Kinetics of Disproportionation of Inorganic Polysulfides in Undersaturated Aqueous Solutions at Environmentally Relevant Conditions

The rate of the reversible homogeneous disproportionation of polysulfides was studied by following the optical absorbance of polysulfide solutions in a continuous plug flow reactor equipped with an on-line photometric detector. In order to avoid heterogeneous slow reactions involving sulfur colloids or precipitate, the reaction was initiated by an abrupt pH change from an undersaturated solution containing predominantly tetrasulfide species to a pH where pentasulfide is the dominant species. The disproportionation was found to follow first order reversible reaction dynamics. At environmentally relevant conditions the characteristic time of the disproportionation reaction is of the order of 10 s. This characteristic time implies that necessary conditions for speciation of the different polysulfide species by chromatography or another separation and subsequent quantification scheme should be of the order of 1 s.     

Anaerobic methane oxidation and a deep H2S sink generate isotopically heavy sulfides in Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO₄²⁻-CH₄ transition where H₂S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H₂S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe²⁺ diffusing up from below. The H₂S-Fe²⁺ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO₄²⁻ and 10 yr for H₂S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO₄²⁻-CH₄ and H₂S-Fe²⁺ cause the trapping of isotopically heavy iron sulfide with δ³⁴S = +15 to +33‰ at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO₄²⁻ diffusing downward into the SO₄²⁻-CH₄ transition has an isotopic composition of +19‰, close to the +23‰ of H₂S diffusing upward. These isotopic compositions are, however, very different from the porewater SO₄²⁻ (+43‰) and H₂S (−15‰) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H₂S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth’s history.     

On the nonlinear dynamics of the boundary layer of intense atmospheric vortex

The paper describes a stationary model of the boundary layer of a large-scale vortex. The model takes into account two types of nonlinearities: (1) advection of the momentum and centrifugal accelerations, that is related to large values of the Rossby number; (2) a nonlinear turbulent friction on the lower boundary (generally speaking, not only quadratic, but also more complicated). Nevertheless, the model may be studied analytically. This approach allows discovery and analysis of several universal regularities, which are not revealed by numerical modeling. The model provides the actual values for the speed of the surface wind and the angle of cross-isobar surface flow in the tropical cyclones.     

The Earth's decelerated rotation and regularities in orientation of its surface lineaments and faults

The Earth's crust faults and lineaments group in clusters with predominant N-S and E-W (System I) and NW-SE and NE-SW (System II) directions. The earthquake epicenters of the Benioff seismofocal zones follow the same regularities. In other words, seismofocal zones (epicenters of earthquakes) constitute a part of the regular network of the Earth's crust and lithosphere faults and lineaments. Mathematical modeling of stress distribution in the lithosphere due to a change of the Earth's ellipsoid compression showed that the principal stresses σ₁ and σ₂ are oriented in N-S and E-W directions, while corresponding shear stresses τ are oriented in NE-SW and NW-SE directions. It is shown that the secular deceleration of the Earth's rotation can be a reasonable mechanism for the change of Earth's ellipsoid compression and, consequently, for the origin of the regular system of faults and lineaments described above.     

On the pair-instability supernovae and gamma-ray burst phenomenon

We present a model of a gamma-ray burst (GRB) related to “very massive” stars. In the framework of our model, the GRB phenomenon is a result of helium burning in degenerate conditions in a massive star (≳130 M _⊙), in which the thermal nuclear burning occurs in the deflagration regime and has a pulsating temporal pattern. The shock runs away from the burning (reaction) zone, which leads to the development of a coronal outflow (jet-like) structure. In our scenario the GRB observable prompt fast rise and decay part can be a result of photon propagation through the hot corona (Comptonization photosphere) of the star. On the other hand, the GRB afterglow is a cooling phase of the expanding and outflowing envelope. Presumably, the X-ray part of the GRB emergent spectrum is formed due to upscattering of soft photons of outer layers of the star off hot coronal electrons, and thus it should have a specific shape of the Comptonization spectrum.     

Vertical distribution of dust particles in the Earth's atmosphere during the 1998 Leonids

Abstract— Photometric observations of the twilight sky were carried out during Leonids 1998. The obtained vertical distributions of aerosol between 20 and 140 km demonstrate the processes of the intrusion of fine meteor dust and its subsequent intra-atmospheric dynamics. The characteristic radii of two fractions of the meteor dust particles were estimated by their sedimentation velocities. They varied within r_p = 0.006–0.06 μm and r_p = 19–81 μm limits depending on an assumed particle density within ρ_p = 0.4–4.0 g cm^?3. The assumption of ρ_p = 2.0 g cm^?3 gave radii of the two fractions to be 0.01 and 30 μm, respectively.     

Evaluation of embankment foundation creep in conditions of deep bedding of roof in permafrost soils

Railroad operating experience in permafrost conditions has shown that deformations of embankments on thawing foun-dations last for a long time. After an initial period of heat settlement due to permafr...