Gas hydrates in shallow deposits of the Amsterdam mud volcano, Anaximander Mountains, Northeastern Mediterranean Sea

We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C₁/C₂₊ ratios <35 and δ¹³C-CH₄ values of ?50.6‰. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas–sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO ₄ ^2? and Ba²⁺ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.     

Mud volcanoes and gas hydrates in the Black Sea: new data from Dvurechenskii and Odessa mud volcanoes

Meteor cruise M52/1 documented the presence of gas hydrates in sediments from mud volcanoes in the Sorokin Trough of the Black Sea. In a mud flow on the Odessa mud volcano, a carbonate crust currently forms in association with anaerobic methane oxidation. Dvurechenskii mud volcano (DMV), a flat-topped mud pie-type structure, appeared to be very active. Pore water in sediments of DMV is enriched in several constituents, such as ammonium and chloride, which seem to originate at depth. High sediment temperatures of up to 16.5 °C in close contact to the ambient bottom water of 9 °C also suggest strong advective transport of material from greater depth. Steep temperature gradients indicate a high fluid and/or mud flux within DMV, which is confirmed by the shape of the pore water profiles. Active fluid expulsion sites are evidenced by direct seafloor observation, and a potential flux of methane from the sediment to the bottom water is indicated by water-column methane measurements.     

南海东沙海域天然气水合物与地质构造的关系

构造作用和构造过程是控制天然气水合物发育和赋存的重要地质因素之一。陆坡区复杂的构造运动能够形成良好的气体运移通道以及欠压实、高孔隙的水合物储集空间。东沙群岛邻近海域具有水深变化大、沉积厚度大、沉积速率高和有机质丰富等天然气水合物有利赋存条件,最新的研究已经在该海域发现了天然气水合物赋存的地球物理证据BSR,针对东沙群岛海域广泛发育的断裂、底辟、海底滑坡等构造,开展了其与天然气水合物成藏的关系研究,可以进一步深入了解天然气水合物在东沙群岛不同地质构造中的分布特征与演化,为该区天然气远景评估提供参考。     

Mud volcanoes and gas hydrates in the Anaximander mountains (Eastern Mediterranean Sea)

Detailed multibeam, sedimentological, and geophysical surveys provide ample new data to confirm that the Anaximander Mountains (Eastern Mediterranean) are an important area for active mud volcanism and gas hydrate formation. More than 3000 km of multibeam track length was acquired during two recent missions and 80 gravity and box cores were recovered. Morphology and backscatter data of the study area have better resolution than previous surveys, and very detailed morphology maps have been made of the known targeted mud volcanoes (Amsterdam, Kazan and Kula), especially the Amsterdam “crater” and the related mud breccia flows. Gas hydrates collected repeatedly from a large area of Amsterdam mud volcano at a sub-bottom depth of around 0.3–1.5 m resemble compacted snow and have a rather flaky form. New gas hydrate sites were found at Amsterdam mud volcano, including the mud flow sloping off to the south. Gas hydrates sampled for the first time at Kazan mud volcano are dispersed throughout the core samples deeper than 0.3 m and display a ‘rice’-like appearance. Relative chronology and AMS dating of interbedded pelagic sediments (Late Holocene hemipelagic, sapropel layer S1 and ash layers) within the mud flows indicate that successive eruptions of Kula mud volcano have a periodicity of about 5–10 kyrs. New mud volcanoes identified on the basis of multibeam backscatter intensity were sampled, documented as active and named “Athina” and “Thessaloniki”. Gas hydrates were sampled also in Thessaloniki mud volcano, the shallowest (1264 m) among all the active Mediterranean sites, at the boundary of the gas hydrate stability zone. Biostratigraphical analyses of mud breccia clasts indicated that the source of the subsurface sedimentary sequences consists of Late Cretaceous limestones, Paleocene siliciclastic rocks, Eocene biogenic limestones and Miocene mudstones. Rough estimations of the total capacity of the Anaximander mud volcanoes in methane gas are 2.56–6.40 km³.     

冲绳海槽天然气水合物与地质构造的关系

海底天然气水合物大多与通过切穿沉积盖层的断裂的上升烃类流体相关,这些高渗透带包括底辟和泥火山等侵入构造,所以海底断裂、底辟和泥火山等构造周围可能赋存天然气水合物;其次,高沉积速率和巨厚沉积层可使有机质迅速掩埋而保存起来,为天然气水合物的生成提供充足物源,因此,邻近陆坡河谷口的海底沉积扇也是天然气水合物赋存的有利地区;另外,由于陆坡区的水合物沉积层比海盆更容易受外界温压变化的影响发生失稳分解,诱发海底滑坡,所以滑坡与天然气水合物赋存之间的关系也非常密切。冲绳海槽邻近海域具有覆水深、沉积厚度大、沉积速率高和有机质丰富等有利赋存条件,目前的研究已经在该海域发现了天然气水合物赋存的地球物理证据BSR,因此,在现有研究基础上开展断裂、泥火山、海底扇、海底滑坡等与天然气水合物相关的构造研究,可以深入了解天然气水合物在不同地质构造中的分布特征与演化,为更精确地评估其资源潜力提供参考。     

Raman spectroscopic and calorimetric observations on natural gas hydrates with cubic structures I and II obtained from Lake Baikal

This study reports measurements of the Raman spectra of Lake Baikal gas hydrates and estimations of the hydration number of methane-rich samples. The hydration number of gas hydrates retrieved from the southern Baikal Basin (crystallographic structure I) was approx. 6.1. Consistent with previous results, the Raman spectra of gas hydrates retrieved from the Kukuy K-2 mud volcano in the central Baikal Basin indicated the existence of crystallographic structures I and II. Measurements of the dissociation heat of Lake Baikal gas hydrates by calorimetry (from the decomposition of gas hydrates to gas and water), employing the hydration number, revealed values of 53.7–55.5?kJ?mol^–1 for the southern basin samples (structure I), and of 54.3–55.5?kJ?mol^–1 for the structure I hydrates and 62.8–64.2?kJ?mol^–1 for the structure II hydrates from the Kukuy K-2 mud volcano.     

Thermal anomalies associated with shallow gas hydrates in the K-2 mud volcano, Lake Baikal

Thermal measurements and hydrate mapping in the vicinity of the K-2 mud volcano in Lake Baikal have revealed a particular type of association of thermal anomalies (29–121?mW?m^–2) near hydrate-forming layers. Detailed coring within K-2 showed that hydrates are restricted to two distinct zones at sub-bottom depths exceeding 70–300?cm. Temperature data from stations with hydrate recovery and degassing features all display low thermal gradients. Otherwise, the thermal gradients within the mud volcano are generally increased. These findings imply a more complicated thermal regime than often assumed for mud volcanoes, with important roles for both fluids and hydrates. The coexistence of neighbouring low and high thermal anomalies is interpreted to result from discharging and recharging fluid activity, rather than hydrate thermodynamics. It is suggested that hydrates play a key role in controlling the fluid circulation pattern at an early stage. At a later stage, the inflow of undersaturated lake water would favour the dissolution of structure I hydrates and the formation of structure II hydrates, the latter having been observed on top of structure I hydrates in the K-2 mud volcano.     

Gas hydrate accumulation at the Håkon Mosby Mud Volcano

Gas hydrate (GH) accumulation is characterized and modeled for the Håkon Mosby mud volcano, ca. 1.5?km across, located on the Norway–Barents–Svalbard margin. Pore water chemical and isotopic results based on shallow sediment cores as well as geothermal and geomorphological data suggest that the GH accumulation is of a concentric pattern controlled by and formed essentially from the ascending mud volcano fluid. The gas hydrate content of sediment peaks at 25% by volume, averaging about 1.2% throughout the accumulation. The amount of hydrate methane is estimated at ca. 10⁸?m³ STP, which could account for about 1–10% of the gas that has escaped from the volcano since its origin.     

Vodyanitskii mud volcano,Sorokin trough,Black Sea: Geological characterization and quantification of gas bubble streams

Vodyanitskii mud volcano is located at a depth of about 2070 m in the Sorokin Trough, Black sea. It is a 500-m wide and 20-m high cone surrounded by a depression, which is typical of many mud volcanoes in the Black Sea. 75 kHz sidescan sonar show different generations of mud flows that include mud breccia, authigenic carbonates, and gas hydrates that were sampled by gravity coring. The fluids that flow through or erupt with the mud are enriched in chloride (up to ∼650 mmol L⁻¹ at ∼150-cm sediment depth) suggesting a deep source, which is similar to the fluids of the close-by Dvurechenskii mud volcano. Direct observation with the remotely operated vehicle Quest revealed gas bubbles emanating at two distinct sites at the crest of the mud volcano, which confirms earlier observations of bubble-induced hydroacoustic anomalies in echosounder records. The sediments at the main bubble emission site show a thermal anomaly with temperatures at ∼60 cm sediment depth that were 0.9 °C warmer than the bottom water. Chemical and isotopic analyses of the emanated gas revealed that it consisted primarily of methane (99.8%) and was of microbial origin (δD-CH₄ = −170.8‰ (SMOW), δ¹³C-CH₄ = −61.0‰ (V-PDB), δ¹³C-C₂H₆ = −44.0‰ (V-PDB)). The gas flux was estimated using the video observations of the ROV. Assuming that the flux is constant with time, about 0.9 ± 0.5 × 10⁶ mol of methane is released every year. This value is of the same order-of-magnitude as reported fluxes of dissolved methane released with pore water at other mud volcanoes. This suggests that bubble emanation is a significant pathway transporting methane from the sediments into the water column.     

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.     

The Norwegian–Barents–Svalbard (NBS) continental margin: Introducing a natural laboratory of mass wasting, hydrates, and ascent of sediment, pore water, and methane

Side-scan sonar mapping and ground-truthing of the Norwegian–Barents–Svalbard continental margin shed new light on shelf glaciation, mass wasting, hydrates, and features like the Håkon Mosby mud volcano (HMMV), reflecting upward mobility of gas, pore fluids, and sediments. Detailed HMMV examination revealed thermal gradients to 10°/m, bottom-water CH₄ and temperature anomalies, H₂S- and CH₄-based chemosynthetic ecosystems, and subbottom methane hydrate (to 25%). Seismic and chemical data suggest HMMV origins at 2–3?km depth within the 6-km-thick depocenter. The HMMV and mound fields bordering the Bjørnøyrenna slide valley and pockmarks bordering the Storegga slide may all have formed in response to sediment failure.     

流体迁移和海底地形与天然气水合物的形成

使用重力取样器、渔网、深潜器等手段,已经在海底及以下浅表层的区域采获天然气水合物样品,但关于浅表层水合物的发育机制、分布规律、与海底地形的关系等问题还缺乏基本认识。根据2006年鄂霍次克海天然气水合物调查航次的调查数据,发现萨哈林东北陆坡区,特别是中、下陆坡区发育大量海底凸起。这些凸起一般呈不对称的丘形,宽几百米,高几十米。与海底沙波、沙脊不同,海底凸起为孤立海底地形,在南北方向上并不连续。海底剖面仪结果清楚地显示古陆坡凸起的发育。现今海底陆坡凸起的幅度普遍地要小于古陆坡凸起的幅度,个别地方古今陆坡凸起的形态有所变化,但大部分古、今陆坡凸起是一一对应的,基本形态没有根本变化。在萨哈林陆坡地区存在两个方向的挤压应力场,分别是由德鲁根盆地向萨哈林陆坡方向的挤压应力场和萨哈林陆坡沿萨哈林走滑断裂向南的挤压应力场,海底陆坡凸起是这两大应力场复合作用的结果。浊反射区中的游离气是底辟构造中的超高压多相物质向上迁移形成的,浊反射区上方对应的海底凸起应该是宏观构造挤压和局部底辟发育叠合的结果,浊反射区上方的海底凸起,在形态等方面应该和其他仅由挤压构造原因形成的凸起有所区别,比如顶部发育裂口等。在底辟构造中,由于游离气体的向上迁移,在整个水合物稳定域中从下到上,直至海底都可能形成水合物。     

南海东北部陆坡天然气水合物区的滑塌和泥火山活动

本文研究了南海东北部陆坡天然气水合物区滑塌和泥火山活动的特征及表现形式,探讨了滑塌和泥火山活动对天然气水合物成藏的影响,提出了滑塌主导和滑塌、泥火山共同作用两种控制模式。根据地震数据、浅层剖面和海底地形数据解释,将研究区划分为规则滑塌区和泥火山活动影响区,并识别出泥火山、泥火山脊、凹槽、凹坑等特征地形。滑塌和泥火山活动是陆坡天然气水合物发育区重要的地形控制因素,两种活动共同作用产生复杂的地形特征。综合多条地震测线中似海底反射层(BSR)形态、连续性和滑塌、泥火山活动的关系,认为滑塌控制的区域,BSR连续,天然气水合物储藏较完整,泥火山活动区天然气水合物储藏也仅受到局部破坏。同时指出滑塌和泥火山活动对研究区长期天然气渗漏活动具有重要作用。     

Gas hydrates and active mud volcanism on the South Shetland continental margin, Antarctic Peninsula

During the Antarctic summer of 2003–2004, new geophysical data were acquired from aboard the R/V OGS Explora in the BSR-rich area discovered in 1996–1997 along the South Shetland continental margin off the Antarctic Peninsula. The objective of the research program, supported by the Italian National Antarctic Program (PNRA), was to verify the existence of a potential gas hydrate reservoir and to reconstruct the tectonic setting of the margin, which probably controls the extent and character of the diffused and discontinuous bottom simulating reflections. The new dataset, i.e. multibeam bathymetry, seismic profiles (airgun and chirp), and two gravity cores analysed by computer-aided tomography as well as for gas composition and content, clearly shows active mud volcanism sustained by hydrocarbon venting in the region: several vents, located mainly close to mud volcanoes, were imaged during the cruise and their occurrence identified in the sediment samples. Mud volcanoes, vents and recent slides border the gas hydrate reservoir discovered in 1996–1997. The cores are composed of stiff silty mud. In core GC01, collected in the proximity of a mud volcano ridge, the following gases were identified (maximum contents in brackets): methane (46 μg/kg), pentane (45), ethane (35), propane (34), hexane (29) and butane (28). In core GC02, collected on the flank of the Vualt mud volcano, the corresponding data are methane (0 μg/kg), pentane (45), ethane (22), propane (0), hexane (27) and butane (25).     

Comparison of marine gas hydrates in sediments of an active and passive continental margin

Two sites of the Deep Sea Drilling Project in contrasting geologic settings provide a basis for comparison of the geochemical conditions associated with marine gas hydrates in continental margin sediments. Site 533 is located at 3191 m water depth on a spit-like extension of the continental rise on a passive margin in the Atlantic Ocean. Site 568, at 2031 m water depth, is in upper slope sediment of an active accretionary margin in the Pacific Ocean. Both sites are characterized by high rates of sedimentation, and the organic carbon contents of these sediments generally exceed 0.5%. Anomalous seismic reflections that transgress sedimentary structures and parallel the seafloor, suggested the presence of gas hydrates at both sites, and, during coring, small samples of gas hydrate were recovered at subbottom depths of 238m (Site 533) and 404 m (Site 568). The principal gaseous components of the gas hydrates wer methane, ethane, and CO₂. Residual methane in sediments at both sites usually exceeded 10 mll^?1 of wet sediment. Carbon isotopic compositions of methane, CO₂, and ΣCO₂ followed parallel trends with depth, suggesting that methane formed mainly as a result of biological reduction of oxidized carbon. Salinity of pore waters decreased with depth, a likely result of gas hydrate formation. These geochemical characteristics define some of the conditions associated with the occurrence of gas hydrates formed by in situ processes in continental margin sediments.     

Characteristics of the bottom simulating reflectors near mud diapirs: offshore southwestern Taiwan

Single-channel seismic recording was carried out off the southwestern coast of Taiwan. Six characteristic seismic facies associated with bottom simulating reflectors (BSRs) and mud diapirs are identified. The existence of reflections which mimic the seafloor, the reverse polarity, weak amplitude blocks, and strong diffraction patterns around the mud diapirs all suggest that gas hydrates exist in the deep-water regions. The bases of the hydrate stability zones upturn in the vicinity of mud volcanoes. The high heat flows of mud volcanoes provide heat sources which destabilize the gas hydrates and upturn the BSRs. Received: 24 March 1999 / Revision accepted: 10 December 1999     

Gas hydrates that outcrop on the sea floor: stability models

 The detection of sea-floor gas hydrates (GHs) proves that they can coexist in contact with seawater. We calculate that sea-floor hydrates undergo rapid dissolution, yet they are maintained by the constant high rate of upward migration of gas-saturated waters. If upward migration originates from a point source, then the thickness of sea-floor hydrates varies with distance from the center of the upwelling (depending on heat flow). However, near-surface fracturing may control the actual points of exit onto the sea floor above. If gas migration rates decrease from the center of the mud volcano to its periphery, a concentric pattern in distribution of temperature, methane concentration, and GH contents can be described.     

Gas hydrate disturbance fabrics of southern Hydrate Ridge sediments (ODP Leg 204): Relationship with texture and physical properties

Soupy and mousse-like fabrics are disturbance sedimentary features that result from the dissociation of gas hydrate, a process that releases water. During the core retrieval process, soupy and mousse-like fabrics are produced in the gas hydrate-bearing sediments due to changes in pressure and temperature conditions. Therefore, the identification of soupy and mousse-like fabrics can be used as a proxy for the presence of gas hydrate in addition to other evidence, such as pore water freshening or anomalously cool temperature. We present here grain-size results, mineralogical composition and magnetic susceptibility data of soupy and mousse-like samples from the southern Hydrate Ridge (Cascadia accretionary complex) acquired during Leg 204 of the Ocean Drilling Program. In order to study the relationship between sedimentary texture and the presence of gas hydrates, we have compared these results with the main textural and compositional data available from the same area. Most of the disturbed analyzed samples from the summit and the western flank of southern Hydrate Ridge show a mean grain size coarser than the average mean grain size of the hemipelagic samples from the same area. The depositional features of the sediments are not recognised due to disturbance. However, their granulometric statistical parameters and distribution curves, and magnetic susceptibility logs indicate that they correspond to a turbidite facies. These results suggest that gas hydrates in the southern Hydrate Ridge could form preferentially in coarser grain-size layers that could act as conduits feeding gas from below the BSR. Two samples from the uppermost metres near the seafloor at the summit of the southern Hydrate Ridge show a finer mean grain-size value than the average of hemipelagic samples. They were located where the highest amount of gas hydrates was detected, suggesting that in this area the availability of methane gas was high enough to generate gas hydrates, even within low-permeability layers. The mineralogical composition of the soupy and mousse-like sediments does not show any specific characteristic with respect to the other samples from the southern Hydrate Ridge.     

The characteristics of gas hydrates recovered from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

Systematic analyses have been carried out on two gas hydrate-bearing sediment core samples, HYPV4, which was preserved by CH₄ gas pressurization, and HYLN7, which was preserved in liquid-nitrogen, recovered from the BPXA-DOE-USGS Mount Elbert Stratigraphic Test Well. Gas hydrate in the studied core samples was found by observation to have developed in sediment pores, and the distribution of hydrate saturation in the cores imply that gas hydrate had experienced stepwise dissociation before it was stabilized by either liquid nitrogen or pressurizing gas. The gas hydrates were determined to be structure Type I hydrate with hydration numbers of approximately 6.1 by instrumentation methods such as powder X-ray diffraction, Raman spectroscopy and solid state ¹³C NMR. The hydrate gas composition was predominantly methane, and isotopic analysis showed that the methane was of thermogenic origin (mean δ¹³C = −48.6‰ and δ_D = −248‰ for sample HYLN7). Isotopic analysis of methane from sample HYPV4 revealed secondary hydrate formation from the pressurizing methane gas during storage.     

Potential for gas hydrate formation at the northwest New Zealand shelf margin - New insights from seismic reflection data and petroleum systems modelling

In this study we provide evidence for methane hydrates in the Taranaki Basin, occurring a considerable distance from New Zealand's convergent margins, where they are well documented. We describe and reconstruct a unique example of gas migration and leakage at the edge of the continental shelf, linking shallow gas hydrate occurrence to a deeper petroleum system. The Taranaki Basin is a well investigated petroleum province with numerous fields producing oil and gas. Industry standard seismic reflection data show amplitude anomalies that are here interpreted as discontinuous BSRs, locally mimicking the channelized sea-floor and pinching out up-slope. Strong reverse polarity anomalies indicate the presence of gas pockets and gas-charged sediments. PetroMod™ petroleum systems modelling predicts that the gas is sourced from elevated microbial gas generation in the thick slope sediment succession with additional migration of thermogenic gas from buried Cretaceous petroleum source rocks. Cretaceous–Paleogene extensional faults underneath the present-day slope are interpreted to provide pathways for focussed gas migration and leakage, which may explain two dry petroleum wells drilled at the Taranaki shelf margin. PetroMod™ modelling predicts concentrated gas hydrate formation on the Taranaki continental slope consistent with the anomalies observed in the seismic data. We propose that a semi-continuous hydrate layer is present in the down-dip wall of incised canyons. Canyon incision is interpreted to cause the base of gas hydrate stability to bulge downward and thereby trap gas migrating up-slope in permeable beds due to the permeability decrease caused by hydrate formation in the pore space. Elsewhere, hydrate occurrence is likely patchy and may be controlled by focussed leakage of thermogenic gas. The proposed presence of hydrates in slope sediments in Taranaki Basin likely affects the stability of the Taranaki shelf margin. While hydrate presence can be a drilling hazard for oil and gas exploration, the proposed presence of gas hydrates opens up a new frontier for exploration of hydrates as an energy source.