The impact of organic fluids on the carbon isotopic compositions of carbonate-rich reservoirs: Case study of the Lucaogou Formation in the Jimusaer Sag,Junggar Basin,NW China

The processes involved in the interaction between organic fluids and carbonates, and the resulting effect on reservoir quality during the evolution and maturation of organic matter remain unclear despite the fact that these processes influence the carbon and oxygen isotopic compositions of carbonates. Here, we provide new insights into these processes using data obtained from a detailed analysis of a mixed dolomitic–clastic and organic-rich sedimentary sequence within the middle Permian Lucaogou Formation in the Junggar Basin of NW China. The techniques used during this study include drillcore observations, thin section petrography, scanning electron microscopy (SEM) and electron probe microanalysis, and carbon and oxygen isotope analyses. Oil grades and total organic carbon (TOC) contents represent the amount of oil charging and the abundance of organic fluids within a reservoir, respectively, and both negatively correlate with the whole-rock δ¹³C and δ¹⁸O of the carbonates in the study area, indicating that organic fluids have affected the reservoir rocks. Secondary carbonates, including sparry calcite and dolomite overgrowths and cements, are common within the Lucaogou Formation. Well-developed sparry calcite is present within dark mudstone whereas the other two forms of secondary carbonates are present within the dolomite-rich reservoir rocks in this formation. Comparing thin section petrology with δ¹³C compositions suggests that the carbon isotopic composition of matrix carbonates varies little over small distances within a given horizon but varies significantly with stratigraphic height as a result of the development of secondary carbonates. The net change in whole-rock δ¹³C as a result of these secondary carbonates ranges from 1.8‰ to 4.6‰, with the secondary carbonates having calculated δ¹³C compositions from −18.6‰ to −8.5‰ that are indicative of an organic origin. The positive correlation between the concentration of Fe within matrix and secondary carbonates within one of the samples suggests that the diagenetic system within the Lucaogou Formation was relatively closed. The correlation between δ¹³C and δ¹⁸O in carbonates is commonly thought to be strengthened by the influence of meteoric water as well as organic fluids. However, good initial correlation between δ¹³C and δ¹⁸O of whole rock carbonates within the Lucaogou Formation (resulted from the evaporitic sedimentary environment) was reduced by organic fluids to some extent. Consequently, the δ¹³C–δ¹⁸O covariations within these sediments are not always reliable indicators of diagenetic alteration by organic fluids or meteoric water.The characteristics and δ¹³C compositions of the sparry calcite within the formation is indicative of a genetic relationship with organic acids as a result of the addition of organic CO₂ to the reservoir. Further analysis suggests that both carbonate and feldspar were dissolved by interaction with organic CO₂. However, dissolved carbonate reprecipitated as secondary carbonates, meaning that the interaction between organic fluids and dolomites did not directly improve reservoir quality, although this process did enhance the dissolution of feldspar and increase porosity. This indicates that the δ¹³C and δ¹⁸O of secondary carbonates and their influence on whole-rock carbonate isotopic values can be used to geochemically identify the effect of organic fluids on closed carbonate-rich reservoir systems.     

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 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.     

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

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

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.     

Authigenic dolomites in the Eocene–Oligocene organic carbon-rich shales from the Polish Outer Carpathians: Evidence of past gas production and possible gas hydrate formation in the Silesian basin

Eocene–Oligocene dolomite concretions and beds from the Grybów and Dukla units of the Polish Outer Carpathians were studied. These rocks occur in the organic carbon-rich, marine and fine-grained deposits of hemipelagic or turbiditic origin. Mineralogic, elemental and stable C and O isotopic composition of the dolomites was determined. Results indicate that the rocks were formed by precipitation of predominantly Fe-rich dolomite cement close to the sediment-water interface prior to significant compaction. The main source of bicarbonate for dolomite formation was bacterial methanogenesis as evidenced by the high δ¹³C values up to 16.6‰. The main source of alkalinity was probably weathering of silicate minerals which might have also liberated Ca and Mg ions for the dolomites to form. The distribution of these dolomites indicates that microbial methane production was widespread in the Silesian basin. Moreover, formation of some dolomites in the Eastern part of the Dukla unit was probably associated with gas hydrates as suggested by the elemental and oxygen isotopic composition of dolomitic matrix. Therefore, the dolomites may serve as a proxy of areas where biogenic methane was produced, where the rocks had high hydrocarbon potential, and where hydrates could have existed.Detailed mineralogic and petrographic analyses allowed for the reconstruction of the diagenetic sequence and the evolution of pore fluids. Textural relationships between successive cement generations indicate that the central parts of the composite dolomite crystals experienced corrosion and that the latest ankerite cement filled the secondary intragranular cavities within those crystals. This observation shows that reconstructions of pore fluid evolution based on core-to-rim analyses of such composite crystals may lead to wrong interpretations. Septarian cracks developed in the dolomites are often filled with multistage cements. The earliest generations are ferroan dolomite and ankerite cements which precipitated within the cracks simultaneously to the ferroan dolomite and ankerite cements from the matrix of the dolomitic rocks which shows that septarian cracking occurred very early, during the final stages of concretionary formation. These cements were followed by the late-diagenetic precipitates, mainly quartz, kaolinite and blocky calcite. This calcite is commonly associated with bitumen which shows that it precipitated during or after oil migration in the decarboxylation zone.     

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.     

Fracturing and cementation of shallow buried Miocene proximal alluvial fan deposits

Fluid flow in fractures and host rocks has been investigated in shallow buried Miocene alluvial fan deposits. A structural, petrographical (optical, CL, SE microscopes and XRD) and geochemical (microprobe and δ¹⁸O-δ¹³C stable isotopes) study has been performed in normal faults affecting Serravalian-Tortonian siliciclastic rocks of the Vallès-Penedès basin. These faults formed during the development of the Vallès-Penedès fault-related syncline, which caused the rotation of the earliest fractures. Faulting occurred continuously before, during and after host rock cementation. Rocks affected by faulting are represented by clay-rich gouges, which formed thanks to the high phyllite clast content within the otherwise clean and mature sandstones and conglomerates. Despite the low permeability of these rocks, cross-fault and fault-parallel fluid flows occurred in most of the faults.Host rocks and veins were cemented by two generations of calcite, i.e. Cc1 and Cc2. Cc1 precipitated from meteoric waters at shallow burial conditions whereas Cc2 precipitated from meteoric waters in a confined aquifer.Palygorskite has been identified in shear zones within the gouges indicating their later formation by interaction of Mg-rich fluids with previous smectites. These fluids probably derived from Miocene seawater expelled from the underlying Transitional–Marine Complex “TMC” by compaction.Sedimentation, fracturing and cementation occurred in a very short lapse time of about 6–7 Ma, between the Serravalian-Tortonian age of the sediments and the end of the extensional tectonics in the Vallès-Penedès fault (Pliocene).     

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

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

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‰.     

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

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

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.     

Hydrothermal dolomite reservoir in the Precambrian Dengying Formation of central Sichuan Basin,Southwestern China

The Precambrian Dengying Formation is maximum buried carbonate reservoir in the Sichuan Basin. Reservoir types are thought to be dominated by sedimentary facies or karst controlled. Precursory sedimentary fabrics have been intensively superimposed by medium-to coarse-grained dolomite in most areas. Dolomitized intervals contain planar and saddle dolomite, quartz, and few hydrothermal replacive minerals. Fluid inclusion analyses of dolomite suggests that rocks are formed at temperatures ranging from 132.6°C to 218.7°C in the presence of dense brines, while the dolomite phases are demonstrated by negative δ¹⁸O and δ¹³C VPDB values. Strontium isotopes enriched in ⁸⁷Sr, and the fluid source could support the conclusion. The dolomites of the Dengying Formation in central Sichuan Basin that formed around basement-rooted wrench faults, in turn mainly oriented towards the North-South and East-West strike-slip faults, are detectable. Lastly, the grabens take the form of negative flower structures-the result of an intra-cratonic rift that took place during the Sinian and early Cambrian period through tensional faulting.Our primary contention is that basement fault, which resulted in the magmatic or deep clastic fluids migration, was key for the formation of the obvious high-temperature coarse dolomite and saddle dolomite replacement. Subsequently, hot fluids that circulated within the matrix dolomite were aided by fractures or vugs and (1) leached into the dolomite, producing vugs and pores; (2) precipitated saddle dolomite, and (3) led to hydrofracturing, fractures enlargement, and further brecciation. The dolomite eventually formed porous hydrocarbon reservoirs through diagenesis. This model better illustrates how fluids that originated from deep basin migration along strike-slip transfer faults and fractures flowed out to structures in Precambrian basement-rooted faults, inheriting the rift in the Cambrian. The data involved offers a fresh perspective pertinent to deep hydrocarbon exploration of dolomite reservoirs in Southwestern China.     

Dolomitization of the lower Ordovician Catoche formation: Implications for hydrocarbon exploration in western Newfoundland

The lower Ordovician St. George Group in Western Newfoundland consists of a sequence of subtidal and peritidal carbonates, which are extensively dolomitized. The current study investigates the diagenetic evolution of the Catoche Formation from the Port aux Choix and Port au Port peninsulas in order to study the controls on reservoir quality in western Newfoundland. The Catoche Formation dolomites are classified into three main generations. Early and pervasive replacement dolomite (D1) indicates that dolomitization began during early stages of diagenesis. Stable isotope and trace element data indicate significant variations between D1 dolomite on the Port aux Choix and Port au Port peninsulas. The depleted δ¹⁸O signature of D1 dolomite fluids (−8.7 ± 1.3‰ VPBD) on the Port aux Choix Peninsula is consistent with partial dolomitization associated with mixing of seawater and meteoric waters on the flanks of structural highs. In contrast δ¹⁸O values (−6.1 ± 0.7‰ VPBD) and trace element data from the Port au Port Peninsula indicate that pervasive D1 was associated with mixing of possibly post evaporitic brines with meteoric waters.Later-stage replacement dolomites (D2) are associated with enhancement in porosity through the development of intercrystalline pores, while latest stage saddle dolomite (D3), significantly occluded the pores in some horizons. D2 dolomite formed due to the influx of warm (>100 °C), saline (>15 eq. wt% NaCl) fluids. Intercrystalline porosity in D2 formed due to the dolomitization of precursor calcite, due to the lower molar volume of dolomite compared to calcite. Therefore porosity development is lower on the Port au Port Peninsula, with no significant volume change during the recrystallization of the pervasive early (D1) dolomicrite. Similarly, extensive porous horizons on the Port aux Choix Peninsula are related to the limited extent of D1 dolomitization. This suggests that the quality of a potential dolomite reservoir is strongly controlled by tectonic and diagenetic history of host carbonates.     

Molecular and isotopic characteristics of gas hydrate-bound hydrocarbons in southern and central Lake Baikal

We investigated the molecular composition (methane, ethane, and propane) and stable isotope composition (methane and ethane) of hydrate-bound gas in sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved from eight gas seep sites, located in the southern and central Baikal basins. Empirical classification of the methane stable isotopes (δ¹³C and δD) for all the seep sites indicated the dominant microbial origin of methane via methyl-type fermentation; however, a mixture of thermogenic and microbial gases resulted in relatively high methane δ¹³C signatures at two sites where ethane δ¹³C indicated a typical thermogenic origin. At one of the sites in the southern Baikal basin, we found gas hydrates of enclathrated microbial ethane in which ¹³C and deuterium were both highly depleted (mean δ¹³C and δD of –61.6‰ V-PDB and –285.4‰ V-SMOW, respectively). To the best of our knowledge, this is the first report of C₂ δ¹³C–δD classification for hydrate-bound gas in either freshwater or marine environments.     

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.     

Impact of basin burial and exhumation on Jurassic carbonates diagenesis on both sides of a thick clay barrier (Paris Basin,NE France)

Several diagenetic models have been proposed for Middle and Upper Jurassic carbonates of the eastern Paris Basin. The paragenetic sequences are compared in both aquifers to propose a diagenetic model for the Middle and Late Jurassic deposits as a whole. Petrographic (optical and cathodoluminescence microscopy), structural (fracture orientations) and geochemical (δ¹⁸O, δ¹³C, REE) studies were conducted to characterize diagenetic cements, with a focus on blocky calcite cements, and their connection with fracturation events. Four generations of blocky calcite (Cal1–Cal4) are identified. Cal1 and Cal2 are widespread in the dominantly grain-supported facies of the Middle Jurassic limestones (about 90% of the cementation), whereas they are limited in the Oxfordian because grain-supported facies are restricted to certain stratigraphic levels. Cal1 and Cal2 blocky spars precipitated during burial in a reducing environment from mixed marine-meteoric waters and/or buffered meteoric waters. The meteoric waters probably entered aquifers during the Late Cimmerian (Jurassic/Cretaceous boundary) and Late Aptian (Early Cretaceous) unconformities. The amount of Cal2 cement is thought to be linked to the intensity of burial pressure dissolution, which in turn was partly controlled by the clay content of the host rocks. Cal3 and Cal4 are associated with telogenetic fracturing phases. The succession of Cal3 and Cal4 calcite relates to the transition towards oxidizing conditions during an opening of the system to meteoric waters at higher water/rock ratios. These meteoric fluids circulated along Pyrenean, Oligocene and Alpine fractures and generated both dissolution and subsequent cementation in Oxfordian vugs in mud-supported facies and in poorly stylolitized grainstones. However, these cements filled only the residual porosity in Middle Jurassic limestones. In addition to fluorine inputs, fracturation also permitted inputs of sulphur possibly due to weathering of Triassic or Purbeckian evaporites or H₂S input during Paleogene times.     

Diagenesis and origin of calcite cement in the Flemish Pass Basin sandstone reservoir (Upper Jurassic): Implications for porosity development

The Flemish Pass Basin is a deep-water basin located offshore on the continental passive margin of the Grand Banks, eastern Newfoundland, which is currently a hydrocarbon exploration target. The current study investigates the petrographic characteristics and origin of carbonate cements in the Ti-3 Member, a primary clastic reservoir interval of the Bodhrán Formation (Upper Jurassic) in the Flemish Pass Basin.The Ti-3 sandstones with average Q_86.0F_3.1R_10.9 contain various diagenetic minerals, including calcite, pyrite, quartz overgrowth, dolomite and siderite. Based on the volume of calcite cement, the investigated sandstones can be classified into (1) calcite-cemented intervals (>20% calcite), and (2) poorly calcite-cemented intervals (porous). Petrographic analysis shows that the dominant cement is intergranular poikilotopic (300–500 μm) calcite, which stared to form extensively at early diagenesis. The precipitation of calcite occured after feldspar leaching and was followed by corrosion of quartz grains. Intergranular calcite cement hosts all-liquid inclusions mainly in the crystal core, but rare primary two-phase (liquid and vapor) fluid inclusions in the rims ((with mean homogenization temperature (T_h) of 70.2 ± 4.9 °C and salinity estimates of 8.8 ± 1.2 eq. wt.% NaCl). The mean δ¹⁸O and δ¹³C isotopic compositions of the intergranular calcite are −8.3 ± 1.2‰, VPDB and −3.0 ± 1.3‰, VPDB, respectively; whereas, fracture-filling calcite has more depleted δ¹⁸O but similar δ¹³C values. The shale normalized rare earth element (REE_SN) patterns of calcite are generally parallel and exhibit slightly negative Ce anomalies and positive Eu anomalies. Fluid-inclusion gas ratios (CO₂/CH₄ and N₂/Ar) of calcite cement further confirms that diagenetic fluids originated from modified seawater. Combined evidence from petrographic, microthermometric and geochemical analyses suggest that (1) the intergranular calcite cement precipitated from diagenetic fluids of mixed marine and meteoric (riverine) waters in suboxic conditions; (2)the cement was sourced from the oxidation of organic matters and the dissolution of biogenic marine carbonates within sandstone beds or adjacent silty mudstones; and (3) the late phases of the intergranular and fracture-filling calcite cements were deposited from hot circulated basinal fluids.Calcite cementation acts as a main controlling factor on the reservoir quality in the Flemish Pass reservoir sandstones. Over 75% of initial porosity was lost due to the early calcite cementation. The development of secondary porosity (mostly enlarged, moldic pores) and throats by later calcite dissolution due to maturation of organic matters (e.g., hydrocarbon and coals), was the key process in improving the reservoir quality.     

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

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

State-of-the-Art of Gas Hydrates and Relative Permeability of Hydrate Bearing Sediments

The methane gas production potential from its hydrates, which are solid clathrates, with methane gas entrapped inside the water molecules, is primarily dependent on permeability characteristics of their bearing sediments. Moreover, the dissociation of gas hydrates, which results in a multi-phase fluid migration through these sediments, becomes mandatory to determine the relative permeability of both gaseous and aqueous fluids corresponding to different hydrate saturations. However, in this context, the major challenges are: (1) obtaining undisturbed in-situ samples bearing gas hydrates; and (2) maintenance of the thermodynamic conditions to counter hydrate dissociation. One of the ways to overcome this situation is synthesis of gas hydrates in laboratory conditions, followed by conducting permeability tests on them. In addition, empirical relationships that relate permeability of the gas hydrate bearing sediments to pore-structure characteristics (viz., pore size distribution and interconnectivity) can also be conceived. With this in view, a comprehensive review of the literature dealing with different techniques adopted by researchers for synthesis of gas hydrates, permeability tests conducted on the sediments bearing them, and analytical and empirical correlations employed for determination of permeability of these sediments was conducted and a brief account of the same is presented in this article.