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.     

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.     

Acoustic investigations of mud volcanoes in the Sorokin Trough, Black Sea

The Sorokin Trough (Black Sea) is characterized by diapiric structures formed in a compressional tectonic regime that facilitate fluid migration to the seafloor. We present acoustic data in order to image details of mud volcanoes associated with the diapirs. Three types of mud volcanoes were distinguished: cone-shaped, flat-topped, and collapsed structures. All mud volcanoes, except for the Kazakov mud volcano, are located above shallow mud diapirs and diapiric ridges. Beyond the known near-surface occurrence of gas hydrates, bottom simulating reflectors are not seen on our seismic records, but pronounced lateral amplitude variations and bright spots may indicate the presence of gas hydrates and free gas.     

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     

Anomalous seismic reflections related to gas/gas hydrate occurrences along the western continental margin of India

Gas hydrates along continental margins are commonly inferred from the presence of bottom simulating reflectors (BSRs) on reflection seismic records. Shale and mud diapirs are often observed in the proximity of BSR-inferred gas hydrates. Analysis of data from documented gas-hydrate occurrences suggests that the areas where mud volcanoes exist on the seafloor are promising locations for sediments with high gas-hydrate concentration. Along the western continental margin of India (WCMI), we have identified several anomalous reflections on single-channel, analogue seismic records in the proximity of BSRs, from which the presence of gas-charged sediments and gas seepages was inferred. These features characterize both the shelf-slope region of the WCMI and the adjoining deep-sea areas. The seismic records also reveal mud/shale diapiric activity and pockmarks near the gas hydrates.     

Geophysical evidence of mud diapirism on the Mediterranean Ridge accretionary complex

Mud volcanoes, mud cones, and mud ridges have been identified on the inner portion of the crestal area, and possibly on the inner escarpment, of the Mediterranean Ridge accretionary complex. Four areas containing one or more mud diapirs have been investigated through bathymetric profiling, single channel seismic reflection profiling, heat flow measurements, and coring. A sequence of events is identified in the evolution of the mud diapirs: initially the expulsion on the seafloor of gasrich mud produces a seafloor depression outlined in the seismic record by downward dip of the host sediment reflectors towards the mud conduit; subsequent eruptions of fluid mud may create a flat topped mud volcano with step-like profile; finally, the intrusion of viscous mud produces a mud cone.The origin of the diapirs is deep within the Mediterranean Ridge. Although a minimum depth of about 400 m below the seafloor has been computed from the hydrostatic balance between the diapiric sediments and the host sediments, a maximum depth, suggested by geometric considerations, ranges between 5.3 and 7 km. The presence of thermogenic gas in the diapiric sediments suggests a better constrained origin depth of at least 2.2 km.The heat flow measured within the Olimpi mud diapir field and along a transect orthogonal to the diapiric field is low, ranging between 16 ± 5 and 41 ± 6 mW m^–2. Due to the presence of gas, the thermal conductivity of the diapiric sediments is lower than that of the host hemipelagic oozes (0.6–0.9 and 1.0–1.15 W m^–1 K^–1 respectively).We consider the distribution of mud diapirs to be controlled by the presence of tectonic features such as reverse faults or thrusts (inner escarpment) that develop where the thickness of the Late Miocene evaporites appears to be minimum. An upward migration through time of the position of the décollement within the stratigraphic column from the Upper Oligocene (diapiric sediments) to the Upper Miocene (present position) is identified.     

Gas hydrates from the continental slope,offshore Sakhalin Island,Okhotsk Sea

Ten gas-vent fields were discovered in the Okhotsk Sea on the northeast continental slope offshore from Sakhalin Island in water depths of 620—1040 m. At one vent field, estimated to be more than 250 m across, gas hydrates, containing mainly microbial methane (¹³C = –64.3), were recovered from subbottom depths of 0.3–1.2 m. The sediment, having lenses and bedded layers of gas hydrate, contained 30–40% hydrate per volume of wet sediment. Although gas hydrates were not recovered at other fields, geochemical and thermal measurements suggest that gas hydrates are present.     

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.     

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.     

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.     

Geochemistry of gas hydrate accumulation offshore NE Sakhalin Island (the Sea of Okhotsk): results from the KOMEX-2002 cruise

Geochemical properties of gas hydrate accumulation associated with an active gas vent on the continental slope offshore northeast Sakhalin Island in the Sea of Okhotsk have been investigated. The pore water chemistry data suggest that the gas hydrates (GHs) were formed in an environment of upward-migrating fluid combined with a mechanism of pore water segregation. The upward infiltration of water enriched mainly by Cl^– and K⁺ species appears to occur on the background of earlier diagenesis processes within the gas vent sediments. The GHs were formed from water with chlorinity ranging from 530 to 570 mM. The ¹⁸O and D of GH water varied from –1.4 to –1.8 and from –13 to –18, respectively, representing a mix of seawater and infiltrating fluid water. A complex interaction of pore water, water of ascending fluid and segregated pore water during hydrate formation is also supported by water content measurements and observed gas hydrate structure. The direction of segregated water is opposite to upward fluid migration. Decreasing activity of the gas vent is inferred by comparing the present top of the recovered hydrate layer with previous observations.     

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.     

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.     

Gas and fluid venting at the Makran accretionary wedge off Pakistan

The Makran accretionary complex shows a distinct bottom-simulating reflector, indicating a thick gas-hydrate-bearing horizon between the deformational front and about 1350 m water depth which seals off the upward flow of gas-charged fluids. A field of presently inactive mud diapirs with elevations up to 65 m was discovered in the abyssal plain seawards of the deformation front, suggesting that in the past conditions were favorable for periodic but localized vigorous mud diapirism. Regional destabilization of the gas hydrate leading to focused flow was observed where deep-penetrating, active faults reach the base of the gas-hydrate layer, as in a deeply incised submarine canyon (2100–2500 m water depth). At this location we discovered seeps of methane and H₂S-rich fluids associated with chemoautotrophic vent faunas (e.g., Calyptogena sp.). Driven by the accretionary wedge dynamics, the landward part of the gas-hydrate layer below the Makran margin is being progressively uplifted. Due to reduced hydrostatic pressure and rising ocean bottom-water temperatures, gas hydrates are progressively destabilized and dissociated into hydrate water, methane and H₂S. Sediment temperatures lie outside the methane stability field wherever water depth is less than 800 m. Above this depth, upward migration of fluids to the seafloor is unimpeded, thus explaining the abundance of randomly distributed gas seeps observed at water depths of 350 to 800 m. Received: 14 June 1999 / Revision accepted: 6 February 2000     

Hydrocarbon gases in deposits from mud volcanoes in the Sorokin Trough, north-eastern Black Sea

Hydrocarbon gases were determined in sediments from three mud volcanoes in the Sorokin Trough. In comparison to a reference station outside the mud volcano area, the deposits are characterized by an enrichment of high-molecular hydrocarbons (C₂–C₄), an absence of unsaturated homologues, a predominance of iso-butane in comparison with n-butane, and the presence of gas hydrate. The molecular composition of the hydrocarbon gases suggests their deep sources and thermogenic origin. In the pelagic sediments at the reference station, the methane concentration is relatively low (up to 49 ml/l); maximum concentrations are reached in deposits of the Dvurechenskii mud volcano (up to 400 ml/l). It was the first time that gas hydrate was sampled at the Dvurechenskii mud volcano. The gas extracted by dissociation of hydrate samples was dominated by methane (99.5%) with low amounts of ethane and propane (less than 0.5%). The isotopic composition of the methane varies between –62 and –66 PDB in ¹³C, and between –185 and –209 SMOW in D, indicating a mainly biogenic origin with an admixture of thermogenic gas.     

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.     

Geophysical and geochemical observations on actively seeping hydrocarbon gases on the south-eastern Yellow Sea continental shelf

In the southeastern Yellow Sea, active seepage of hydrocarbon gases has been observed by high-resolution (3.5 kHz) seismic profiling both in 1987 and 2001, occurring through a large number of plumes from the topmost pre-Holocene sedimentary layer. It is strong enough to compensate for current speed, extending vertically up to the sea surface. The gas seepage often appears to be explosive to form craters and diapirs, although pockmarks are rare due to the redistribution of mobile palimpsest sands. In core-top seawater and sediments, the gases are characterized by high amounts of C₂, homogenous ¹³C₁ values and a large difference (19.7 on average) between ¹³C₁ (–55.2 to –53.6 PDB) and ¹³C₂ (–36.8 to –32.5 PDB) values. The gases are considered to be generated with a smaller amount of C₁ at the early thermal cracking stage of labile source materials, after which the C₂ gas is enriched in ¹³C by diffusion or biological alternation at the generation or accumulation site. The homogenous ¹³C₁ values may be one of the geochemical characteristics of gases acquired at depth which are less altered in the case of rapid diffusive gas migration to the seafloor.     

Acoustic evidences of gas in the continental slope sediments of the Gulf of Cadiz (E Atlantic)

Detailed reviews of high-resolution acoustic studies in the continental slope of the Gulf of Cadiz has revealed the following gas-related features: acoustic turbidity and blanking, bright spots, ancient and modern pockmarks, high-amplitude diffractions, acoustic plumes and turbidity in the water column, and BSRs. The origin of the gas is believed to be biogenic and thermogenic. The BSR-like acoustic anomalies occur intermittently in some areas of the upper slope and tend to occur in the volcanoes/diapirs. The pressure–temperature conditions deduced for the location of those acoustic anomalies do not correspond to the conditions of stability of gas hydrates. It is suggested that these volcanoes/diapirs intrusions may locally induce anomalously higher pore pressure conditions on the immediately surrounding sediments, affecting the stability field of the gas hydrates.     

Salt tectonics in the Cap Boujdour Area,Aaiun Basin,NW Africa

Seismic reflection data indicate the Moroccan salt basin extends to the Cap Boujdour area in the Aaiun Basin. Two salt diapir structures have been identified and several areas of collapsed strata indicate probable salt removal at the shelf edge. The presence of salt in this area correlates to the conjugate southern George's Bank Basin and the Baltimore Canyon area, and it is suggested that the salt extends southward from the known salt diapir province in the George's Bank Basin southward to the Great Stone Dome. The paucity of salt diapirs is attributed to the thick carbonate and anhydrite sequence, which was deposited soon after salt deposition that inhibited halokinesis. The presence of salt along this large segment of the Atlantic margin should increase its hydrocarbon potential with traps created around salt diapirs and provision of migration pathways from deep potential source rocks in the early Cretaceous and Jurassic strata to shallower levels.     

Authigenic minerals from the Paola Ridge (southern Tyrrhenian Sea): Evidences of episodic methane seepage

Paola Ridge, along the NW Calabrian margin (southern Tyrrhenian Sea), is one of the few reported deep sea sites of precipitation of authigenic carbonates in the Tyrrhenian Sea. Here, the changing composition of the seeping fluids and the dynamic nature of the seepage induced the precipitation of pyrite, siderite and other carbonate phases. The occurrence of this array of authigenic precipitates is thought to be related to fluctuation of the sulfate-methane transition zone (SMTZ).Concretions of authigenic minerals formed in the near sub-bottom sediments of the Paola Ridge were investigated for their geochemical and isotopic composition. These concretions were collected in an area characterized by the presence of two alleged mud volcanoes and three mud diapirs. The mud diapirs are dotted by pockmarks and dissected by normal faults, and are known for having been a site of fluid seepage for at least the past 40 kyrs. Present-day venting activity occurs alongside the two alleged mud volcanoes and is dominated by CO₂-rich discharging fluids. This discover led us to question the hypothesis of the mud volcanoes and investigate the origin of the fluids in each different domed structure of the study area.In this study, we used stable isotopes (carbon and oxygen) of carbonates coupled with rare earth element (REE) composition of different carbonate and non-carbonate phases for tracing fluid composition and early diagenesis of authigenic precipitates. The analyses on authigenic precipitates were coupled with chemical investigation of venting gas and sea-water.Authigenic calcite/aragonite concretions, from surficial sediments on diapiric structures, have depleted ¹³C isotopic composition and slightly positive δ¹⁸O values. By contrast, siderite concretions, generally found within the first 6 m of sediments on the alleged mud volcanoes, yielded positive δ¹³C and δ¹⁸O values. The siderite REE pattern shows consistent LREE (light REE) fractionation, MREE (medium REE) enrichment and positive Gd and La anomalies. As shown by the REE distribution, the ¹³C-depleted composition and their association with chemosymbiotic fauna, calcite/aragonite precipitated at time of moderate to high methane flux close to the seafloor, under the influence of bottom seawater. Authigenic siderite, on the other hand, formed in the subseafloor, during periods of lower gas discharges under prolonged anoxic conditions within sediments in equilibrium with ¹³C-rich dissolved inorganic carbon (DIC) and ¹⁸O-rich water, likely related to methanogenesis and intermittent venting of deep-sourced CO₂.