Ga remains hexa-coordinated and binds to the silicon tetrahedra via the GaO₆ octahedron corners, has also been detected. These species are similar to those found for Al³⁺ in acid solutions. Thus, as for aluminum, silicic acid greatly hampers Ga hydrolysis and enhances Ga mobility in natural waters via the formation of gallium-silicate complexes.