TERBIUM P-NITROBENZOATE HYDRATE

There are no discrete molecules of the title compound, catena-poly[{triaquaterbium-tris-beta-(p-nitro-benzoato)-O,O':O;O:O,O';O:O'-aqua(p-nitroben-zoato-O,O')terbium}-bis-mu-(p-nitrobenzoato-O:O') hydrate], [Tb2(C7H4NO4)6(H2O)5], in the crystal structure.

Geophysical signatures associated with fluid flow and gas hydrate occurrence in a tectonically quiescent sequence, Qiongdongnan Basin, South China Sea

Interpretation of high-resolution two-dimensional (2D) and three-dimensional (3D) seismic data collected in the Qiongdongnan Basin, South China Sea reveals the presence of polygonal faults, pockmarks, gas chimneys and slope failure in strata of Pliocene and younger age. The gas chimneys are characterized by low-amplitude reflections, acoustic turbidity and low P-wave velocity indicating fluid expulsion pathways. Coherence time slices show that the polygonal faults are restricted to sediments with moderate-amplitude, continuous reflections. Gas hydrates are identified in seismic data by the presence of bottom simulating reflectors (BSRs), which have high amplitude, reverse polarity and are subparallel to seafloor. Mud diapirism and mounded structures have variable geometry and a great diversity regarding the origin of the fluid and the parent beds. The gas chimneys, mud diapirism, polygonal faults and a seismic facies-change facilitate the upward migration of thermogenic fluids from underlying sediments. Fluids can be temporarily trapped below the gas hydrate stability zone, but fluid advection may cause gas hydrate dissociation and affect the thickness of gas hydrate zone. The fluid accumulation leads to the generation of excess pore fluids that release along faults, forming pockmarks and mud volcanoes on the seafloor. These features are indicators of fluid flow in a tectonically-quiescent sequence, Qiongdongnan Basin. Geofluids (2010) 10, 351-368.

Genetic model of the hydrate system in the fine grain sediments in the northern continental slope of South China Sea

Gas hydrate samples were obtained firstly in China by drilling on the northern margin of South China Sea (SCS). To understand the formation mechanism of this unique accumulation system, this paper discusses the factors controlling the formation of the system by accurate geophysical interpretation and geological analysis, based on the high precision 2-D and 3-D multichannel seismic data in the drilling area. There are three key factors controlling the accumulation of the gas hydrate system in fine grain sediment: (1) large volume of fluid bearing methane gas Joins the formation of gas hydrate. Active fluid flow in the northern South China Sea makes both thermal gas and/or biogenic gas migrate into shallow strata and form hydrate in the gas hydrate stability zone (GHSZ). The fluid flow includes mud diapir and gas chimney structure. They are commonly characterized by positive topographic relief, acoustic turbidity and push-down, and low reflection intensity on seismic profiles. The gas chimneys can reach to GHSZ, which favors the development of BSRs. It means that the active fluid flow has a close relationship with the formation and accumulation of gas hydrate. (2) The episodic process of fracture plays an important role in the generation of gas hydrate. It may provide the passage along which thermogenic or biogenic gas migrated into gas hydrate stability zone (GHSZ) upward. And it increases the pore space for the growth of hydrate crystal. (3) Submarine landslide induced the anomalous overpressure activity and development of fracture in the GHSZ. The formation model of high concentration gas hydrate in the drilling sea area was proposed on the basis of above analysis.

Gas hydrate associated with mud diapirs in southern Okinawa Trough

Many mud diapirs have been recognized in southern Okinawa Trough by a multi-channel seismic surveying on R/V KEXUE I in 2001. Gas hydrates have been identified, by the seismic reflection characteristics, the velocity analysis and the impedance inversion. Geothermal heat flow around the central of the mud diapir has been determined theoretically by the Bottom Simulating Reflectors (BSRs). Comparing the BSR derived and the measured heat flow values, we infer that the BSR immediately at the top of the mud diapirs indicate the base of the saturated gas hydrate formation zone (BSGHFZ), but not, as we ordinarily know, the base of the gas hydrate stability zone (BGHSZ), which could be explained by the abnormal regional background heat flow and free gas flux associated with mud diapirs. As a result, it helps us to better understand the generation mechanism of the gas hydrates associated with mud diapirs and to predict the gas hydrate potential in the southern Okinawa Trough. (C) 2008 Elsevier Ltd. All rights reserved.

Gas hydrate occurrence on the continental slope of the northern South China Sea

High-resolution multi-channel seismic data and geological samples were collected during two research cruises of the R/V FENDOU 4 in 1999 and 2000. Studies on these data and samples together with results from sites 1143-1145 and 1148 of ODP Leg 184 suggest that the geological structure on the continental slope of the northern South China Sea is favorable for the formation of gas hydrates. Bottom simulating reflectors (BSRs) and geochemical anomalies which indicate the existence of gas hydrates have been recognized in sediments of the Xisha Trough, the Dongsha Rise and the accretionary wedge of the Manila subduction zone. These gas hydrates are generated by two different mechanisms depending on the tectonic regime and the seismic and geochemical characteristics. The first applies to the passive continental margin of the nor-them South China Sea on the Dongsha Rise and in the Xisha Trough. The gas hydrates are associated with diapiric structures, active faults, slumps and gravity flows as well as high Late Cenozoic sedimentation rates. Their seismic expression includes BSRs, seismic blanking zones and velocity anomalies. The second mechanism is operative on the active continental margin along the Manila subduction zone, especially in the accretionary wedge. Here, gas hydrate occurrence is marked by widespread BSRs and acoustic 'pull-down' possibly related to the existence of free gas in the sediments beneath the BSR. The thickness of the seismic blanking zones averages 250 m, suggesting that the stable gas hydrate zone has about the same thickness. (c) 2005 Elsevier Ltd. All rights reserved.

The stability zone of gas hydrate in the slope of East China Sea and neighboring trough basin area

We analyze the distribution of temperature and heat flow of the sea floor sediment in the area of East China Sea slope and West basin area of the Okinawa Trough. Based on the Sonar Buoy and OBS data, 6 velocity layers are recognized, each of which has velocity of 1.8(1.8 similar to 2.2) km/s,2.2(2.0 similar to 2.5)km/s,2.8 (2.7 similar to 3.2)km/s,3.4 similar to 3.6km/s,4.2(4.1 similar to 4.7)km/s and 5.1km/s, respectively. The upper velocity layer of 1.8 similar to 2.2 km/s corresponds to the Quaternary sediment stratum. The layer with velocity 3.4 similar to 4.2km/s is the Pliocene sediment stratum. The area that is suitable for stable existence of gas hydrate by the temperature and pressure is 70,000km(2) about 1/10 the total area of East China Sea. The thickness of the stability zone ranges from 400m (Middle Part of Okinawa Trough) to 1100m (North and South Part of Okinawa Trough). The Quaternary and Pliocene layers are suitable for stable exitence of gas hydrate. According to the tectonic stability and heat flow, the north part and south part of the Okinawa Trough are the most perspective area for the gas hydrate explorations.

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.