Mineralogical and geochemical features of authigenic carbonates on seepings and hydrothermal fields (By the examples of the Black Sea reefs and the mounds of the lost city field)

Two genetically different types of authigenic carbonate mounds are studied: those within an active hydrothermal field related to serpentinite protrusions in the zone of intersection of a transform fracture zone and the Mid-Atlantic Ridge, and those in an active field of methane seepings in the Dnieper canyon of the Black sea. The general geochemical conditions under which authigenic carbonate formation occurs in the two fields considered were found. They include the presence of reduced H₂S, H₂, and CH₄ gases at the absence of free oxygen; the high alkalinity of the waters participating in the carbonate formation; the similarity of the textural and structural features of authigenic aragonite, which represents the initial mineral of the carbonate matter of the mounds; the paragenesis of aragonite with sulfide minerals; and the close relation of carbonate mounds with communities of sulfate-reducing and methane-oxidizing microorganisms. A new mechanism of formation of hydrothermal authigenic carbonates is suggested; it implies their microbial sulfate reduction over the hydrogen of the fluid in the subsurface zone (biosphere) of mixing between the hydrothermal solution and the adjacent seawater.     

Northern Gulf of Mexico continental slope

The hummocky continental slope in the northwestern Gulf of Mexico is the result of active salt tectonism and accompanying faulting. Fluid and gassy hydrocarbons rise through the sediment column and along faults causing the formation of gas hydrates, gassy sediments, mud volcanoes and mounds, chemosynthetic communities and authigenic carbonates, reefs, and hardgrounds. Salt activity coupled with processes associated with relative sea level fluctuations create a feedback relationship resulting in the above-mentioned phenomena as well as others such as seafloor erosion at great water depths.     

南海北部陆坡九龙甲烷礁冷泉碳酸盐岩沉积岩石学特征

本文对南海北部陆坡九龙甲烷礁采集的两个冷泉碳酸盐岩样品TVG-1和TVG-11进行了矿物学、岩石学和碳氧同位素分析研究。X射线衍射分析（XRD）结果表明,自生矿物主要为文石、白云石和高镁方解石等,碎屑矿物含量较少。TVG-11中存在大量的文石,而TVG-1只保留了已转化为方解石的文石假象,据此可以推断TVG-1的形成要早于TVG-11。扫描电镜（SEM）显微结构特征显示,自生矿物主要是通过细菌的厌氧氧化作用,直接从冷泉中沉淀出来的。碳、氧同位素测试结果显示,碳酸盐岩具有强δ^13C亏损和一定程度的δ^18O富集的特征,TVG-1和TVG-11的δ^13C值分别为-46．22％。和-52．88％,均低于-40%,表明碳源于微生物作用的甲烷厌氧氧化,是指示该海域存在冷泉的重要证据;TVG-1和TVG-11的δ^18O值分别为3．19‰和4．07‰,存在一定程度的δ^18O富集。碳氧同位素和矿物的显微结构特征都说明九龙甲烷礁碳酸盐岩是烃类渗漏微生物作用而形成的自生碳酸盐岩,可能是天然气水合物分解引起的沉积,显示该区存在水合物的可能性很大。     

Hydrocarbon-derived carbonate buildups of the northern Gulf of Mexico continental slope: A review of submersible investigations

Hydrocarbon-derived and microbially mediated authigenic carbonates occur over the entire depth range of the northern Gulf of Mexico slope. These carbonates consist of nodules and incipient nodules in surface sediments, hardgrounds and isolated slabs, and moundlike buildups of up to 10–20 m relief above the surrounding seafloor. The authigenic carbonates are characterized by ¹³C negative values in the range –18 to –55 (PDB) suggesting mixing of seawater carbon with¹³C-depleted carbon sources ranging from crude oil to biogenic methane. Near the shelf edge, carbonates are diluted with biogenic material produced by reefs—bioherms developed at low sea level stands. Fossil-poor carbonates over salt diapirs of the upper and middle slope formed in the shallow subsurface and have been exhumed by the combined processes of uplift and physical erosion. Middle and lower slope carbonates are generally rich in fossil shells of chemosynthetic organisms. Mg calcite pelloidal matrix and acicular to botryoidal aragonitic void-filling cements are common petrographic features of these hydrocarbonderived carbonates. At two sites carbonates are mixed with barite.     

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.     

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.     

Gas seepage, pockmarks and mud volcanoes in the near shore of SW Taiwan

In order to understand gas hydrate related seafloor features in the near shore area off SW Taiwan, a deep-towed sidescan sonar and sub-bottom profiler survey was conducted in 2007. Three profiles of high-resolution sub-bottom profiler reveal the existence of five gas seeps (G96, GS1, GS2, GS3 and GS4) and one pockmark (PM) in the study area. Gas seeps and pockmark PM are shown in lines A and C, while no gas venting feature is observed along line B. This is the first time that a gas-hydrate related pockmark structure has been imaged off SW Taiwan. The relatively high backscatter intensity in our sidescan sonar images indicates the existence of authigenic carbonates or chemosynthetic communities on the seafloor. More than 2,000 seafloor photos obtained by a deep-towed camera (TowCam) system confirm the relatively high backscatter intensity of sidescan sonar images related to bacteria mats and authigenic carbonates formation at gas seep G96 and pockmark PM areas. Water column gas flares are observed in sidescan sonar images along lines A and C. Likewise, EK500 echo sounder images display the gas plumes above gas seep G96, pockmark PM and gas seep GS1; the gas plumes heights reach about 150, 100 and 20 m from seafloor, respectively. Based on multichannel seismic reflection (MCS) profiles, an anticline structure trending NNE-SSW is found beneath gas seep G96, pockmark PM and gas seep GS2. It implies that the gas venting features are related to the anticline structure. A thermal fluid may migrate from the anticline structure to the ridge crest, then rises up to the seafloor along faults or fissures. The seafloor characteristics indicate that the gas seep G96 area may be in a transitional stage from the first to second stage of a gas seep self-sealing process, while the pockmark PM area is from the second to final stage. In the pockmark PM area, gas venting is observed at eastern flank but not at the bottom while authigenic carbonates are present underneath the pockmark. It implies that the fluid migration pathways could have been clogged by carbonates at the bottom and the current pathway has shifted to the eastern flank of the pockmark during the gas seep self-sealing process.     

The Porcupine Bank Canyon coral mounds: oceanographic and topographic steering of deep-water carbonate mound development and associated phosphatic deposition

The head of a canyon system extending along the western Porcupine Bank (west of Ireland) and which accommodates a large field of giant carbonate mounds was investigated during two cruises (INSS 2000 and TTR-13). Multibeam and sidescan sonar data (600?C1,150?m water depth) suggest that the pre-existing seabed topography acts as a significant factor controlling mound distribution and shape. The mounds are concentrated along the edges of the canyon or are associated with a complex fault system traced around the canyon head, comprising escarpments up to 60?m high and several km long. The sampling for geochemical and petrographic analysis of numerous types of authigenic deposits was guided by sidescan sonar and video recordings. Calcite-cemented biogenic rubble was observed at the top and on the flanks of the carbonate mounds, being associated with both living and dead corals (Lophelia pertusa, Madrepora oculata and occasional Desmophyllum cristagalli). This can plausibly be explained by dissolution of coral debris facilitated by strong currents along the mound tops and flanks. In turn, the dissolved carbon is recycled and precipitated as interstitial micrite. Calcite, dolomite and phosphatic hardgrounds were identified in samples from the escarpment framing the eastern part of the survey area. The laterally extensive phosphatic hardgrounds represent a novel discovery in the region, supplying hard substrata for the establishment of new coral colonies. Based on existing knowledge of regional oceanographic conditions, complemented with new CTD measurements, it is suggested that water column stratification, enhanced bottom currents, and upwelling facilitate the deposition of organic matter, followed by phosphatisation leading to the formation of phosphate-glauconite deposits. The occurrence of strong bottom currents was confirmed by means of video observations combined with acoustic and sampling data, providing circumstantial evidence of fine- to medium-grained sand. Evidently, slope breaks such as escarpments and deep-water canyon headwalls are important structural elements in the development of mature carbonate mounds induced by deep-water coral growth. Stable isotope data show no evidence of methane-derived carbon in the carbonates and lithified sediments of the Porcupine Bank Canyon mounds.     

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.     

Initial stage of the hydrothermal ore accumulation within the field at 9°50′ N on the East Pacific Rise

In 2003, several hydrothermal mounds located at 9°50′ N on the East Pacific Rise were described and sampled during the expedition of R/V Akademik Mstislav Keldysh during dives of Mir deep-sea manned submersibles. These hydrothermal mounds were formed during a few recent years after the volcanic activity in this region that occurred in 1991. The studies of the chemical and mineralogical compositions of the hydrothermal deposits of these mounds and of the chemical composition of the principal sulfide minerals helped to describe the initial stage of the formation of the hydrothermal circulation system and the initiation of the hydrothermal ore formation.     

Sea-floor features related to hydrocarbon seeps in deepwater carbonate-mud mounds of the Gulf of Cádiz: from mud flows to carbonate precipitates

Underwater images taken from deepwater carbonate-mud mounds located along the continental margin of the Gulf of Cádiz (eastern Central Atlantic) have identified a great variety of hydrocarbon seep-related geomorphic features that exist on the sea floor. An extensive photographic survey was made along the Guadalquivir Diapiric Ridge, after detailed examination of the main mounds identified on previous swath bathymetry coverage, high-resolution seismic imagery, dredge and gravity core data. Recognised fluid-induced geomorphic features include seep precipitates, named here generically as hydrocarbon-derived authigenic carbonates (HDACs), mud-breccia flows and piping/rills, at scales ranging from metres to centimetres. Based on the viscosity, texture, morphology, and the nature of observed features, we have categorized the geomorphic seeps into the following types: mud-breccia flows and liquid seepages, which can be grouped as highly viscous and viscous mud-breccia flows, gassy mud-breccia flows, and small-scale piping/rills; HDACs types, including massive crusts, “honeycombed” carbonate crusts, nodular aggregated crusts, steeply dipping to vertical slabs, and pipe-like formations (chimneys). These widespread geomorphic features observed along the carbonate-mud mounds reveal alternate periods of (1) active mud-flow extrusion (mud-volcano formation), (2) reduced seepage activity, with the formation of extensive carbonate features by chemosynthetic organisms, and (3) formation of hardgrounds and colonisation by non-chemosynthetic organisms such as deepwater corals (e.g. Lophelia pertusa, Madrepora oculata). The formation of large amounts of HDACs is related to the microbially mediated oxidation of hydrocarbon fluids (biogenic and thermogenic) during periods of slower fluid venting. This has led to the hypothesis that these carbonate-mud mounds could be built up by alternating episodes of varying fluid-venting rates, with peaks that may have been triggered by tectonic events (e.g. high-seismicity periods) and slower rates controlled by climate/oceanographic factors (e.g. glacial to interglacial climatic transitions, increasing shallow subsurface hydrate formation, and sealing of sea-floor fluid venting).     

Association among active seafloor deformation, mound formation, and gas hydrate growth and accumulation within the seafloor of the Santa Monica Basin, offshore California

Seafloor blister-like mounds, methane migration and gas hydrate formation were investigated through detailed seafloor surveys in Santa Monica Basin, offshore of Los Angeles, California. Two distinct deep-water (≥ 800 m water depth) topographic mounds were surveyed using an autonomous underwater vehicle (carrying a multibeam sonar and a chirp sub-bottom profiler) and one of these was explored with the remotely operated vehicle Tiburon. The mounds are > 10 m high and > 100 m wide dome-shaped bathymetric features. These mounds protrude from crests of broad anticlines (~ 20 m high and 1 to 3 km long) formed within latest Quaternary-aged seafloor sediment associated with compression between lateral offsets in regional faults. No allochthonous sediments were observed on the mounds, except slumped material off the steep slopes of the mounds. Continuous streams of methane gas bubbles emanate from the crest of the northeastern mound, and extensive methane-derived authigenic carbonate pavements and chemosynthetic communities mantle the mound surface. The large local vertical displacements needed to produce these mounds suggests a corresponding net mass accumulation has occurred within the immediate subsurface. Formation and accumulation of pure gas hydrate lenses in the subsurface is proposed as a mechanism to blister the seafloor and form these mounds.     

日本海西部大陆坡自生碳酸盐的特征与成因

对日本海西部大陆坡沉积物柱状样中的自生碳酸盐样品进行了X射线衍射、扫描电镜、地球化学和碳氧同位素组成的系统研究。X射线衍射和扫描电镜分析结果表明,碳酸盐主要组成矿物为颗粒状自生高镁方解石微晶,放射状自生文石微晶仅在一个层位出现。结合碳酸盐的地球化学组成,认为研究区碳酸盐来自于富Ca2+、Mg2+和HCO3-流体的沉淀。中度亏损的13C(-33.85‰～-39.53‰)表明碳来自于甲烷的厌氧氧化,同时,这也是研究区海底存在甲烷冷泉的重要证据。重氧同位素比值(5.28‰～5.31‰)则指示着富18O流体来源,而该流体应源于天然气水合物的分解。综上可知,研究区碳酸盐来自于研究区甲烷冷泉上升流的沉淀,指示着海底更深处天然气水合物的存在与分解。     

Manganese carbonates in the upper quaternary sediments of the Deryugin basin (Sea of Okhotsk)

The mineral and chemical compositions of authigenic carbonates are studied by several methods in a sediment core obtained from the axial zone of the Deryugin riftogenic basin. Manganese carbonates (kutnahorite, rhodochrosite) associated with manganiferous calcite, manganiferous pyrite, and nontronite are first identified in the Sea of Okhotsk. Manganese carbonates in the Holocene diatomaceous ooze were presumably formed due to diagenetic transformation of sedimentary manganese hydroxides, organic matter, and biogenic silica, while those found in the underlying turbidites precipitated owing to the intermittent influx of endogenic fluids migrating along sand interbeds.     

Late Pliocene Mega Debris Flow Deposit and Related Fluid Escapes Identified on the Antarctic Peninsula Continental Margin by Seismic Reflection Data Analysis

We have obtained improved images of a debris flow deposit through the reprocessing of multichannel seismic reflection data between Drifts 6 and 7 of the continental rise of the Pacific margin of the Antarctic Peninsula. The reprocessing, primarily aimed at the reduction of noise, relative to amplitude preservation, deconvolution, also included accurate velocity analyses. The deposit is dated as upper Pliocene (nearly 3.0 Ma) via correlation to Sites 1095 and 1096 of the Ocean Drilling Program (ODP) Leg 178. The estimated volume is about 1800 km³ and the inferred provenance from the continental slope implies a run out distance exceeding 250 km. The dramatic mass-wasting event that produced this deposit, unique in the sedimentary history of this margin, is related to widespread late Pliocene margin erosion. This was associated with a catastrophic continental margin collapse, following the Antarctic ice sheet expansion in response to global cooling. The seismic data analysis also allowed us to identify diffractions and amplitude anomalies interpreted as expressions of sedimentary mounds at the seafloor overlying narrow high-velocity zones that we interpret as conduits of fluid expulsion hosting either methane hydrates or authigenic carbonates. Fluid expulsion was triggered by loading of underlying sediments by the debris flow deposits and may have continued until today by input of fluids from sediment compaction following the deep diagenesis of biogenic silica.     

Tectonic control of the oil-rich large igneous-carbonate-salt province of the South Atlantic rift

The Early Cretaceous South Atlantic Magmatic Province (SAMP), which includes the Paraná-Etendeka LIP, produced about 8 million km³ of tholeiitic basalt and diabase over an area of 4 million km². Huge pre-salt oil reserves, discovered in 2007 by Petrobras in non-marine carbonates, are estimated at more than 45 billion barrels. Here we show the close causal relationship of the southward increasing width of the wedge-shaped South Atlantic rift with the similarly southward increase in igneous activity, in the thicknesses of non-marine carbonate and salt, and in the size of oil reserves, all controlled mainly by South America’s early clockwise rotation away from Africa about a pole in its northeast. Large diabase dike swarms transversal to the rift witness to South America’s rotation that opened in its wake the southward widening South Atlantic rift. Westward increasing pressure on the Equatorial margin by South America’s clockwise rotation forced open the Benue trough and created pre-late-Aptian folds in the Demerara Plateau and in Brazil’s Solimões (Upper Amazonas) basin. Prerift and synrift volcanic activity increases southward, culminating in the Parana-Etendeka LIP and in the offshore volcanic SDRSs that continue southward to the Cape Basin. Berriasian-Valanginian rift sediments deposited from about 145 Ma, 10 Ma before the flood basalts of the Parana-Etendeka LIP. The largest transversal dike swarm continued in the proto-Walvis Ridge that separated the central South Atlantic endorheic rift basin from the sea in the south; erosion and leaching of basalts supplied Ca, Mg, and SiO₂ to the endorheic basin for the deposition of non-marine carbonates and authigenic clays. Basalt flows intercalated with carbonates nearly until salt deposition about 113 Ma. Hypogenic leaching of carbonates by mantle-derived CO₂ created optimal reservoirs. Supergiant oil deposits occur where the widest endorheic basin and the volcanic province overlap.     

Using iron speciation in authigenic carbonates from hydrocarbon seeps to trace variable redox conditions

Seepage of hydrocarbon-rich fluids out of the marine sedimentary column is characterized by temporal changes of flow intensity and resultant spatially variable redox conditions. Authigenic carbonates at marine hydrocarbon seeps provide excellent geological and geochemical archives that serve to explore seepage dynamics over time. In this study, we investigated the potential of Mössbuaer spectroscopy and Fe contents of seep-related authigenic carbonates from the Congo Fan, the Gulf of Mexico, and the Black Sea for reconstructing past redox conditions and fluid seepage activity at cold seeps. The Fe speciation observed by Mössbauer spectroscopy and Fe contents suggest that (1) the Congo Fan carbonates precipitated in a sulfidic environment, (2) the formation conditions of seep carbonates were variable at the Gulf of Mexico seep site, ranging from oxic to suboxic and anoxic and even spanning into the methanogenic zone, and (3) the stratified water column of the Black Sea or suboxic condition resulted in low Fe contents of Black Sea carbonates. The study reveals that Fe speciation can provide constraints on the wide range of redox conditions that imprinted seep carbonates during the life span of seepage. Similarly, Mössbauer spectroscopy – particularly when used in combination with the analysis of redox-sensitive elements – is a promising tool to trace variable redox conditions in marine paleoenvironments other than seeps.     

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‰.     

Asphalt mounds and associated biota on the Angolan margin

Release of hydrocarbons from sediments is important in increasing habitat heterogeneity on deep ocean margins. Heterogeneity arises from variation in abiotic and biotic conditions, including changes in substratum, geochemistry, fluid flow, biological communities and ecological interactions. The seepage of heavy hydrocarbons to the seafloor is less well studied than most other cold seep systems and may lead to the formation of asphalt mounds. These have been described from several regions, particularly the Gulf of Mexico. Here, we describe the structure, potential formation and biology of a large asphalt mound province in Block 31SE Angola. A total of 2254 distinct mound features was identified by side-scan sonar, covering a total area of 3.7 km² of seafloor. The asphalt mounds took a number of forms from small (<0.5 m diameter; 13% observations) mounds to large extensive (<50 m diameter) structures. Some of the observed mounds were associated with authigenic carbonate and active seepage (living chemosynthetic fauna present in addition to the asphalt). The asphalt mounds are seabed accumulations of heavy hydrocarbons formed from subsurface migration and fractionation of reservoir hydrocarbons primarily through a network of faults. In Angola these processes are controlled by subsurface movement of salt structures. The asphalt mounds were typically densely covered with epifauna (74.5% of mounds imaged had visible epifauna) although individual mounds varied considerably in epifaunal coverage. Of the 49 non-chemosynthetic megafaunal taxa observed, 19 taxa were only found on hard substrata (including asphalt mounds), 2 fish species inhabited the asphalt mounds preferentially and 27 taxa were apparently normal soft-sediment fauna. Antipatharians (3.6±2.3% s.e.) and poriferans (2.6±1.9% s.e.) accounted for the highest mean percentage of the observed cover, with actinarians (0.9±0.4% s.e.) and alcyonaceans (0.4±0.2% s.e.) covering smaller proportions of the area. Asphalt mounds represent a common and important habitat on several margin systems globally and should be recognised in future environmental assessment and management of these areas.     

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.