Authigenic Mg-calcite at a cold methane seep site in the Laptev Sea

Authigenic minerals were studied in Holocene shelf sediments of the Laptev Sea (cold methane seep site, water depth 71 m). The study presents the first finds of large hard carbonate concretions with Mg-calcite cement in recent sediments of the Arctic shelf seas. These concretions differ from previously reported glendonites and concretions from bottom sediments of the White Sea, Kara Sea, Sea of Okhotsk, etc. A study of the morphology, microstructure, and composition of these newly reported concretions revealed the multistage formation of carbonates (structural varieties of Mg-calcite and aragonite). It was shown that organic matter played an important role in the formation of authigenic carbonates, i.e., in the formation of sedimentary–diagenetic Mg-calcite. The role of methane as a possible source for authigenic carbonate formation was estimated. It was found that methane-derived Mg-calcite accounts for 17–35% of concretion materials. Mg-calcite had δ¹³С-С_carb values between–24 and–23‰ and δ¹³С-С_org values between–44.5 and–88.5‰.     

Fluid sources and stable isotope signatures in authigenic carbonates from the Northern Apennines,Italy

Authigenic carbonates are frequently associated with methane cold-seep systems, which extensively occur in various geologic settings worldwide. Of interest is the relation between the fluids involved in their formation and the isotopic signals recorded in the carbonate cements. Along the Northern Apennines foothills (Italy), hydrocarbons and connate waters still seeping nowadays are believed to be the primary sources for the formation of fossil authigenic carbonate found in Plio-Pleistocene marine sediments. Four selected outcrops of dolomitic authigenic carbonates were analysed to compare signature of seeping fluids with fractionation of stable carbon and oxygen isotopes recorded in the carbonate.Along the foothills, deep methane-rich fluids spontaneously rise to the surface through mud volcanoes or are exploited in wells drilled nearby to the fossil Plio-Pleistocene authigenic carbonates. The plumbing system providing fluids to present-day cold seeps was structurally achieved in Late Miocene and Plio-Pleistocene. δ¹³C values of methane, which vary from −51.9 to −43.0‰ VPDB, indicate that gas composition from the deep hydrocarbon reservoirs is relatively uniform along the foothills. On the contrary, δ¹³C in fossil authigenic carbonates strongly varies among different areas and also within the same outcrop.The different carbon sources that fed the investigated carbonates were identified and include: thermogenic methane from the deep Miocene reservoirs, ¹³C-enriched CO₂ derived from secondary methanogenesis and microbial methane from Pliocene successions buried in the Po Plain. The δ¹³C variability documented among samples from a single outcrop testifies that the authigenic carbonates might represent a record of varying biogeochemical processes in the hydrocarbon reservoirs. The sources of stable oxygen isotopes in authigenic carbonates are often ascribed to marine water. Oxygen isotopic fractionation in the dolomite cements indicates that marine pore water couldn't be the sole source of oxygen. δ¹⁸O values provide a preliminary evidence that connate waters had a role in the carbonates precipitation. The concomitant occurrence of active cold seepages and fossil record of former plumbing systems suggests that generation and migration of hydrocarbons are long-lasting and very effective processes along the Northern Apennines foothills.     

Authigenic carbonates related to active seepage of methane-rich hot brines at the Cheops mud volcano,Menes caldera (Nile deep-sea fan,eastern Mediterranean Sea)

On the passive margin of the Nile deep-sea fan, the active Cheops mud volcano (MV; ca. 1,500 m diameter, ~20–30 m above seafloor, 3,010–3,020 m water depth) comprises a crater lake with hot (up to ca. 42 °C) methane-rich muddy brines in places overflowing down the MV flanks. During the Medeco2 cruise in fall 2007, ROV dives enabled detailed sampling of the brine fluid, bottom lake sediments at ca. 450 m lake depth, sub-surface sediments from the MV flanks, and carbonate crusts at the MV foot. Based on mineralogical, elemental and stable isotope analyses, this study aims at exploring the origin of the brine fluid and the key biogeochemical processes controlling the formation of these deep-sea authigenic carbonates. In addition to their patchy occurrence in crusts outcropping at the seafloor, authigenic carbonates occur as small concretions disseminated within sub-seafloor sediments, as well as in the bottom sediments and muddy brine of the crater lake. Aragonite and Mg-calcite dominate in the carbonate crusts and in sub-seafloor concretions at the MV foot, whereas Mg-calcite, dolomite and ankerite dominate in the muddy brine lake and in sub-seafloor concretions near the crater rim. The carbonate crusts and sub-seafloor concretions at the MV foot precipitated in isotopic equilibrium with bottom seawater temperature; their low δ¹³C values (–42.6 to –24.5‰) indicate that anaerobic oxidation of methane was the main driver of carbonate precipitation. By contrast, carbonates from the muddy lake brine, bottom lake concretions and crater rim concretions display much higher δ¹³C (up to –5.2‰) and low δ¹⁸O values (down to –2.8‰); this is consistent with their formation in warm fluids of deep origin characterized by ¹³C-rich CO₂ and, as confirmed by independent evidence, slightly higher heavy rare earth element signatures, the main driver of carbonate precipitation being methanogenesis. Moreover, the benthic activity within the seafloor sediment enhances aerobic oxidation of methane and of sulphide that promotes carbonate dissolution and gypsum precipitation. These findings imply that the coupling of carbon and sulphur microbial reactions represents the major link for the transfer of elements and for carbon isotope fractionation between fluids and authigenic minerals. A new challenge awaiting future studies in cold seep environments is to expand this work to oxidized and reduced sulphur authigenic minerals.     

Formation of methane-related authigenic carbonates in a highly dynamic biogeochemical system in the Krishna–Godavari Basin,Bay of Bengal

We report the abundant occurrence of authigenic Fe-rich carbonate, high Mg-calcite (HMC) and low Mg-calcite from 11 cores recovered from the Krishna–Godavari Basin (K–G Basin), Bay of Bengal. The cores were collected as part of the Indian gas hydrate exploration program on board R/V Marion Dufresne (MD-161: May, 2007) in different environments, including mounds (mud diapirs), mass flows, and hemipelagic sediments over a range of water depths from 647 to 2079 m. Authigenic carbonates range in size from 1 mm to 12 cm and display various morphologies like roundish or platy (micro-) nodules and tube-like forms. From the cores, 173 carbonate samples have been investigated for their depth distribution, mineralogy, geochemical and stable isotopic composition. The stable carbon isotopic composition of 46 out of 88 measured carbonate samples are around −50‰ which allows the differentiation into methane-related carbonates (HMC), especially at Sites 8 and 15, but also in low abundance at Sites 1, 5, 9 and 12. Results indicate that the carbonates at Site 8 and 15 represent paleo methane seepage locations. The Fe-rich carbonates occur abundantly at many sites in the K–G Basin. Their varying carbon isotopic composition indicates that probably not only sulfate reduction through organic matter degradation but also methanogenesis are the responsible processes for their formation.     

Mineral-forming and diagenetic processes related to Tertiary hydrocarbon seepage at the Bohemian Massif/Outer Western Carpathians interface: Evidence from the Hrabůvka quarry,Moravia, Czech Republic

Ancient hydrocarbon seepage occurred in the Hrabůvka quarry at the boundary between the basement of the Bohemian Massif (represented by folded Lower Carboniferous siliciclastics of the Culm facies) and Tertiary sedimentary cover of the Carpathian Foredeep (formed by Lower Badenian siliciclastics and calcareous clays). The unconsolidated Lower Badenian sediments contain lithified domains composed of limestone and breccias with limestone cement, whereas the basement rocks are cut by subvertical neptunic dykes filled up by limestone and calcite-marcasite-pyrite veinlets representing sealed fluid conduits. The deeply negative δ¹³C values of both vein calcite and limestone (down to −38.1‰ V-PDB) indicate that oxidation of hydrocarbons was the major source of carbon for authigenic mineralization. A fluid inclusion study suggests low fluid temperatures (<50 °C) and low and variable salinities of aqueous fluids associated with hydrocarbons (0.7–6.7 wt. % NaCl eq.). The variability of δ¹⁸O values of authigenic carbonates (−1.7 to −8.2‰ V-PDB) could reflect either slight changes in temperature of escaping fluids (mostly within 15 °C), and/or some mixing with meteoric waters. The low δ³⁴S values of vein marcasite (∼–20‰ V-CDT) are consistent with bacterial reduction of sulfate in the hydrothermal system. Low C₁/(C₂+C₃) ratios in hydrocarbon gas extracted from authigenic carbonates (9.9 and 5.8) as well as the high δ¹³C values of methane (−31.8 and −32.4‰ V-PDB) are compatible with a thermogenic source of hydrocarbons. REE data indicate sequestration of REE from finely dispersed detrital material in the apical part of the hydrothermal system. The available data are compatible with two possible scenarios of fluid origin. The hydrocarbons could have been leached from underlying Paleozoic sedimentary sequence by aqueous fluids that infiltrated into the basement after Tertiary tectonic reactivation. Alternatively, an external source of hydrocarbon-bearing fluids can be found in the adjacent Outer Western Carpathians flysch nappes containing petroleum-producing lithologies. Nevertheless, a regional flow of hydrocarbon-bearing fluids is evidenced by the occurrence of very similar hydrocarbon-bearing vein mineralizations in a wider area.     

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.     

Evidence of subsurface anaerobic biodegradation of hydrocarbons and potential secondary methanogenesis in terrestrial mud volcanoes

The assessment of gas origin in mud volcanoes and related petroleum systems must consider post-genetic processes which may alter the original molecular and isotopic composition of reservoir gas. Beyond eventual molecular and isotopic fractionation due to gas migration and microbial oxidation, investigated in previous studies, we now demonstrate that mud volcanoes can show signals of anaerobic biodegradation of natural gas and oil in the subsurface. A large set of gas geochemical data from more than 150 terrestrial mud volcanoes worldwide has been examined. Due to the very low amount of C₂₊ in mud volcanoes, isotopic ratios of ethane, propane and butane (generally the best tracers of anaerobic biodegradation) are only available in a few cases. However, it is observed that ¹³C-enriched propane is always associated with positive δ¹³C_CO2 values, which are known indicators of secondary methanogenesis following anaerobic biodegradation of petroleum. Data from carbon isotopic ratio of CO₂ are available for 134 onshore mud volcanoes from 9 countries (Azerbaijan, Georgia, Ukraine, Russia, Turkmenistan, Trinidad, Italy, Japan and Taiwan). Exactly 50% of mud volcanoes, all releasing thermogenic or mixed methane, show at least one sample with δ¹³C_CO2 > +5‰ (PDB). Thermogenic CH₄ associated with positive carbon isotopic ratio of CO₂ generally maintains its δ¹³C-enriched signature, which is therefore not perturbed by the lighter secondary microbial gas. There is, however, high variability in the δ¹³C_CO2 values within the same mud volcanoes, so that positive δ¹³C_CO2 values can be found in some vents and not in others, or not continuously in the same vent. This can be due to high sensitivity of δ¹³C_CO2 to gas–water–rock interactions or to the presence of differently biodegraded seepage systems in the same mud volcano. However, finding a positive δ¹³C_CO2 value should be considered highly indicative of anaerobic biodegradation and further analyses should be made, especially if mud volcanoes are to be used as pathfinders of the conditions indicative of subsurface hydrocarbon accumulations in unexplored areas.     

Seafloor geological studies above active gas chimneys off Egypt (Central Nile Deep Sea Fan)

Four mud volcanoes of several kilometres diameter named Amon, Osiris, Isis, and North Alex and located above gas chimneys on the Central Nile Deep Sea Fan, were investigated for the first time with the submersible Nautile. One of the objectives was to characterize the seafloor morphology and the seepage activity across the mud volcanoes. The seepage activity was dominated by emissions of methane and heavier hydrocarbons associated with a major thermal contribution. The most active parts of the mud volcanoes were highly gas-saturated (methane concentrations in the water and in the sediments, respectively, of several hundreds of nmol/L and several mmol/L of wet sediment) and associated with significantly high thermal gradients (at 10 m below the seafloor, the recorded temperatures reached more than 40 °C). Patches of highly reduced blackish sediments, mats of sulphide-oxidizing bacteria, and precipitates of authigenic carbonate were detected, indicative of anaerobic methane consumption. The chemosynthetic fauna was, however, not very abundant, inhibited most likely by the high and vigorous fluxes, and was associated mainly with carbonate-crust-covered seafloor encountered on the southwestern flank of Amon. Mud expulsions are not very common at present and were found limited to the most active emission centres of two mud volcanoes, where slow extrusion of mud occurs. Each of the mud volcanoes is fed principally by a main narrow channel located below the most elevated areas, most commonly in the centres of the structures. The distribution, shape, and seafloor morphology of the mud volcanoes and associated seeps over the Central Nile Deep Sea Fan are clearly tectonically controlled.     

Exhumed hydrocarbon-seep authigenic carbonates from Zakynthos Island (Greece): Concretions not archaeological remains

In Zakynthos Island (Greece), authigenic cementation of marine sediment has formed pipe-like, disc and doughnut-shaped concretions. The concretions are mostly composed of authigenic ferroan dolomite accompanied by pyrite. Samples with >80% dolomite, have stable isotope compositions in two groups. The more indurated concretions have δ¹⁸O around +4‰ and δ¹³C values between −8 and −29‰ indicating dolomite forming from anaerobic oxidation of thermogenic methane (hydrocarbon seep), in the sulphate-methane transition zone. The outer surfaces of some concretions, and the less-cemented concretions, typically have slightly heavier isotopic compositions and may indicate that concretion growth progressed from the outer margin in the ambient microbially-modified marine pore fluids, inward toward the central conduit where the isotopic compositions were more heavily influenced by the seep fluid. Sr isotope data suggest the concretions are fossil features, possibly of Pliocene age and represent an exhumed hydrocarbon seep plumbing system. Exposure on the modern seabed in the shallow subtidal zone has caused confusion, as concretion morphology resembles archaeological stonework of the Hellenic period.     

Methane-derived authigenic carbonates from active hydrocarbon seeps of the St. Lawrence Estuary,Canada

Nearly 2000 pockmarks with diameters ranging from a few tens of meters up to 700 m are present on the seafloor of the St. Lawrence Estuary in eastern Canada. Coring of some pockmarks resulted in the recovery of various-sized and shaped carbonate concretions in a predominantly silty mud matrix. Petrographic and geochemical data on four authigenic carbonate concretions are reported as well as data from shell material in the unconsolidated sediment. Video observations and echo-sounder images indicate that the sampled pockmarks are actively gas venting. The video images show significant look-alike microbial mats in areas where gas is venting. The carbonate concretions are primarily made up of carbonate cements with varying percentage of shell fragments, micrite particles and fine-grained clastics. Orthorhombic crystal morphology and diagenetic fabrics including isopachous layers and botryoids characterize the aragonite cement. Oxygen isotopes ratios for the cement crusts do not record any thermal anomaly at the site of precipitation with δ¹⁸O_VPDB ratios (+3‰) in equilibrium with cold (5 °C) deep marine waters, whereas significant negative δ¹³C_VPDB ratios (−9.9 to −33.5‰) for cement and shell material within concretions indicate that the carbonates largely derive from the microbial oxidation of methane. The δ¹³C_VPDB ratios of aragonite shells (−2.7 to −5.6‰) taken from unconsolidated sediments at some distance from the concretions/vents show variable dilution of HCO₃⁻ with negative δ¹³C_VPDB ratios derived from microbial oxidation of methane with isotopically normal (0‰) marine bicarbonate. These results are in agreement with other lines of evidence suggesting that pockmarks formed through the recent and still active release of gas from a reservoir within the Paleozoic sedimentary succession.     

Mud volcanoes—a significant source of atmospheric methane

Mud volcanoes are recognized as a significant geological source of atmospheric carbon, particularly as methane gas. This paper considers the total number of mud volcanoes, types and frequency of their activity, quantities of emissions during quiescence and eruption, and composition of venting gases. Mud volcanoes approximate 1,950 prominent individuals worldwide and about 60 to 65 erupt every year. They sporadically or continuously emit to the atmosphere considerable volumes of gas, mainly methane, in average volumes of 3.3 to 3.6×10⁶ m³ per year during quiescent periods, and about 12×10⁶ m³ to more than 350×10⁶ m³ per single eruption. The total annual amount of methane emitted to the atmosphere through mud volcanoes is estimated to be about 5 Tg, containing almost equal quantities of fossil and modern carbon.     

Isotopic composition of dissolved inorganic carbon in subsurface sediments of gas hydrate-bearing mud volcanoes, Lake Baikal: implications for methane and carbonate origin

We report on the isotopic composition of dissolved inorganic carbon (DIC) in pore-water samples recovered by gravity coring from near-bottom sediments at gas hydrate-bearing mud volcanoes/gas flares (Malenky, Peschanka, Peschanka 2, Goloustnoe, and Irkutsk) in the Southern Basin of Lake Baikal. The δ¹³C values of DIC become heavier with increasing subbottom depth, and vary between ?9.5 and +21.4‰ PDB. Enrichment of DIC in ¹³C indicates active methane generation in anaerobic environments near the lake bottom. These data confirm our previous assumption that crystallization of carbonates (siderites) in subsurface sediments is a result of methane generation. Types of methanogenesis (microbial methyl-type fermentation versus CO₂-reduction) were revealed by determining the offset of δ¹³C between dissolved CH₄ and CO₂, and also by using δ¹³C and δD values of dissolved methane present in the pore waters. Results show that both mechanisms are most likely responsible for methane generation at the investigated locations.     

Three generations of mud volcanoes on the Louisiana continental slope

Three mud volcanoes were identified in a small area of the upper continental slope of the Gulf of Mexico. One is actively accreting by small, intermittent eruptions of gas and fluid mud. Eruptions occur from a pool of gas- and oil-saturated muds that upwell and spill over the central crater edge and down the flanks of the coneshaped buildup. A second structure, a possible sand volcano, is in the last stages of activity, with only slight evidence of gas-saturated sediments. The third structure is a dormant mud volcano with furrowed sides and scattered authigenic carbonate plates and rubble but no venting of gas or fluids.     

Discovery of the southwest Dongsha Island mud volcanoes amid the northern margin of the South China Sea

The Dongsha Basin, circling Dongsha Island that is amid the northern margin of the South China Sea, is characterized by thin (∼0.5 km) Cenozoic sediments veneering on thick (up to 5 km) Mesozoic strata. Recently, several geophysical and geological surveys, including multiple channel reflection seismic, sub-bottom profiling and benthic dredging, have been conducted on the slope southwest to the Dongsha Island, where the water depth varies from 400 m to 2000 m. A novel discovery is numerous submarine mud volcanoes of various sizes over there, typically 50–200 m high and 0.5–5 km wide. Geophysical profiles document their unusual features, e.g., roughly undulating seafloor, high-amplitude seabed reflectivity, foggy hyperbolic diffractions up to 50 m in water column above seabed, and internal reflection chaos and wipe-out down to 2–3 km level or deeper below the seabed. Benthic dredging from the mud volcanoes gives abundant faunas of high diversity, e.g., scleractinian (stony coral), gorgonian, black coral, thiophil tubeworm, glass sponge, bryozoan etc., indicating booming chemosynthetic community, among which the Lophelia pertusa-like coral and the Euretidae-like glass sponges are the first reports in the South China Sea. Concomitantly with them, there are also abundant authigenic carbonate nodules and slabs, raw, brecciated and breccias with bio-clasts congregation. Besides, there coexist massive mudflows and allogenic coarse-grained quartz, feldspar and tourmaline most likely brought out by mud volcanism. Geochemical analysis of the bottom water samples give dissolved methane concentration up to 4 times higher than the background average. These results lend comprehensive evidences for the ongoing and historical mud volcanism. The escaping methane gas is inferred to source mainly from the Mesozoic strata. Occupying a large province of the deep water slope, ca. 1000 km² or more, the mud volcanoes is prospective for gas hydrate and natural gas for the Dongsha Basin.     

Authigenic barite nodules and carbonate concretions in the Upper Devonian shale succession of western New York – A record of variable methane flux during burial

Authigenic barite nodules associated with modestly ¹³C-depleted calcium carbonate concretions and ³⁴S-enriched pyrite at the bottom of the Upper Devonian Hanover Shale of western New York provide evidence of sulfate reduction coupled with anaerobic oxidation of methane (AOM). The methane, much of it biogenic in origin, may have diffused upward from Middle Devonian Marcellus Shale and perhaps the Upper Ordovician Utica Shale. Strong ³⁴S enrichment and high δ³⁴S/δ¹⁸O values of the barite nodules reflect: (1) substantial kinetic fractionation induced by microbial sulfate reduction perhaps intensified by a low seawater sulfate recharge rate and (2) upward delivery of Ba²⁺- and CH₄- bearing pore fluid sourced within underlying sulfate-depleted deposits. However, the association of authigenic calcium carbonate and barite in the same stratigraphic interval, especially the presence of barite overgrowths on carbonate concretions, is not consistent with what is known of AOM-related mineralization of a sediment column passing downward through the sulfate–methane transition (SMT). The documented early formation of authigenic carbonate followed by barite observed relations may reflect a diminished rate of methanogenesis and/or CH₄ supply. The tempered methane flux would have induced the SMT to descend the sediment column enabling barite to form within the same stratigraphic horizon that ¹³C-depleted calcium carbonate had most recently precipitated. Diminished methane flux may have been caused by burial-related passage of the organic-rich Marcellus Shale below the depth of peak biogenic methane generation and its replacement at that depth interval by organic-lean deposits of the upper part of the Hamilton Group. Subsidence of the SMT would have increased the preservation potential of authigenic barite. However, continued survival of the labile barite as it eventually moved through the SMT suggests that the underlying sulfate-depleted zone was strongly enriched in Ba²⁺.     

Authigenic carbonates from active methane seeps offshore southwest Africa

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2–5?m length indicates a maximum age of about 60,000–80,000?years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (–61.0?<?δ¹³C ‰ V-PDB?<?–40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4?<?δ¹⁸O ‰ V-PDB?<?+6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ¹⁸O values might reflect the contribution of ¹⁸O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby providing enough Ca²⁺ ions for pore solutions to reach gypsum saturation; this is thought to be promoted by the bio-irrigation and burrowing activity of benthic fauna. The δ¹⁸O–δ¹³C patterns identified in the authigenic carbonates are interpreted to reflect variations in the rate of AOM during the last glacial–interglacial cycle, in turn controlled by variably strong methane fluxes through the pockmarks. These results complement the conclusions of Kasten et al. in this special issue, based on authigenic barite trends at the Hydrate Hole and Worm Hole pockmarks which were interpreted to reflect spatiotemporal variations in AOM related to subsurface gas hydrate formation–decomposition.     

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     

Seismic expression of sedimentary volcanism on the continental slope,northern Gulf of Mexico

High-resolution geophysical data define acoustically amorphous, mounded structures on the upper, middle, and lower continental slope of the northern Gulf of Mexico. Physical samples and observations within this unique seismic facies show gassy sediments, sometimes in hydrated form and, in places, as chemosynthetic communities. The geologic setting of these mounds suggests that the process of formation falls on the continuum of mud volcanoes to mud diapirs.     

南黄海自生黄铁矿成因及其环境指示意义

样品为１９８９年采自南黄海，利用显微镜，电子显微镜，电子探针和化学分析方法，对自生黄铁矿的形态，成份和同位素特征进行研究，在此基础上就其成因与形成环境的关系进行初步探讨。研究结果表明，自生黄铁矿集合体形态可以分为聚莓，单莓和细粒３种，霉体特征的形态是早期成岩作用阶段沉积物随机堆积的结果，可以作了沉积成因黄铁矿的形态标型黄铁矿微量成份特征显示其沉积成因，同时亦表现对泥质沉积物地球化学背景值的继承性，     

Fossil Foraminifera from four active mud volcanoes in the Gulf of Mexico

Samples were collected for foraminiferal studies by the Johnson Sea-Link I and II manned submersibles on the Louisiana continental slope. This paper documents that the mud, extruded onto the sea floor from depth by four mud volcanoes, ranges in age from Miocene to Pleistocene based on studies of the planktonic foraminiferal fauna. The vents are in water depths ranging from 300 to 690 m located in Garden Banks Block 382, Green Canyon Blocks 143 and 272, and Mississippi Canyon Block 929. Two mud volcanoes in GB 382 and MC 929 also have rich fossil foraminiferal microfaunas. We suggest that the extrusion of fossil sediments onto the sea floor during the Quaternary is a reasonable explanation for frequent occurrences of displaced fossil microfaunas encountered at depth in wells drilling on the flanks of salt diapirs in the slope environment. Results of this study have important implications for age dating subsurface sediments in bathyal locations.