Geochemistry of pore waters from the Xisha Trough, northern South China Sea and their implications for gas hydrates

This paper reports all available geochemical data on sediments and pore waters from the Xisha Trough on the northern continental margin of the South China Sea. The methane concentrations in marine sediments display a downhole increasing trend and their carbon isotopic compositions (δ ¹³C = −25 to −51‰) indicate a thermogenic origin. Pore water Cl⁻ concentrations show a range from 537 to 730 mM, and the high Cl⁻ samples also have higher concentrations of Br⁻, Na⁺, K⁺, and Mg²⁺, implying mixing between normal seawater and brine in the basin. The SO₄ ²⁻ concentrations of pore waters vary from 19.9 to 36.8 mM, and show a downhole decreasing trend. Calculated SMI (sulfate-methane interfaces) depths and sulfate gradients are between 21 and 47 mbsf, and between −0.7 and −1.7 mM/m, respectively, which are similar to values in gas hydrate locations worldwide and suggest a high methane flux in the basin. Overall, the geochemical data, together with geological and geophysical evidence, such as the high sedimentation rates, high organic carbon contents, thick sediment piles, salt and mud diapirs, active faulting, abundant thermogenic gases, and occurrence of huge bottom simulating reflector (BSR), are suggestive of a favorable condition for occurrence of gas hydrates in this region.     

Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.     

Prototype measurements and small-scale model tests of wave overtopping at shallow rubble-mound breakwaters: the Ostia-Rome yacht harbour case

The paper presents the comparison between the results of small-scale model tests and prototype measurements of wave overtopping at a rubble-mound breakwater. The specific structure investigated is the west breakwater of the yacht harbour of Rome at Ostia (Italy) and is characterized by a gentle seaward slope (1/4) and by a long, shallow foreshore. The laboratory tests firstly aimed at carefully reproducing two measured storms in which overtopping occurred and was measured. The tests have been carried out in two independent laboratories, in a wave flume and in a wave basin, hence using a two-dimensional (2-D) and a three-dimensional (3-D) setup. In the 2-D laboratory tests no overtopping occurred during the storm reproductions; in the 3-D case discharges five to ten times smaller than those observed in prototype have been measured. This indicates the existence of model and scale effects. These effects have been discussed on the basis of the results of several parametric tests, which have been carried out in both laboratories, in addition to the storm reproductions, varying wave and water level characteristics. Final comparison of all the performed tests with 86 prototype measurements still suggests the existence of scale and model effects that induce strong underestimation of overtopping discharge at small scale. The scale reproduction of wave breaking on the foreshore, together with the 3-D features of the prototype conditions and the absence of wind stress in the laboratory measurements, have been individuated as the main sources of scale and model effects. The paper also provides a comparison between the data and a largely used formula for wave overtopping discharges in the presence of structures similar to the one at hand. The suitable value of a roughness factor that appears in that formula is investigated and good agreement is found with other recent researches on rubble-mound breakwaters.     

A predictive numerical model for potential mapping of the gas hydrate stability zone in the Gulf of Cadiz

This paper presents a computational model for mapping the regional 3D distribution in which seafloor gas hydrates would be stable, that is carried out in a Geographical Information System (GIS) environment. The construction of the model is comprised of three primary steps, namely: (1) the construction of surfaces for the various variables based on available 3D data (seafloor temperature, geothermal gradient and depth-pressure); (2) the calculation of the gas function equilibrium functions for the various hydrocarbon compositions reported from hydrate and sediment samples; and (3) the calculation of the thickness of the hydrate stability zone. The solution is based on a transcendental function, which is solved iteratively in a GIS environment.The model has been applied in the northernmost continental slope of the Gulf of Cadiz, an area where an abundant supply for hydrate formation, such as extensive hydrocarbon seeps, diapirs and fault structures, is combined with deep undercurrents and a complex seafloor morphology. In the Gulf of Cadiz, the model depicts the distribution of the base of the gas hydrate stability zone for both biogenic and thermogenic gas compositions, and explains the geometry and distribution of geological structures derived from gas venting in the Tasyo Field (Gulf of Cadiz) and the generation of BSR levels on the upper continental slope.     

Geochemical overview and undiscovered gas resources generated from Hamitabat petroleum system in the Thrace Basin,Turkey

Since the first drill in 1957, three oil, 19 gas and condensate fields have been discovered in the Thrace Basin. However, any petroleum system with its essential elements and processes has not been assigned yet. This study consists of two parts, (1) geochemical overview of the previous work in order to get a necessary help to construct a petroleum system and (2) calculation of quantitative undiscovered hydrocarbon resources generated from this system. An extensive overview study showed that the primary reservoir and source rocks in the Thrace Basin are the Middle Eocene Hamitabat sandstones and shales, respectively, hence it appears that the most effective petroleum system of the Thrace Basin becomes the Hamitabat (!) petroleum system. Currently, 18.5 billion m³ of in-place gas, 2.0 million m³ (12.7 million bbl) in-place waxy oil as well as minor amount of associated condensate were discovered from this system. This study showed that the regional distribution of the oil and gas fields almost overlapped with the previously constructed pod of active Hamitabat shales implying that short and up-dip vertical migration pathway of hydrocarbons from the source to trapping side was available. Thermal model demonstrated that hydrocarbon generation from the Hamitabat shales commenced in the Early Miocene. The amount of quantitative gas generation based on the mean-original TOC = 0.94 wt%, mean-original HI = 217 HC/g TOC and the volume of the pod of active source rock = 49 km³ is approximately 110 billion m³ of gaseous hydrocarbons that results in a high generation–accumulation efficiency of 17% when 18.5 billion m³ of already discovered hydrocarbons are considered.     

The thermal structure of the Dvurechenskii mud volcano and its implications for gas hydrate stability and eruption dynamics

The sediment temperature distribution at mud volcanoes provides insights into their activity and into the occurrence of gas hydrates. If ambient pressure and temperature conditions are close to the limits of the gas hydrate stability field, the sediment temperature distribution not only limits the occurrence of gas hydrates, but is itself influenced by heat production and consumption related to the formation and dissociation of gas hydrates. Located in the Sorokin Trough in the northern Black Sea, the Dvurechenskii mud volcano (DMV) was in the focus of detailed investigations during the M72/2 and M73/3a cruises of the German R/V Meteor and the ROV Quest 4000 m in February and March 2007. A large number of in-situ sediment temperature measurements were conducted from the ROV and with a sensor-equipped gravity corer. Gas hydrates were sampled in pressurized cores using a dynamic autoclave piston corer (DAPC). The thermal structure of the DMV suggests a regime of fluid flow at rates decreasing from the summit towards the edges of the mud volcano, accompanied by intermittent mud expulsion at the summit. Modeled gas hydrate dissociation temperatures reveal that the gas hydrates at the DMV are very close to the stability limits. Changes in heat flow due to variable seepage rates probably do not result in changes in sediment temperature but are compensated by gas hydrate dissociation and formation.     

Provenance of deep-water reservoir sandstones from the Jubarte oil field,Campos Basin,Eastern Brazilian Margin

The provenance of the Maastrichtian deep-water reservoir sandstones from the Jubarte oil field (Campos Basin, eastern Brazil), was studied using an integrated approach that included quantitative petrography, conventional heavy mineral analysis, garnet mineral chemistry and zircon geochronology. The reservoirs are predominantly coarse, poorly-sorted sandstones with feldspathic composition derived from uplifted basement terrains. The fourth- and fifth-order depositional sequences analyzed show no major variations in composition or in provenance through time. However, variations in apatite:tourmaline presents potential to be used as a parameter for sandstone correlation within the field. The composition of heavy minerals indicates derivation from high temperature and low-to-medium pressure aluminous metapelitic rocks, from granites and subordinate mafic rocks, derived from the Cabo Frio Tectonic Domain and the Oriental terrain of Ribeira orogen, characterizing a supply route from SW to NE. The low ZTR index, as well as the absence of low-grade stable heavy minerals and of metasedimentary rock fragments, suggest that by the end of Cretaceous all supracrustal, low-grade terrains had already been totally eroded, and that plutonic, infracrustal rocks were exposed, similarly to the present situation.     

热带风暴过程中珊瑚礁坪示踪砂运移的现场实验研究

１９９５年１０月在小东海珊瑚礁海岸的礁坪上进行了示踪砂运动的现场实验。本次实验对浪,流以及示踪砂采样作了同步观测。根据所获的实验数据,分析在９５１６号热带风暴天气过程礁坪上示踪砂运移的基本规律。在一级近似下,测定并计算了泥沙在波生流作用下的漂移速度与流速比因子０．００２,混合深度小于２ｃｍ。这一结果与其它已往结果相比明显小得多。     

Distribution and expression of gas seeps in a gas hydrate province of the northeastern Sakhalin continental slope, Sea of Okhotsk

Multidisciplinary surveys were conducted to investigate gas seepage and gas hydrate accumulation on the northeastern Sakhalin continental slope (NESS), Sea of Okhotsk, during joint Korean–Russian–Japanese expeditions conducted from 2003 to 2007 (CHAOS and SSGH projects). One hundred sixty-one gas seeps were detected in a 2000 km² area of the NESS (between 53°45′N and 54°45′N). Active gas seeps in a gas hydrate province on the NESS were evident from features in the water column, on the seafloor, and in the subsurface: well-defined hydroacoustic anomalies (gas flares), side-scan sonar structures with high backscatter intensity (seepage structures), bathymetric structures (pockmarks and mounds), gas- and gas-hydrate-related seismic features (bottom-simulating reflectors, gas chimneys, high-amplitude reflectors, and acoustic blanking), high methane concentrations in seawater, and gas hydrates in sediment near the seafloor. These expressions were generally spatially related; a gas flare would be associated with a seepage structure (mound), below which a gas chimney was present. The spatial distribution of gas seeps on the NESS is controlled by four types of geological structures: faults, the shelf break, seafloor canyons, and submarine slides. Gas chimneys that produced enhanced reflection on high-resolution seismic profiles are interpreted as active pathways for upward gas migration to the seafloor. The chimneys and gas flares are good indicators of active seepage.     

古新世—始新世最热事件对地球表层循环的影响及其触发机制

古新世—始新世最热事件（PETM, Paleocene Eocene Thermal Maximum）是发生在古新世—始新世交界时的一次全球性的气候突变事件。它造成了大洋环流模式的突然倒转和海水盐度、大气湿度的迅速上升。海洋表层生态系统和陆地生态系统生产力迅速上升,许多属种的植物、动物、微生物生活范围向高纬区扩大;大洋底栖微生物发生集群灭绝。现代哺乳动物的主要属种（灵长类、奇蹄类及偶蹄类）产生,哺乳动物演化进程发生重大改变。地球表层碳循环系统发生不同程度的碳同位素负偏移,全球碳循环系统发生大规模搅动。对于PETM的触发机制,主流的观点认为是海底天然气水合物突然释放造成巨量甲烷迅速进入表层系统引发的碳循环系统内部反馈。而对于甲烷释放的原因,又存在着减压释放和热释放两种解释;此外还有科学家用岩浆作用和地外星体撞击来解释PETM的发生。