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.     

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.     

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。     

Seep mounds on the Southern Vøring Plateau (offshore Norway)

Multidisciplinary study of seep-related structures on Southern Vøring Plateau has been performed during several UNESCO/IOC TTR cruises on R/V Professor Logachev. High-resolution sidescan sonar and subbottom profiler data suggest that most of the studied fluid discharge structures have a positive relief at their central part surrounded by depression. Our data shows that the present day fluid activity is concentrated on the top of these “seep mounds”. Number of high hydrocarbon (HC) gas saturated sediment cores and 5 cores with gas hydrate presence have been recovered from these structures. δ¹³C of methane (between −68 and −94.6‰ VPDB) and dry composition of the gas points to its biogenic origin. The sulfate depletion generally occurs within the upper 30–200 cm bsf and usually coincides with an increase of methane concentration. Pore water δ¹⁸O ranges from 0.29 to 1.14‰ showing an overall gradual increase from bottom water values (δ¹⁸O ∼ 0.35‰). Although no obvious evidence of fluid seepage was observed during the TV surveys, coring data revealed a broad distribution of living Pogonophora and bacterial colonies on sea bottom inside seep structures. These evidences point to ongoing fluid activity (continuous seepage of methane) through these structures. From other side, considerable number and variety of chemosynthetic macro fauna with complete absence of living species suggest that present day level of fluid activity is significantly lower than it was in past. Dead and subfossil fauna recovered from various seep sites consist of solemyid (Acharax sp.), thyasirid and vesicomyid (cf. Calyptogena sp.) bivalves belonging to chemosymbiotic families. Significant variations in δ¹³C (−31.6‰ to −59.2‰) and δ¹⁸O (0.42‰ and 6.4‰) of methane-derived carbonates collected from these structures most probably related to changes in gas composition and bottom water temperature between periods of their precipitation. This led us to ideas that: (1) seep activity on the Southern Vøring Plateau was started with large input of the deep thermogenic gas and gradually decries in time with increasing of biogenic constituent; (2) authigenic carbonate precipitation started at the near normal deep sea environments with bottom water temperature around +5 °C and continues with gradual cooling up to negative temperatures recording at present time.     

Authigenic carbonates from the eastern Black Sea as an archive for shallow gas hydrate dynamics – Results from the combination of CT imaging with mineralogical and stable isotope analyses

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area (“Batumi seep area”) located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups.     

Seabed morphology and gas venting features in the continental slope region of Krishna–Godavari basin,Bay of Bengal: Implications in gas-hydrate exploration

Increased oil and gas exploration activity has led to a detailed investigation of the continental shelf and adjacent slope regions of Mahanadi, Krishna–Godavari (KG) and Cauvery basins, which are promising petroliferous basins along the eastern continental margin of India. In this paper, we analyze the high resolution sparker, subbottom profiler and multibeam data in KG offshore basin to understand the shallow structures and shallow deposits for gas hydrate exploration. We identified and mapped prominent positive topographic features in the bathymetry data. These mounds show fluid/gas migration features such as acoustic voids, acoustic chimneys, and acoustic turbid layers. It is interesting to note that drilling/coring onboard JOIDES in the vicinity of the mounds show the presence of thick accumulation of subsurface gas hydrate. Further, geological and geochemical study of long sediment cores collected onboard Marion Dufresne in the vicinity of the mounds and sedimentary ridges shows the imprints of paleo-expulsion of methane and sulfidic fluid from the seafloor.     

西气东输管道工程中卫黄河穿越隧道场地工程地质条件评价

西气东输工程中卫黄河穿越隧道长1197.77m,高4.3m,宽5.6m。隧道入口高于黄河水位28m,出口高于黄河水位45m。隧道顶板高程为1130m。位于黄河水下100m。隧道场地围岩为寒武系磨盘井组灰绿色、银灰色浅变质中厚层细粒长石石英砂岩、千枚状板岩、绢云母化千枚岩。围岩为弱风化Ⅲ～Ⅳ类岩石。透水率为4～67Lu,纵波波速为500～3300m.s-1。BQ为300～400。变形模量为6.11～9.22GPa。泊松比（）0.14～0.24。内摩擦角（）为42.1～44.7。地下水为基岩裂隙水。含水层为寒武系浅变质岩,受大气降水渗入补给,单井涌水量为1.0～50m3.d-1。隧道轴线穿越区岩体较完整较破碎,未有全新活动断层。隧道位置选择和开挖深度设计是可行的。施工和长期运营是安全的。