Waulsortian-like mounds of the Mississippian Pekisko Formation, Northwestern Alberta: Petrographic and chemical attributes

The Tournasian age Pekisko carbonates in the Normandville Field (northwestern Alberta) form waulsortian-like, bryozoan/crinoid mounds that developed in fairly deep, low energy, cool water systems, close to the ramp margin. Three main depositional environments occur: (1) crinoidal apron with wackestone, grainstone and floatstone facies; (2) mound flank with grainstone, wackestone, packstone and floatstone facies dipping 35°; and (3) bryozoan mound core, composed of rudstone and floatstone facies with fenestrate bryozoa, minor crinoids and carbonate mud. Local highs due to fault-bounded blocks, created from the collapse of the Devonian Peace River High, may have controlled the location of mound nucleation.Diagenesis of the bryozoan/crinoid mounds included calcite cementation, compaction, dolomitization, silicification, and hydrocarbon emplacement events. The mound core facies contains submarine fascicular optic calcite and bladed/prismatic calcite cements, and later ferroan, brightly luminescent, pore-filling blocky spar cement. The crinoid apron facies contains syntaxial cement associated with crinoids, and the ferroan blocky spar cement. The mounds are dominantly limestone; however, in one well, dolomite dominates the lower section. Four types of dolomite have been identified: partial replacive; chemical-compaction-related, pervasive dolomite and saddle dolomite cement. All dolomites are non-stoichiometric (CaCO₃ mole% 56.6–62.6). The partial, zoned replacive dolomite replaces micrite and syntaxial rim calcite in mound flank and crinoid apron facies. The chemical compaction-related dolomite is found along dissolution seams and stylolites and has similar CL characteristics to the replacive dolomite. The pervasive dolomite is fabric destructive and has dull cores and bright rims in CL. Saddle dolomite (0.15 mm) has brightly-luminescent, concentric zoning and occurs in vugs and fossil pore spaces.Chemical and isotopic analysis of the bryozoan/crinoid mounds indicate that the original marine signatures in micrite, early cements, some crinoids and brachiopods have been preserved. However, carbon isotopic values for some crinoids, matrix and dolomite show more positive values compared to known Mississippian carbonate values. Recrystallization during shallow burial has reset the oxygen isotopic composition of some crinoids and micrite. Oxygen and carbon isotopic compositions of most dolomites overlap with altered crinoids and early calcite cements. However, saddle dolomites have lighter δ¹⁸O values, similar to saddle dolomites from the Devonian Wabamun Group in this area. The isotopic variations in later ferroan calcite cements show an inverted-J trend, possibly due to variable amounts of water-rock interaction. While the Sr-isotopic ratio of submarine calcite cement coincides with that of Mississippian seawater, the later ferroan calcite cement is more radiogenic, indicating a different source of fluids.     

Petrological and geochemical constraints on diagenesis and deep burial dissolution of the Ordovician carbonate reservoirs in the Tazhong area,Tarim Basin,NW China

Deeply buried (4500–7000 m) Ordovician carbonate reservoirs in the Tazhong area, Tarim Basin, NW China show obvious heterogeneity with porosity from null in limestones and sweet dolostones to 27.8% in sour dolostones, from which economically important oils, sour gas and condensates are currently being produced. Petrographic features, C, O, Sr isotopes were determined, and fluid inclusions were analyzed on diagenetic calcite, dolomite and barite from Ordovician reservoirs to understand controls on the porosity distribution. Ordovician carbonate reservoirs in the Tazhong area are controlled mainly by initial sedimentary environments and eo-genetic and near-surface diagenetic processes. However, vugs and pores generated from eogenetic and telogenetic meteoric dissolution were observed to have partially been destroyed due to subsequent compaction, filling and cementation. In some locations or wells (especially ZG5-ZG7 Oilfield nearby ZG5 Fault), burial diagenesis (e.g. thermochemical sulfate reduction, TSR) probably played an important role in quality improvement towards high-quality reservoirs. C2 calcite and dolomite cements and barite have fluid inclusions homogenization temperatures (Ths) from 86 to 113 °C, from 96 to 128 °C and from 128 to 151 °C, respectively. We observed petrographically corroded edges of these high-temperature minerals with oil inclusions, indicating the dissolution must have occurred under deep-burial conditions. The occurrence of TSR within Ordovician carbonate reservoirs is supported by C3 calcite replacement of barite, and the association of sulfur species including pyrite, anhydrite or barite and elemental sulfur with hydrocarbon and ¹²C-rich (as low as −7.2‰ V-PDB) C3 calcite with elevated Ths (135–153 °C). The TSR may have induced burial dissolution of dolomite and thus probably improved porosity of the sour dolostones reservoirs at least in some locations. In contrast, no significant burial dissolution occurred in limestone reservoirs and non-TSR dolostone reservoirs. The deeply buried sour dolostone reservoirs may therefore be potential exploration targets in Tarim Basin or elsewhere in the world.     

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.     

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.     

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.     

Saddle dolomite and calcite cements as records of fluid flow during basin evolution: Paleogene carbonates,United Arab Emirates

Field observations indicate that tectonic compression, anticline formation and concomitant uplift events of marine Paleogene carbonates in eastern United Arab Emirates, which are related to the Zagros Orogeny, have induced brecciation, karstification, and carbonate cementation in vugs and along faults and fractures. Structural analysis, stable isotopes and fluid inclusion microthermometry are used to constrain the origin and geochemical evolution of the fluids. Fluid flow was related to two tectonic deformation phases. Initially, the flux of moderately ⁸⁷Sr-rich basinal NaCl–MgCl₂–H₂O brines along reactivated deep-seated strike-slip faults have resulted in the precipitation of saddle dolomite in fractures and vugs and in dolomitization of host Eocene limestones (δ¹⁸O_V-PDB −15.8‰ to −6.2‰; homogenization temperatures of 80–115 °C and salinity of 18–25 wt.% eq. NaCl). Subsequently, compression and uplift of the anticline was associated with incursion of meteoric waters and mixing with the basinal brines, which resulted in the precipitation of blocky calcite cement (δ¹⁸O_V-PDB −22‰ to −12‰; homogenization temperatures of 60–90 °C and salinity of 4.5–9 wt.% eq. NaCl). Saddle dolomite and surrounding blocky calcite have precipitated along the pre- and syn-folding E–W fracture system and its conjugate fracture sets. The stable isotopes coupled with fluid-inclusion micro-thermometry (homogenization temperatures of ≤50 °C and salinity of <1.5 wt.% eq. NaCl) of later prismatic/dogtooth and fibrous calcites, which occurred primarily along the post-folding NNE–SSW fracture system and its conjugate fracture sets, suggest cementation by descending moderately ⁸⁷Sr-rich, cool meteoric waters. This carbonate cementation history explains the presence of two correlation trends between the δ¹⁸O_V-PDB and δ¹³C_V-PDB values: (i) a negative temperature-dependent oxygen isotope fractionation trend related to burial diagenesis and to the flux of basinal brines, and (ii) positive brine-meteoric mixing trend. This integrated study approach allows better understanding of changes in fluid composition and circulation pattern during evolution of foreland basins.     

Gravels in the Daxing conglomerate and their effect on reservoirs in the Oligocene Langgu Depression of the Bohai Bay Basin,North China

The Daxing conglomerate reservoir has become an important exploration target in the Langgu Depression of the Bohai Bay Basin. In this paper, gravel composition, void space, poroperm characteristics and hydrocarbon productivity of the Daxing conglomerate in the third member of the Oligocene Shahejie Formation (Es3) are studied in detail to understand the impact of gravel type on reservoir quality based on cores, petrographic thin-sections, scanning electron microscope (SEM) photos, porosity, permeability and well test data. The Daxing conglomerate is composed of limestone and dolomite gravels. The void space of the Daxing conglomerate includes intragravel and intergravel pores as well as fissures. Intragravel pores are dominated by gravel type. They develop as intergranular pores, intergranular dissolved pores, intragranular dissolved pores and few intercrystalline pores in limestone gravels, whereas in dolomite gravels they develop as intercrystalline pores, intercrystalline dissolved pores, dissolved pores and cavities, few intergranular pores and intergranular dissolved pores. The analysis shows that dolomite conglomerates provide better reservoir quality than limestone conglomerates. Microscopically, areal porosity in dolomite gravels is higher than that in limestone gravels. Macroscopically, porosity and permeability of conglomerates that are dominated by dolomite gravels (dolomite conglomerates) are better than those of conglomerates dominated by limestone gravels (limestone conglomerates). The dolomite conglomerates are superior to the limestone conglomerate with regard to hydrocarbon productivity at the level of parent rock and gravel properties. Poroperm characteristics and hydrocarbon productivity of dolomite reservoirs in the middle Proterozoic Changcheng and Jixian Systems (parent rocks of dolomite gravels) are better than those of the limestone reservoirs in the lower Paleozoic, Cambrian and Ordovician (parent rocks of limestone gravels). Gravel properties, including grain structure, physical nature and dissolution velocity cause the dolomite conglomerates to have more intercrystalline pores, fissures and secondary dissolved pores than limestone conglomerates.     

Pristine or altered: low-Mg calcite shells survived from massive dolomitization? A case study from Miocene carbonates

Low-Mg calcite shells have been widely used to reconstruct the chemistry of ancient seawater. There is always a question: are the shells chemically pristine? This paper presents the isotope and elemental geochemistry of low-Mg calcite bivalve shells in late Miocene platform carbonates, SE Spain. The platform carbonates were extensively dolomitized, and limestone is restricted to older stratal units, and to units mainly in topographically higher and more landward strata. Low-Mg calcite oyster shells were completely dissolved out in the basinward dolomite, but are well preserved in the limestone. These shells appear to retain the original growth microstructures, based on hand samples. Under the microscope, however, dissolution and recrystallization, as well as pristine growth lines are all present. Sr isotopes in these shells range from that of normal Miocene seawater to radiogenic values. δ¹⁸O and δ¹³C values, and Mg, Sr, and Na concentrations in these shells are rather variable. The high end members are consistent with the typical values of modern/late Miocene normal-seawater low-Mg calcite shells, whereas the low end members are close to those of diagenetic calcite cements, which have low δ¹⁸O, δ¹³C, Sr and Na values, and radiogenic Sr. The Nijar shells were altered physically and chemically to different degrees by diagenesis, although these shells are consistent with some “criteria” of unalteration. The isotopic and trace-element data collected in altered and pristine (or less altered) portions coexisting in the same shells are clearly differentiable. Quantitative simulation of covariations of geochemical pairs indicates that solid mixing of unaltered and altered portions by sampling is consistent with the variations in isotopic and elemental data recorded in the Nijar shells. The geological significance of this study is that ancient fabric-retentive calcite shells may have been altered geochemically although they may appear pristine. Calcite shells that underwent intensive diagenesis should be examined rigorously under the microscope, coupled with investigations of multiple geochemical proxies to assess chemical alteration. Only the data of unaltered shells can be used to reconstruct the chemistry of ancient seawater.     

Diagenetic evolution of the upper Cretaceous limestone and sandstone exhumed reservoirs in the western Basque–Cantabrian Basin,North Spain

The Basque–Cantabrian Basin (NE Spain) has been considered one of the most interesting areas for hydrocarbon exploration in the Iberian Peninsula since the 60th to 70th of last century. This basin is characterized by the presence of numerous outcrops of tar sands closely associated with fractures and Triassic diapirs. The aims of this work is to establish the diagenetic evolution of the Upper Cretaceous reservoir rocks with special emphasis in the emplacement of oil and their impact on reservoir quality. The studied rocks are constituted of carbonates and sandstones that contain massive quantities of bitumen filling vugs and fractures.Petrographic results indicate that the carbonate rocks from Maestu outcrops are bioclastic grainstones and wackestones, whereas the tar sandstones from Atauri and Loza outcrops are dominated by quartzarenites and subordinated subarkoses. The paragenetic sequence of the main diagenetic phases and processes include, pyrite, bladed and drusy calcite cement, calcite overgrowths, silicification of bioclasts and microcrystalline rhombic dolomite cement, and first stage of oil emplacement, blocky calcite cement, coarse crystalline calcite cement, calcitized dolomite, calcite veins, saddle dolomite and stylolites filled by the second phase of oil entrance. Together with the above mentioned diagenetic alterations, the arenites are affected by early kaolinitization of feldspars and the scarce formation of clay rim and epimatrix of illite. All sandstones and dolomitized carbonate rocks show high intercrystalline and intergranular porosity which is full by biodegraded hydrocarbons (solid bitumen). The biodegradation affects alkanes, isoprenoids and partially hopanes and steranes saturated hydrocarbons. Aromatics hydrocarbons, like naphthalenes, phenanthrenes, dibenzothiophenes and triaromatics are also affected by biodegradation. Results indicate that the first HC emplacement corresponds to early stage of calcite and dolomite cementation, and the second and more important emplacement is related to fracturation processes resulting in the formation of excellent reservoirs.     

Fluid flow reconstruction in karstified Panormide platform limestones (north-central Sicily): Implications for hydrocarbon prospectivity in the Sicilian fold and thrust belt

Diagenetic analysis based on field and petrographic observations, isotope and microthermometric data was used to reconstruct the fluid flow history of the Cretaceous shallow water limestones from the Panormide platform exposed in north-central Sicily. Analysis focused on diagenetic products in cavities and dissolution enlarged fractures of the karstified limestones that occur just below a regional unconformity. The fluid flow history could be broken down into five stages that were linked to the kinematic and burial history of the region. (1) Petrography (zoned cathodoluminescence and speleothem textures) and stable isotopes (6.5 < δ¹⁸O_V-PDB < ?3.5‰ and 0 < δ¹³C_V-PDB < ?14‰) indicate that the earliest calcite phase was associated with karstification during emergence of the platform. Limestone dissolution at this stage is important with regard to possible reservoir creation in the Panormide palaeogeographic domain. (2) Fine-grained micrite sedimentation, dated as latest Cretaceous by nannopalaeontology and its ⁸⁷Sr/⁸⁶Sr isotope ratio (0.7078), marks replacement by marine fluids during subsequent submergence of the karstified platform. (3) The following calcite cement was still precipitated by marine-derived fluids (?7.0 < δ¹⁸O_V-PDB < ?5.0‰ and ?3.0 < δ¹³C_V-PDB < 0.5‰/T_m = ?2 to ?5 °C), but at increasingly higher temperatures (T_h = 60–120 °C). This has been interpreted as precipitation during Oligocene foredeep burial. (4) Hot (T_h = 130–180 °C), low saline (T_m < ?2.5 °C) fluids with increasingly higher calculated δ¹⁸O_SMOW signatures (+6 to +14‰) subsequently invaded the karst system. These fluids most likely migrated during fold and thrust belt development. The low salinity and relatively high δ¹⁸O_SMOW signatures of the fluids are interpreted to be the result of clay dewatering reactions. The presence of bitumen and associated fluorite with hydrocarbon inclusions at this stage in the paragenesis constrains the timing of oil migration in the region. (5) Finally, high saline fluids with elevated ⁸⁷Sr/⁸⁶Sr (0.7095–0.7105) signatures invaded the karst system. This last fluid flow event was possibly coeval with localized dolomitization and calcite cementation along high-angle faults of Pliocene age, as suggested by identical radiogenic signatures of these diagenetic products.     

Structurally controlled hydrothermal dolomites in Albian carbonates of the Asón valley,Basque Cantabrian Basin,Northern Spain

Shallow marine carbonate sedimentation dominated during the Albian in the western part of the Basque Cantabrian Basin in Northern Spain, forming the large Ramales Platform. This platform originated on a less subsiding tectonic block facing deeper and more subsiding areas to the south and east, which were created by tectonic activity in the Basin. Fracture-related hydrothermal dolomites hosted in these Albian carbonates are well exposed in the Asón valley area. Mapping in the studied area revealed several dolomite bodies related to main faults that cut the stratification almost at right angles. The bodies show a vertical development along fault-strike up to 900 m thick from which kilometre-scale branches expand following the stratification. Dolomitization is pervasive and independent of the limestone facies. Main dolomite facies are fine replacive, sucrosic and saddle. Petrography, C, O and Sr isotopes and fluid-inclusion analysis support a polyphase hydrothermal dolomitization at fluid temperatures between 75 °C and 240 °C and highly variable salinity of up to 22 wt.% NaCl. Fine dolomite replaced limestone first and then, sucrosic and saddle dolomites replaced part of the first dolomite and cemented newly created fracture porosity together with different calcite cements. Zebra dolomites and hydroclastic breccias are products of this later stage. Burial analysis of the host rock supports maximum burial temperatures of 80 °C and intense tectonic activity from the Albian to Turonian with a latest Albian peak subsidence. Albian stretching of the crust and subsequent ascent of the isotherms in the area is suggested to have produced sufficient heat to the dolomitizing fluids. The structural analysis indicates a strong transtensional tectonic activity in the studied area during Albian to Turonian time with the creation of an overstep between W–E trending and N–S trending faults. Fluids moved from subsiding areas to fractured uplifted parts of the Ramales Platform, enhanced by diapiric activity.     

Fluid circulation and formation of minerals and bitumens in the sedimentary rocks of the Outer Carpathians – Based on studies on the quartz–calcite–organic matter association

Different methods have been used to examine minerals and/or solid bitumens in three adjacent Carpathian regions of Poland, Ukraine and Slovakia. The minerals fill smaller and larger veins and cavities, where they occur either together or separately. They usually co-occur with the solid bitumens. All δ¹³C_PDB values measured for calcite lie in a relatively wide interval between −6.25‰ and +1.54‰, while most values fall into the narrower interval from below 0 to about −3‰. The general range of calcite δ¹⁸O results for the whole studied region is between +17.13‰ and +25.23‰ VSMOW or from about −11 to −5‰ VPDB, while the majority of these values are between +20.0 and 23.5‰ VSMOW (−10.53 and −8.00‰ PDB, respectively). δ¹⁸O_VSMOW results for quartz vary between +23.2 and 27.6. The carbonate percentage determined in some samples falls between from <2% CaCO₃ to >90% CaCO₃, while the TOC values changes from 0.09% to over 70%.The aliphatic fraction predominates in all studied samples, mainly in bitumens and oils. The composition of the aliphatic fraction is relatively homogeneous and points to a strong aliphatic, oil-like paraffin character of the bitumens. Such a composition is characteristic of the Carpathian oils and different from the rocks studied that contain the higher percentage of a polar fraction. The content of the aliphatic fraction in bitumens is only slightly higher than that in two oils used for comparison. The distribution of n-alkanes is variable in rocks, solid bitumens as well as inclusions in quartz and calcite. Two groups of bitumens may be distinguished. Those with a predominance of long-chain n-alkanes in the C₂₅–C₂₇ interval (in some cases from C₂₃–C₂₅ and without or with a very low concentration of short-chain n-alkanes in the interval of C₁₄–C₂₁) show also a high content of isoprenoids i.e. of pristane (Pr) and phytane (Ph). In all but one bitumen samples, Pr predominates over Ph. The second group comprises oils and rock samples with a characteristic predominance of short-chain n-alkanes in the interval from C₁₃–C₁₉ and a low percentage of the long-chain n-alkanes from the n-C₂₇–n-C₃₃ interval. Pristane and phytane exhibit a concentration comparable to that of C₁₇ and C₁₈ n-alkanes with a Pr predominance over Ph. Due to high maturity, only small amounts of the most stable compounds from the hopane group have been observed in the samples, also oleanane in one case. Among the aromatic hydrocarbons, phenanthrene and its methyl- and dimethyl-derivatives are dominant in bitumens, source rocks and inclusions in calcite and quartz. Occurrence of cyclohexylbenzene and its alkyl-derivatives as well as cyclohexylfluorenes in solid bitumens suggest that they formed from oil accumulations under the influence of relatively high temperatures in oxidizing conditions.Homogenization temperatures for aqueous/brine inclusions in quartz within the Dukla and Silesian units (Polish and Ukrainian segments) are between 125 and 183.9 °C, while salinities are low in the interval of 0.2–5.5 wt% NaCl eq. The inclusions in calcite homogenize at higher temperatures of almost 200 °C and the brine displays higher salinity than the fluid in the quartz. Two quartz generations may be distinguished by inclusion and isotope characteristics and the macroscopic diversity. Oil inclusions homogenize at 95 °C. One phase inclusions in quartz contain methane, CO₂ and nitrogen in variable proportions.     

The role of diagenesis and depositional facies on pore system evolution in a Triassic outcrop analogue (SE Spain)

This study aims at unravelling the diagenetic history and its effect on the pore system evolution of the Triassic redbeds exposed in SE Spain (TIBEM¹), an outcrop analogue of the TAGI (Trias Argilo-Gréseux Inférieur) reservoir (Berkine-Ghadames Basin, Algeria). Similar climatic, base level and tectonic conditions of aforementioned alluvial formations developed analogue fluvial facies stacking patterns. Furthermore, interplay of similar detrital composition and depositional facies in both formations resulted in analogue early diagenetic features. Petrographic observations indicate lithic subarkosic (floodplain facies) and subarkosic (braidplain facies) compositions which are considered suitable frameworks for potential reservoir rocks. Primary porosity is mainly reduced during early diagenesis through moderate mechanical compaction and formation of K-feldspar overgrowth, gypsum, dolomite and phyllosilicate cements. Early mesodiagenesis is testified by low chemical compaction and quartz cementation. Telodiagenetic calcite filling fractures and K-feldspar dissolution determined the final configuration of analysed sandstones. Mercury injection-capillary pressure technique reveals overbank deposits in the floodplain as the least suitable potential reservoirs because of their lowest open porosity (OP < 16%), permeability (k < 5 mD) and small dimensions. On the other hand, braidplain deposits show the highest values of such properties (OP up to 31.6% and k > 95 mD) and greater thickness and lateral continuity, so being considered the best potential reservoir. The accurate estimation of TIBEM microscale attributes can provide important input for appraisal and enhanced oil recovery performance in TAGI and in others reservoirs consisting on similar fluvial sandy facies.     

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.     

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.     

The role played by carbonate cementation in controlling reservoir quality of the Triassic Skagerrak Formation,Norway

Anomalously high porosities up to 30% at burial depth of >3000 m along with varying amounts and types of carbonate cements occur in the fluvial channel sandstone facies of the Triassic Skagerrak Formation, Central Graben, Norway. However, porosities of the Skagerrak Formation are lower in the Norwegian sector than in the UK sector. In this study, petrographic analysis, core examination, scanning electron microscopy, elemental mapping, carbon and oxygen isotope, fluid inclusion and microgeometry analysis are performed to determine the diagenesis and direct influence on reservoir quality, with particular focus on the role played by carbonate cementation. The sandstones are mainly fine-grained lithic-arkosic to sub-arkosic arenites and display a wide range of intergranular volumes (2.3%–43.7% with an average of 23.6%). Porosity loss is mainly due to compaction (av. 26.6%) with minor contribution from cementation (av. 12.1%). The carbonate cements are patchy in distribution (from trace to 20.7%) and appear as various types e.g. calcretes (i.e. calcareous concreted gravels), poikilitic sparite and sparry ferroan dolomite, and euhedral or/and aggregated ankerite/ferroan dolomite crystals. This study highlights the association of carbonate precipitation with the remobilisation of carbonate from intra-Skagerrak calcretes during early burial stage i.e. <500 m. During deeper burial, compaction is inhibited by carbonate cements, resulting high intergranular volume of up to 32% and 29% for fine- and medium-grained sandstones, respectively. Carbonate cement dissolution probably results from both meteoric water flow with CO₂ during shallow burial, and organic CO₂ and carboxylic acid during deep burial. The maximum intergranular volume enhanced by dissolution of early carbonate cements is calculated to 8% and 5% for fine- and medium-grained sandstones, respectively. Compaction continues to exert influence after dissolution of carbonate cements, which results in a loss of ∼6% intergranular volume for fine- and medium-grained sandstones. Reservoir quality of the Norwegian sector is poorer than that of the UK sector due to a lower coverage of clay mineral coats e.g. chlorite, later and deeper onset of pore fluid overpressure, lower solubility of carbonate compared to halite, and a higher matrix content.     

Multiple dolomitization and later hydrothermal alteration on the Upper Cambrian-Lower Ordovician carbonates in the northern Tarim Basin,China

Thick Upper Cambrian-Lower Ordovician carbonates were deposited on a shallow marine platform in the northern Tarim Basin, which were extensively dolomitized, particularly for the Upper Cambrian carbonates. The resulting dolomite rocks are predominantly composed of matrix dolomites with minor cement dolomites. Based on petrographic textures, matrix dolomites consist of very finely to finely crystalline, nonplanar-a to planar-s dolomite (Md1), finely to medium crystalline, planar-e(s) dolomite (Md2), and finely to coarsely crystalline, nonplanar-a dolomite (Md3). Minor cement dolomites include finely to medium crystalline, planar-s(e) dolomite (Cd1) and coarsely crystalline, nonplanar saddle dolomite (Cd2), which partially or completely fill dissolution vugs and fractures; these cements postdate matrix dolomites but predate later quartz and calcite infills. Origins of matrix and cement dolomites and other diagenetic minerals are interpreted on the basis of petrography, isotopic geochemistry (O, C and Sr), and fluid inclusion microthermometry. Md1 dolomite was initially mediated by microbes and subsequently precipitated from slightly modified brines (e.g., evaporated seawater) in near-surface to very shallow burial settings, whereas Md2 dolomite was formed from connate seawater in association with burial dissolution and localized Mg concentration (or cannibalization) in shallow burial conditions. Md3 dolomite, however, was likely the result of intense recrystallization (or neomorphism) upon previously-formed dolomites (e.g., Md1 or Md2 dolomite) as the host carbonates were deeply buried, and influenced by later hydrothermal fluids. Subsequent cement dolomite and quartz crystals precipitated from higher-temperature, hydrothermal fluids, which were contributed more or less by the extensive Permian large igneous province (LIP) activity in Tarim Basin as evidenced by less radiogenic Sr in the cement and parts of matrix dolomites. This extensive abnormal hydrothermal activity could also have resulted in recrystallization (or neomorphism) on the previous matrix dolomites. Faults/fractures likely acted as important conduit networks which could have channeled the hydrothermal fluids from depths. However, the basin uplift triggered by the Late Hercynian Orogeny from the Late Permian would have facilitated downward infiltration of meteoric water and dilution of hydrothermal fluids, resulting in precipitation of later calcites in which lighter C and more radiogenic Sr components demonstrate such a switch of fluid properties. This study provides a useful analogue to understand the complicated dolomitizing processes and later hydrothermal alteration intimately related to the Permian LIP activity within Tarim Basin and elsewhere.     

Characteristics,genesis and parameters controlling the development of a large stratabound HTD body at Matienzo (Ramales Platform,Basque–Cantabrian Basin,northern Spain)

At Matienzo (Basque–Cantabrian Basin, northern Spain), a large stratabound HTD body (4 by 2 km² and 80–400 m thick) delimited by two parallel sinistral strike-slip faults is exposed in Aptian carbonates. The margins of the HTD body are characterised by dolomite “tongues” indicating that some limestone beds were more prone to dolomitisation. However, no clear relationship between HTD occurrence and precursor limestone facies can be established. Massive limestone beds, as found at the top of the HTD body, act as barriers to hydrothermal processes, since no dolomite is present in or above these beds. Three types of dolomites have been differentiated, i.e. 1) matrix, 2) coarse crystalline and 3) zebra dolomite. The distribution of the dolomite types is attributed to ascending fluid flow and changing degree of dolomite oversaturation.The dolomite body was formed by two dolomitisation phases under burial conditions. No indications for a synsedimentary/early diagenetic dolomitisation have been observed. The first dolomitisation phase is characterized by ferroan dolomite and the second by non-ferroan dolomite. The two HTD phases are characterised by depleted δ¹⁸O-values (ranging between −10‰ and −16‰ V-PDB), δ¹³C-values similar to the Aptian–Albian marine signature and homogenisation temperatures of primary fluid inclusions between 120 °C and 150 °C. The dolomitising fluid was enriched in ⁸⁷Sr compared to Aptian seawater, excluding the latter as an unmodified fluid source for dolomitisation. Microthermometry of primary fluid inclusions indicates that the dolomitising fluid evolved from a moderate saline (9.7 – 14.0 wt% NaCl) to a more saline (10.9 – 21.0 wt% NaCl) H₂O–NaCl brine. The dolomitising fluid likely originated from evaporated seawater. Fluid circulation through the dolomitised strata is inferred to have taken place during the tectonically active period of the late Albian throughout which important sinistral-strike slip movements along basement faults occurred.