Characteristics of shallow gas hydrate in Okhotsk Sea

Multidisciplinary field investigations were carried out in Okhotsk Sea by R/V Akademik M.A. Lavrentyev (LV) of the Russian Academy of Sciences (RAS) in May 2006, supported by funding agencies from Korea, Russia, Japan and China. Geophysical data including echo-sounder, bottom profile, side-scan-sonar, and gravity core sample were obtained aimed to understand the characteristics and formation mechanism of shallow gas hydrates. Based on the geophysical data, we found that the methane flare detected by echo-sounder was the evidence of free gas in the sediment, while the dome structure detected by side-scan sonar and bottom profile was the root of gas venting. Gas hydrate retrieved from core on top of the dome structure which was interbedded as thin lamination or lenses with thickness varying from a few millimeters to 3 cm. Gas hydrate content in hydrate-bearing intervals visually amounted to 5%-30% of the sediment volume. This paper argued that gases in the sediment core were not all from gas hydrate decomposition during the gravity core lifting process, free gases must existed in the gas hydrate stability zone, and tectonic structure like dome structure in this paper was free gas central, gas hydrate formed only when gases over-saturated in this gas central, away from these structures, gas hydrate could not form due to low gas concentration.

Authigenic sulfide minerals and their sulfur isotopes in sediments of the northern continental slope of the South China Sea and their implications for methane flux and gas hydrate formation

This is a report of the study of the authigenic sulfide minerals and their sulfur isotopes in a sediment core (NH-1) collected on the northern continental slope of the South China Sea, where other geophysical and geochemical evidence seems to suggest gas hydrate formation in the sediments. The study has led to the findings: (1) the pyrite content in sediments was relatively high and its grain size relatively large compared with that in normal pelagic or hemipelagic sediments; (2) the shallowest depth of the acid volatile sulfide (AVS) content maximum was at 437.5 cm (> 2 mu mol/g), which was deeper than that of the authigenic pyrite content maximum (at 141.5-380.5 cm); (3) delta S-34 of authigenic pyrite was positive (maximum: +15 parts per thousand) at depth interval of 250-380 cm; (4) the positive delta S-34 coincided with pyrite enrichment. Compared with the results obtained from the Black Sea sediments by Jorgensen and coworkers, these observations indicated that at the NH-1 site, the depth of the sulfate-methane interface (SMI) would be or once was at about 437.5-547.5 cm and the relatively shallow SMI depth suggested high upward methane fluxes. This was in good agreement with the results obtained from pore water sulfate gradients and core head-space methane concentrations in sediment cores collected in the area. All available evidence suggested that methane gas hydrate formation may exist or may have existed in the underlying sediments.

Low-amplitude BSRs and gas hydrate concentration on the northern margin of the South China Sea

The passive northern continental margin of the South China Sea is rich in gas hydrates, as inferred from the occurrence of bottom-simulating reflectors (BSR) and from well logging data at Ocean Drilling Program (ODP) drill sites. Nonetheless, BSRs on new 2D multichannel seismic reflection data from the area around the Dongsha Islands (the Dongsha Rise) are not ubiquitous. They are confined to complex diapiric structures and active fault zones located between the Dongsha Rise and the surrounding depressions, implying that gas hydrate occurrence is likewise limited to these areas. Most of the BSRs have low amplitude and are therefore not clearly recognizable. Acoustic impedance provides information on rock properties and has been used to estimate gas hydrate concentration. Gas hydrate-bearing sediments have acoustic impedance that is higher than that of the surrounding sediments devoid of hydrates. Based on well logging data, the relationship between acoustic impedance and porosity can be obtained by a linear regression, and the degree of gas hydrate saturation can be determined using Archie's equation. By applying these methods to multichannel seismic data and well logging data from the northern South China Sea, the gas hydrate concentration is found to be 3-25% of the pore space at ODP Site 1148 depending on sub-surface depth, and is estimated to be less than values of 5% estimated along seismic profile 0101. Our results suggest that saturation of gas hydrate in the northern South China Sea is higher than that estimated from well resistivity log data in the gas hydrate stability zone, but that free gas is scarce beneath this zone. It is probably the scarcity of free gas that is responsible for the low amplitudes of the BSRs.

Estimation of gas hydrate saturation using constrained sparse spike inversion: Case study from the northern South China Sea

Bottom-simulating reflectors (BSRs) were observed beneath the seafloor in the northern continental margin of the South China Sea (SCS). Acoustic impedance profile was derived by Constrained Sparse Spike Inversion (CSSI) method to provide information on rock properties and to estimate gas hydrate or free gas saturations in the sediments where BSRs are present. In general, gas hydrate-bearing sediments have positive impedance anomalies and free gas-bearing sediments have negative impedance anomalies. Based on well log data and Archie's equation, gas hydrate saturation can be estimated. But in regions where well log data is not available, a quantitative estimate of gas hydrate or free gas saturation is inferred by fitting the theoretical acoustic impedance to sediment impedance obtained by CSSI. Our study suggests that gas hydrate saturation in the Taixinan Basin is about 10 - 20% of the pore space, with the highest value of 50%, and free gas saturation below BSR is about 2 - 3% of the pore space, that can rise to 8 - 10% at a topographic high. The free gas is non-continuous and has low content in the southeastern slope of the Dongsha Islands. Moreover, BSR in the northern continental margin of the SCS is related to the presence of free gas. BSR is strong where free gas occurs.

Factors affecting the estimation of gas hydrate and free gas saturation

Attenuations of different types of gas hydrate cementation in fluid-saturated porous solids are discussed. The factors affecting estimation of gas hydrate and free gas saturation are analyzed. It is suggested that porosity of sediment, the P wave velocity model and methods of calculating elastic modulus are key factors in the estimation of gas hydrate and free gas saturations. Attenuation of gas hydrate-bearing sediment is closely related with the cementation types of gas hydrate. Negative anomalies of quality factors indicate that gas hydrate deposits away from grain as part of fluid. Positive anomalies of the quality factors indicate that gas hydrate contacts with solid and changes the elastic modulus of matrix. Low frequency velocity and high frequency velocity models are used to estimate gas hydrate and free gas saturation in the Blake Ridge area according to the well log data of the hole 995 in ODP leg 164. The gas hydrate saturation obtained by low frequency velocity is 10% similar to 20% of the pore space and free gas saturation is 0.5% similar to 1% of the pore space. The gas hydrate saturation obtained by high frequency velocity is 5% similar to 10% of the pore space and free gas saturation is 1% similar to 2% of the pore space.

Bottom simulating reflector and gas seepage in Okinawa Trough: Evidence of gas hydrate in an active back-arc basin

To look for gas hydrate, 22 multi-channel and 3 single-channel seismic lines on the East China Sea (ECS) shelf slope and at the bottom of the Okinawa Trough were examined. It was found that there was indeed bottom simulating reflector (BSR) occurrence, but it is very rare. Besides several BSRs, a gas seepage was also found. As shown by the data, both the BSR and gas seepage are all related with local geological structures, such as mud diapir, anticline, and fault-controlled graben-like structure. However, similar structural "anomalies" are quite common in the tectonically very active Okinawa Trough region, but very few of them have developed BSR or gas seepage. The article points out that the main reason is probably the low concentration of organic carbon of the sediment in this area. It was speculated that the rare occurrence of gas hydrates in this region is governed by structure-controlled fluid flow. Numerous faults and fractures form a network of high-permeability channels in the sediment and highly fractured igneous basement to allow fluid circulation and ventilation. Fluid flow in this tectonic environment is driven primarily by thermal buoyancy and takes place on a wide range of spatial scales. The fluid flow may play two roles to facilitate hydrate formation: to help gather enough methane into a small area and to modulate the thermal regime.

Catena-Poly[[[tetra-mu(2)-aqua-heptaaqua-(mu(2)-benzene-1,3,5-tricarboxylato)-mu(3)-hydroxido-trinickel(II)sodium]-mu(4)-benzene-1,3,5-tricarboxylato]sesqui-hydrate]

The title coordination polymer, {[Ni3Na(OH)(C9H3O6)(2)( H2O)(11)] center dot 1.5H(2)O}(n), is built up from three independent Ni-II ions and one Na-I cation bridged by benzene-2,4,6-tricarboxylate ( BTC) ligands and water molecules. Three Ni-II ions are bridged by three bidentate carboxylate groups of three BTC ligands, two aqua ligands and one OH- unit, to form a trinuclear metal cluster. The Na-I cation is bonded to the Ni-II cluster by two bridging water molecules. One of the three BTC ligands bridges neighbouring clusters into one-dimensional chains, which are further connected through a complex hydrogen-bonding scheme, forming a three-dimensional suprastructure. The title complex is isomorphous with the previously reported Co-II complex.

Low temperature X-ray crystallographic structures of two lamotrigine analogues: (I) 2-methyl,3-amino, 5-imino-6-(2,3-dichlorophenyl)-1,2,4-triazine water solvate and (II) 2-methyl,3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine isethionate, hemi-hydrate

The X-ray crystal structures of two lamotrigine derivatives (I) 2-methyl, 3-amino, 5-imino-6-(2, 3-dichlorophenyl)-1,2,4-triazine, C10H9Cl2N5, as the hemi hydrate and (II) 2-methyl,3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine, C10H10Cl2N5, as the isethionate-water solvate, have been carried out at liquid nitrogen temperature. A detailed comparison of the two structures is given. Both are monoclinic and centrosymmetric, with (I) in space group C2/c, and (II) in space group P2(1)/n. For (I) the unit cell dimensions are a = 19.5466(10), b = 7.5483(4), c = 15.7861(8) angstrom, beta = 91.458(3)degrees, volume = 2328.4(2) angstrom(3), Z = 8, density = 1.590 Mg/m(3); for (II). For (II) the unit cell dimensions are a = 6.0566(2), b = 11.0084(4) c = 23.9973(9) angstrom, beta = 92.587(3)degrees, volume = 1598.35(10) angstrom(3), Z = 4, density = 1.597 Mg/m(3). For (I) final R indices [I > 2sigma(I)] are R1 = 0.0356, wR2 = 0.0782 and R indices (all data) are R1 = 0.0424, wR2 = 0.0817. For (II) final R indices [I > 2sigma(I)] are R1 = 0.0380, wR2 = 0.0871 and R indices (all data) R1 = 0.0558, wR2 = 0.0949. Both structures have a molecule of water of crystallization and (II) also includes a solvated CH3SO3. Comparisons are made between the two structures. Structure (I) is very unusual in having a = NH group at position C5' on the triazine ring. No other examples of this particular substitution, which is usually -NH2, have been reported.

New families of enantiopure cyclohexenone cis-diol, o-quinol dimer and hydrate metabolites from dioxygenase-catalysed dihydroxylation of phenols

Toluene dioxygenase-catalysed cis-dihydroxylation of phenols has led to the discovery of new enantiopure cyclohexenone cis-diol, o-quinol dimer and phenol hydrate metabolites having synthetic potential.

EFFECT OF ULTRASOUND ON THE KINETICS OF REDUCTION OF HEXACYANOFERRATE(III) BY THIOSULFATE IONS MEDIATED BY RUTHENIUM DIOXIDE HYDRATE

Ultrasound promotes the reduction of hexacyanoferrate(III) by thiosulfate ions mediated by RuO2 . xH(2)O under diffusion-controlled conditions. There is a strong correlation between the measured first-order rate constant and the absorbance of the dispersion, which, in turn, is closely related to the specific surface area of the catalyst. The enhancement in rate with ultrasonic irradiation appears to be largely associated with the dispersive action of the ultrasound on the aggregated particles of RuO2 . xH(2)O. The rate of reaction increases with increasing %duty cycle and ultrasonic intensity. The measured overall activation energies for the reaction with and without ultrasound, i.e. 18 +/- 1 and 20 +/- 1 kJ mol(-1), respectively, are very similar to those expected for a diffusion-controlled reaction. The homogeneous reaction is not promoted by ultrasound.

KINETICS OF REDUCTION OF HEXACYANOFERRATE(III) BY THIOSULFATE IONS MEDIATED BY RUTHENIUM DIOXIDE HYDRATE

The kinetics of reduction of hexacyanoferrate(III) by excess thiosulfate, mediated by RuO2.xH2O, are investigated. At high concentrations of S2O32- (0.1 mol dm-3) the kinetics of Fe(CN)63- reduction are first order with respect to [Fe(CN)63-] and [RuO2.xH2O] and independent of [Fe(CN)64-], [S2O32-] and [S4O62-]. At relatively low concentrations Of S2O32- (0.01 mol dm-3) and in the presence of appreciable concentrations of Fe(CN)64- and S4O62- (0.01 mol dm-3) the kinetics depend directly upon [Fe(CN)63-] and [RuO2.xH2O] and inversely upon [Fe(CN)64-]. Both sets of kinetics can be rationalised using an electrochemical model of redox catalysts in which a reversible reduction reaction [Fe(CN)63- + e- --> Fe(CN)64-] is coupled to an irreversible oxidation reaction (s2O32- - e- --> 1/2S4O62-), by a dispersion of RuO2.xH2O microelectrodes. At high concentrations Of S2O32- this model predicts that the kinetics of Fe(CN)63- reduction are controlled by the rate of diffusion of the Fe(CN)63- ions to the RuO2.xH2O particles. The kinetics observed at low concentrations of S2O32- are predicted by the electrochemical model, assuming that the Tafel slope for the oxidation Of S2O32- to S4O62- on the RuO2.xH2O particles is 56.4 mV decade-1.

OXIDATION OF RUTHENIUM(II) TRIS(2,2'-BIPYRIDINE) IONS BY THALLIC IONS IN NITRIC-ACID, MEDIATED BY RUTHENIUM DIOXIDE HYDRATE - AN EXAMPLE OF REVERSIBLE HETEROGENEOUS REDOX CATALYSIS

The kinetics of the oxidation of Ru(bpy)32+ to Ru(bpy)33+ by T13+ ions, catalyzed by a dispersion of RuO2-xH2O in 3 mol dm-3 HNO3, are reported as a function of [Ru(bpy)32+], [Tl3+], [Tl+], [RuO2.xH2O], and temperature. The kinetics of Ru(bpy)32+ oxidation fit an electrochemical model of redox catalysis involving electron transfer between the two electrochemically reversible redox couples, i.e. Ru(bpy)33+/Ru(bpy)32+ and Tl3+/Tl+, mediated by the dispersion of microelectrode particles of RuO2.xH2O. In this model, the rate of reaction is assumed to be controlled by the diffusion of Ru(bpy)32+ toward, and Ru(bpy)33+ away from, the catalyst particles. The Arrhenius activation energy for the catalyzed reaction is 25.9 +/- 0.7 kJ mol-1, and the changes in enthalpy and entropy for the reaction are 36 +/- 2 kJ mol-1 and 127 +/- 6 J mol-1 K-1, respectively. This work describes a rare example of reversible heterogeneous redox catalysis.

OXIDATIVE DISSOLUTION OF RUTHENIUM DIOXIDE HYDRATE BY PERIODATE IONS

The results of a kinetic study of the oxidative dissolution of ruthenium dioxide hydrate to ruthenium tetroxide by periodate ions, IO4-, in acidic solution are described. The kinetics of dissolution give a good fit to a 'soft-centre' model in which the particles of RuO2.xH2O are assumed to be monodispersed, spherical but inhomogeneous in composition, comprising a difficult-to-corrode outer shell and a more easy-to-corrode inner core. In this work metaperiodate appears to act as a two-electron oxidant. The observed kinetics fit a reaction scheme in which the rate-determining step is the reaction between a surface site and an adsorbed IO4 ion and there is competitive adsorption by any IO3- present. In the absence and presence of an excess of IO3- ions, the overall activation energy for the corrosion reaction was determined to be 38 +/- 2 and 54 +/- 4 kJ mol-1, respectively.

OXIDATION OF WATER BY MNO4- MEDIATED BY THERMALLY ACTIVATED RUTHENIUM DIOXIDE HYDRATE

The kinetics of oxidation of water to oxygen by MnO4-, mediated by thermally activated ruthenium dioxide hydrate, has been studied. The rate of catalysis is 0.8 order with respect to the surface concentration of MnO4- (which in turn appears to fit a Langmuir adsorption isotherm) and proportional to the catalyst concentration, but is independent of the concentration of manganese(II) ions. The catalysed reaction appears to have an activation energy of 50 +/- 1 kJ mol-1. These observed kinetics are readily rationalised using an electrochemical model in which the catalyst particles act as microelectrodes providing a medium for electron transfer between the highly irreversible oxidation of water to O2 and the highly irreversible reduction of MnO4- to Mn2+.