Authigenic carbonates from methane seeps of the Congo deep-sea fan

Submersible investigations with the ROV Victor 6000 of some pockmark structures on the seafloor of the Congo deep-sea fan have shown that they are active venting sites of methane-rich fluids, associated with abundant fauna and carbonate crusts. Moreover, methane hydrates have been observed both outcropping and deep in the sediments in the centre of the “Regab” giant pockmark. Authigenic carbonates, mostly calcite sometimes mixed with aragonite, are cementing the sedimentary matrix components and fauna; diatoms are abundant but only as moulds, indicating that biogenic silica dissolution occurred in situ synchronous with carbonate precipitation. The occurrence of diagenetic barite and pyrite in some carbonate crusts demonstrates that they can be formed either within the sulphate/methane transition zone or deeper in sulphate-depleted sediments. The oxygen isotopic compositions of the diagenetic carbonates (3.17–6.01‰ V-PDB) indicate that precipitation occurred with bottom seawater mixed with a variable contribution of water from gas hydrate decomposition. The very low carbon isotopic compositions of the diagenetic carbonates (−57.1 to −27.75‰ V-PDB) demonstrate that carbon derives mostly from the microbial oxidation of methane.     

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.     

A contribution to the reconstruction of Miocene seepage from authigenic carbonates of the northern Apennines (Italy)

Authigenic carbonates from outcrops of the northern Apennines consist of small and irregular lenses and exhibit numerous features indicative of cold-seep settings. Detailed petrographic, mineralogical and geochemical studies from two Miocene deposits are presented. The first carbonate outcrop, named Fosso Riconi, is located in the foredeep basin of the Apenninic chain, whereas the second deposit represents a satellite basin called Sarsetta. The stable isotope data from specific carbonate minerals show a wide range of values well known from other palaeoseeps of the Apennine Mountains. The majority of seep carbonates are formed by low-Mg calcite and ankerite. Those minerals have δ¹³C values between ?7 and ?23‰ V-PDB, suggesting variable amounts of carbonate derived from oxidized methane, seawater (dissolved inorganic carbon) and sedimentary organic matter. Dolomite samples have the lowest δ¹³C values (?30.8 to ?39.0‰ V-PDB), indicating methane as the main carbon source. The findings suggest an evolutionary formation of the seeps and development of authigenic carbonates influenced by the activity of chemosynthetic organisms, of which large lucinid clams are preserved. Bioirrigation by the clams controlled the sediment–water exchange, and is here considered as an explanation for the anomalous Mg content of the calcite. We hypothesize that the seep carbonates were formed during periods of active methane-rich seepage, whereas during periods of slow seepage carbonate formation was reduced. Despite different geological settings, the two examined deposits of Sarsetta and Fosso Riconi show similar features, suggesting that a common pattern of fluid circulation played a major role in carbonate formation at both seep sites.     

Mineralization of vestimentiferan tubes at methane seeps on the Congo deep-sea fan

Vestimentiferan tube worms are prominent members of modern methane seep communities and are totally reliant as adults on symbiotic sulphide-oxidizing bacteria for their nutrition. The sulphide is produced in the sediment by a biochemical reaction called the anaerobic oxidation of methane (AOM). A well-studied species from the Gulf of Mexico shows that seep vestimentiferans ‘mine’ sulphide from the sediment using root-like, thin walled, permeable posterior tube extensions, which can also be used to pump sulphate and possibly hydrogen ions from the soft tissue back into the sediment to increase the local rate of AOM. The ‘root-balls’ of exhumed seep vestimentiferans are intimately associated with carbonate nodules, which are a result of AOM. We have studied vestimentiferan specimens and associated carbonates from seeps at the Kouilou pockmark field on the Congo deep-sea fan and find that some of the posterior ‘root’ tubes of living specimens are enclosed with carbonate indurated sediment and other, empty examples are partially or completely replaced by the carbonate mineral aragonite. This replacement occurs from the outside of the tube wall inwards and leaves fine-scale relict textures of the original organic tube wall. The process of mineralization is unknown, but is likely a result of post-mortem microbial decay of the tube wall proteins by microorganisms or the precipitation from locally high flux of AOM derived carbonate ions. The aragonite-replaced tubes from the Kouilou pockmarks show similar features to carbonate tubes in ancient seep deposits and make it more likely that many of these fossil tubes are those of vestimentiferans. These observations have implications for the supposed origination of this group, based on molecular divergence estimates.     

海底甲烷缺氧氧化与冷泉碳酸盐岩沉淀动力学研究进展

海底缺氧带甲烷氧化作用是一个重要的甲烷生物地球化学过程,已被许多地球化学现象所证实。甲烷缺氧氧化有效地减少了渗漏到海水和大气中的甲烷通量,但目前仅有的数据还不能很好地限定甲烷缺氧氧化在全球甲烷循环和全球碳循环中的作用。甲烷缺氧氧化的机理还存在争议,很可能是一个“反甲烷生成”过程。在许多天然气渗漏发育区域,由于甲烷缺氧氧化作用引起环境碱度的增加而沉淀冷泉碳酸盐岩,在海底表层沉积物中形成块状碳酸盐岩结壳。但冷泉碳酸盐岩生成所需的物理化学和生物地球化学条件在很大程度上还不清楚。数值计算表明,孔隙水中溶解足够量的甲烷、冷泉渗漏强度适中、较小的生物扰动作用有利于冷泉碳酸盐岩的生成,而过高的沉积速率则抑制冷泉碳酸盐岩结壳的生成。因此,海底发育冷泉碳酸盐岩可以指示天然气渗漏系统的演化特征。     

High-resolution isotopic records (δ 18O and δ 13C) and cathodoluminescence study of lucinid shells from methane seeps of the Eastern Mediterranean

We present high-resolution isotopic records and cathodoluminescence studies of recently dead and live bivalve specimens from cold seeps, in an attempt to reconstruct environmental conditions during organism growth, and thereby the possible variability of fluid-venting activity at the seafloor. Shells of the burrowing lucinid Myrtea aff. amorpha were collected at three localities near actively venting methane seeps in the Eastern Mediterranean deep sea, using the Nautile submersible during two French oceanographic cruises: from the Kazan mud volcano, in the vicinity of the Anaximander mounts (MEDINAUT cruise, 1998), and from the central pockmark province and the Amon mud volcano of the Nile deep-sea fan (NAUTINIL cruise, 2003). The oxygen and carbon isotope compositions of 18 shells from the various localities, and also from different sites at the same locality show a rather strong scatter (1.8 < δ ¹⁸O‰ < 3.4; −10.2 < δ ¹³C‰ < 2.2), and values lower than those expected for carbonate precipitated at equilibrium with present-day bottom waters. This means that warm methane-rich fluids were mixed with bottom seawater during precipitation of shell carbonates. We have tried to determine ontogenetic age of two shells by using cathodoluminescence as a sclerochronological proxy, because the direct counting of carbonate increments was not possible in these specimens. There is a relatively good correspondence between cathodoluminescence trends and oxygen isotope profiles that might support the link between manganese incorporation during growth and temperature. Eight specimens of lucinid shells were selected for high-resolution isotopic profiling. A few shells exhibit decreasing δ ¹⁸O and δ ¹³C values from the umbo to the actively growing ventral shell margin, which can be attributed to the commonly observed physiologically controlled deceleration of growth with increasing organism age, this metabolic effect corresponding to the increase of incorporation of respiratory CO₂. A few shells exhibit high-frequency δ ¹⁸O variations with an amplitude of about 1.5‰ that might be related to temperature variations controlled by fluid-venting activity. One shell from the pockmark province of the Nile deep-sea fan records a strong, sharp δ ¹³C decrease of about 9‰, and extending over a 5-mm interval in the shell that can be related to a major methane release event. Another shell from the Kazan mud volcano exhibits a progressive increase of δ ¹³C values from −10‰ to 0‰ with age, which might indicate decreasing methane flow throughout the organism’s life. This study has demonstrated that bivalve shells from deep-sea cold seeps represent good indicators of variability in seepage activity of methane-rich fluids, at various scales in both space and time. Although the precise chronology of the observed events was not established, because shell growth rate is not known in this case, this remains a priority for future studies in such environments.     

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.     

南海神狐海域沉积物自生黄铁矿和石膏S同位素特征及对甲烷渗漏强度的示踪

The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane(AOM) coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor(cmbsf) in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values(δ~(34) S) of pyrite vary greatly(from –46.6‰ to –12.3‰ V-CDT) and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction(OSR) and is influenced by AOM with depth.The relative high abundance and δ~(34) S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone(SMTZ).The sulfur isotopic composition of gypsum(from–25‰ to –20.7‰) is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO_2,iron(Ⅲ) and oxygen driven by the SMTZ location shift to great depths.The δ~(34) S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.     

Methane seepage in the Shenhu area of the northern South China Sea: constraints from carbonate chimneys

Two authigenic carbonate chimneys were recovered from the Shenhu area in the northern South China Sea at approximately 400 m water depth. The chimneys’ mineralogy, isotopic composition, and lipid biomarkers were studied to examine the biogeochemical process that induced the formation of the chimneys. The two chimneys are composed mostly of dolomite, whereas the internal conduits and semi-consolidated surrounding sediments are dominated by aragonite and calcite. The specific biomarker patterns (distribution of lipids and their depleted δ¹³C values) indicate the low occurrence of methanotrophic archaea ANME-1 responsible for the chimneys’ formation via anaerobic oxidation of methane. A significant input of bacteria/planktonic algae and cyanobacteria to the carbon pool during the precipitation of the carbonate chimneys is suggested by the high contributions of short-chain n-alkanes (69% of total hydrocarbons) and long-chain n-alcohols (on average 56% of total alcohols). The oxygen isotopic compositions of the carbonate mixtures vary from 3.1‰ to 4.4‰ in the dolomite-rich chimneys, and from 2.1‰ to 2.5‰ in the internal conduits, which indicates that they were precipitated from seawater-derived pore waters during a long period covering the last glacial and interglacial cycles. In addition, the mixture of methane and bottom seawater dissolved inorganic carbon could be the carbon sources of the carbonate chimneys.     

Oxygen-total inorganic carbon dioxide relationship in the Pacific Ocean

The total inorganic carbon dioxide-oxygen relationship in the ocean has been studied previously using two different approaches, one of which is theoretical and the other is statistical. Discrepancies between the two sets of results have been solved in this work by applying multiple linear regression analysis to express total inorganic carbon dioxide, normalized to constant S‰, as a function of potential temperature and total alkalinity and oxygen normalized to constant S ‰. Results of the regression are in agreement with the assumption that total alkalinity changes in the open ocean are only due to S ‰ changes and calcium carbonate dissolution or precipitation; and with Redfield's model for the prediction of the total inorganic carbon dioxide-oxygen ratio for the biochemical oxidation.     

Variations of methane induced pyrite formation in the accretionary wedge sediments offshore southwestern Taiwan

The accretionary wedge of offshore southwestern Taiwan contains abundant deposits of gas hydrate beneath the sea floor. High concentrations of methane in pore waters are observed at several locations with little data concerning historical methane venting available. To understand temporal variation of methane venting in sediments over geologic time, a 23-m-long Calypso piston core (MD05-2911) was collected on the flank of the Yung-An Ridge. Pore water sulfate, dissolved sulfide, dissolved iron, methane, sedimentary pyrite, acid volatile sulfide, reactive iron, organic carbon and nitrogen as well as carbonate δ¹³C were analyzed.Three zones with markedly different pyrite concentration were found at the study site. Unit I sediments (>20 mbsf) were characterized with a high amount of pyrite (251–380 μmol/g) and a δ¹³C-depleted carbonate, Unit II sediments (15–20 mbsf) with a low pyrite (15–43 μmol/g) and a high content of iron oxide mineral and Unit III sediments (<10 mbsf) by a present-day sulfate–methane interface (SMI) at 5 m with a high amount of pyrite (84–221 μmol/g) and a high concentration of dissolved sulfide.The oscillation records of pyrite concentrations are controlled by temporal variations of methane flux. With an abundant supply of methane to Unit I and III, anaerobic methane oxidation and associated sulfate reduction favor diagenetic conditions conducive for significant pyrite formation. No AOM signal was found in Unit II, characterized by typical organically-limited normal marine sediments with little pyrite formation. The AOM induced pyrite formation near the SMI generates a marked pyrite signature, rendering such formation of pyrite as a useful proxy in identifying methane flux oscillation in a methane flux fluctuate environment.     

Reservoir characteristics and their effects on hydrocarbon accumulation in lacustrine turbidites in the Jiyang Super-depression,Bohai Bay Basin,China

A great difference exists between the hydrocarbon charging characteristics of different Tertiary lacustrine turbidites in the Jiyang Super-depression of the Bohai Bay Basin, east China. Based on wireline log data, core observation and thin-section analyses, this study presents detailed reservoir property data and their controlling effects from several case studies and discusses the geological factors that govern the hydrocarbon accumulation in turbidite reservoirs. The lacustrine fluxoturbidite bodies investigated are typically distributed in an area of 0.5–10 km², with a thickness of 5–20 m. The sandstones of the Tertiary turbidites in the Jiyang Super-depression have been strongly altered diagenetically by mechanical compaction, cementation and mineral dissolution. The effect of compaction caused the porosity to decrease drastically with the burial depths, especially during the early diagenesis when the porosity was reduced by over 15%. The effect of cementation and mineral dissolution during the late-stage diagenesis is dominated by carbonate cementation in sandstones. High carbonate cement content is usually associated with low porosity and permeability. Carbonate dissolution (secondary porosity zone) and primary calcite dissolution is believed to be related to thermal maturation of organic matter and clay mineral reactions in the surrounding shales and mudstone. Two stages of carbonate cementation were identified: the precipitation from pore-water during sedimentation and secondary precipitation in sandstones from the organic acid-dissolved carbonate minerals from source rocks. Petrophysical properties have controlled hydrocarbon accumulation in turbidite sandstones: high porosity and permeability sandstones have high oil saturation and are excellent producing reservoirs. It is also noticed that interstitial matter content affects the oil-bearing property to some degree. There are three essential elements for high oil-bearing turbidite reservoirs: excellent pore types, low carbonate cement (<5%) and good petrophysical properties with average porosity >15% and average permeability >10 mD.     

Gas hydrate decomposition recorded by authigenic barite at pockmark sites of the northern Congo Fan

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates “from above”. As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.     

Theoretical considerations about the reactions of calcification in sea water

We examine the concentration variations of the different parameters X of the carbonate system in seawater when calcium carbonate precipitation occurs. Variations are expressed as ∂[X]/∂[Ca²⁺]. Four different cases are considered: spontaneous chemical precipitation; calcification combined with photosynthetic activity under a constant ΔCT/Δ[Ca²⁺] ratio; precipitation under constant p_CO2 and precipitation under constant [Ca²⁺]·[CO₃²⁻] ionic concentration product. The last condition should be maintained by an ecosystem which, thanks to the regulation of its calcifying and photosynthetic activity, would absorb 1 mol of carbon for organic tissue each time 1 mol of CaCO₃ is formed. This stoichiometric ratio would allow the activity of these biological communities to go on in practically closed systems during periods compatible with their growth or development cycles.     

南沙海槽表层沉积自生石膏-黄铁矿组合的成因及其对天然气渗漏的指示意义

南海海槽是潜在的天然气水合物发育区,在表层沉积物中分布有石膏-黄铁矿组合。通过对石膏、黄铁矿的形貌特征、矿物组成、化学元素、硫同位素等的分析,讨论和揭示了石膏-黄铁矿组合的成岩环境、形成机理及其与天然气渗漏的关系。石膏集合体为土块状和多孔状、玫瑰状,表面分布有孔洞或微孔,黄铁矿为莓球状、球粒结块状和虫管状。不同形状的石膏、黄铁矿的化学成分没有明显差别。石膏-黄铁矿的形成机理是海底渗漏的天然气与硫酸盐发生缺氧甲烷氧化反应,产物HS^-与沉积物中的Fe^2＋反应产生FeS并转变为黄铁矿,在形成FeS的过程中产生的H^＋促进碳酸盐溶解,Ca^2＋与SO4^2-达到过饱和沉淀出重。^34S的石膏。因此,石膏-黄铁矿组合是海底存在天然气渗漏的证据,这一发现对开展南沙海槽潜在天然气水舍物的调查以及对天然气渗漏事件的研究具有一定的科学意义。     

Organic geochemistry of sediments from chemosynthetic communities,Gulf of Mexico slope

We used a research submersible to obtain 33 sediment samples from chemosynthetic communities at 541–650 m water depths in the Green Canyon (GC) area of the Gulf of Mexico slope. Sediment samples from beneath an isolated mat of H₂S-oxidizing bacteria at GC 234 contain oil (mean = 5650 ppm) and C₁–C₅ hydrocarbons (mean = 12,979 ppm) that are altered by bacterial oxidation. Control cores away from the mat contain lower concentrations of oil (mean = 2966 ppm) and C₁–C₅ hydrocarbons (mean = 83.6 ppm). Bacterial oxidation of hydrocarbons depletes O₂ in sediments and triggers bacterial sulfate reduction to produce the H₂S required by the mats. Sediment samples from GC 185 (Bush Hill) contain high concentrations of oil (mean = 24,775 ppm) and C₁–C₅ hydrocarbons (mean = 11,037 ppm) that are altered by bacterial oxidation. Tube worm communities requiring H₂S occur at GC 185 where the sea floor has been greatly modified since the Pleistocene by accumulation of oil, thermogenic gas hydrates, and authigenic carbonate rock. Venting to the water column is suppressed by this sea-floor modification, enhancing bacterial activity in sediments. Sediments from an area with vesicomyid clams (GC 272) contain lower concentrations of oil altered by bacterial oxidation (mean = 1716 ppm) but C₁–C₅ concentrations are high (mean = 28,766 ppm). In contrast to other sampling areas, a sediment associated with the methanotrophic Seep Mytilid I (GC 233) is characterized by low concentration of oil (82 ppm) but biogenic methane (C₁) is present (8829 ppm).     

Pore fluid evolution,distribution and water-rock interactions of carbonate cements in red-bed sandstone reservoirs in the Dongying Depression,China

The compositions, distribution and its interaction with rocks of the evolving pore fluids controls the distribution of carbonate cements and reservoir storage spaces. The reservoir quality of the red-bed sandstone reservoirs in the Dongying Depression was investigated by an integrated and systematic analysis including carbonate cement petrology, mineralogy, carbon and oxygen isotope ratios and fluid inclusions. The investigation was also facilitated by probing the mineral origins, precipitation mechanisms, pore fluid evolution and distribution, and water-rock interaction of carbonate cements and their influences on reservoir quality. Diagenetic-evolving fluids in the interbedded mudstones are the main source for the precipitation of calcite cements that completely fill the intergranular volume (CFIV calcite) with heavier oxygen and carbon isotopes. The ferro-carbonate cements in the reservoir sandstone are enriched in lighter carbon and oxygen isotopes. In addition to the cations released by the conversion of clay minerals in reservoirs, products of organic acid decarboxylation and the associated feldspar dissolution process provide important sources for such carbonate cementation. The carbon isotopes of CO₂ and the oxygen isotopic composition of fluids equilibrated with the CFIV calcite, ferro-calcite, dolomite and ankerite cements indicate that the pore in the red-bed reservoirs experienced high salinity fluids, which evolved from the early-formed interbedded mudstones, through organic acid input and to organic acid decarboxylation. Pore fluids from nearby mudstones migrated from the edge to the centre of sandbodies, causing strong calcite cementation along the sandbody boundaries and forming tight cementation zones. Pore fluids associated with organic CO₂ and acids and organic acid decarboxylation are mainly distributed in the internal portion of sandbodies, causing feldspar dissolution and precipitation of ferro-carbonate cements. The distribution of pore fluids caused the zonal distribution of carbonate cements in sandbodies during different periods. This may be advantageous to preserve the porosity of reservoirs as exemplified by the distribution of high-quality reservoirs in the red-bed sandbodies.     

Depositional and diagenetic controls on deeply-buried Eocene sublacustrine fan reservoirs in the Dongying Depression,Bohai Bay Basin,China

This paper investigates the reservoir potential of deeply-buried Eocene sublacustrine fan sandstones in the Bohai Bay Basin, China by evaluating the link between depositional lithofacies that controlled primary sediment compositions, and diagenetic processes that involved dissolution, precipitation and transformation of minerals. This petrographic, mineralogical, and geochemical study recognizes a complex diagenetic history which reflects both the depositional and burial history of the sandstones. Eogenetic alterations of the sandstones include: 1) mechanical compaction; and 2) partial to extensive non-ferroan carbonate and gypsum cementation. Typical mesogenetic alterations include: (1) dissolution of feldspar, non-ferroan carbonate cements, gypsum and anhydrite; (2) precipitation of quartz, kaolinite and ferroan carbonate cements; (3) transformation of smectite and kaolinite to illite and conversion of gypsum to anhydrite. This study demonstrates that: 1) depositional lithofacies critically influenced diagenesis, which resulted in good reservoir quality of the better-sorted, middle-fan, but poor reservoir quality in the inner- and outer-fan lithofacies; 2) formation of secondary porosity was spatially associated with other mineral reactions that caused precipitation of cements within sandstone reservoirs and did not greatly enhance reservoir quality; and 3) oil emplacement during early mesodiagenesis (temperatures > 70 °C) protected reservoirs from cementation and compaction.     

Hydrocarbon-derived imprints in olistostromes of the Early Serravallian Marnoso-arenacea Formation,Romagna Apennines (northern Italy)

Evidence of hydrocarbon venting within slumped bodies associated with the siliciclastic, dominantly turbiditic, Marnoso-arenacea Formation (Umbria-Romagna structural domain, Romagna Apennine, northern Italy) is documented with sedimentological, faunal, and geochemical data. Specifically,¹³C-depleted carbonate concretions and limestones and clusters of chemosynthetic clams (Vesicomyidae) have been identified in the marls of the Le Caselle Olistostrome and other slumped bodies contained within the Early Serravallian section of the Marnoso-arenacea Fm. Most of the olistostrome marls and limestones are extrabasinal and must have slid from a source area located several kilometers southwest of their present position. Thus, they presumably pertain to the Vicchio Marls Formation of the northeastern (outer) Tuscan structural domain, with possible minor contributions from the epi-Ligurian Bismantova Fm. It is suggested that venting of methane in the source area of the olistostromes permitted the establishment of exotic chemosynthetic communities and promoted the precipitation of carbonate concretions and limestones. According to the field evidence, these materials were later subjected to multistep downslope remobilization and were eventually carried into the Marnoso-arenacea basin through gravity mass transport.     

Rare earth element geochemistry in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reduction as dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE (∑REE) concentrations is evident immediately below the sediment–water interface, which can be related to early diagenetic release of REEs into pore water resulting from the re-mineralization of particulate organic matter. The highest pore water ∑REE concentrations were measured close to the sediment–water interface at ~2 cm depth. Distinct shale-normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shale-normalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in ∑REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.