Primary dolomite in the Late Triassic Travenanzes Formation,Dolomites, Northern Italy: Facies control and possible bacterial influence

In the late Carnian (Late Triassic), a carbonate‐clastic depositional system including a distal alluvial plain, flood basin and sabkha, tidal flat and shallow carbonate lagoon was established in the Dolomites (Northern Italy). The flood basin was a muddy supratidal environment where marine carbonates and continental siliciclastics interfingered. A dolomite phase made of sub‐micrometre euhedral crystals with a mosaic microstructure of nanometre‐scale domains was identified in stromatolitic laminae of the flood basin embedded in clay. This dolomite is interpreted here as primary and has a nearly stoichiometric composition, as opposed to younger early diagenetic (not primary) dolomite phases, which are commonly calcian. This primary dolomite was shielded from later diagenetic transformation by the clay. The stable isotopic composition of dolomite was analyzed along a depositional transect. The δ¹³C values range between ca ?6‰ and +4‰, with the most ¹³C‐depleted values in dolomites of the distal alluvial plain and flood basin, and the most ¹³C‐enriched in dolomites of the tidal flat and lagoon. Uniform δ¹⁸O values ranging between 0‰ and +3‰ were found in all sedimentary facies. It is hypothesized that the primary dolomite with mosaic microstructure nucleated on extracellular polymeric substances secreted by sulphate reducing bacteria. A multi‐step process involving sabkha and reflux dolomitization led to partial replacement and overgrowth of the primary dolomite, but replacement and overgrowth were facies‐dependent. Dolomites of the landward, clay‐rich portion of the sedimentary system were only moderately overgrown during late dolomitization steps, and partly retain an isotopic signature consistent with bacterial sulphate reduction with δ¹³C as low as ?6‰. In contrast, dolomites of the marine, clay‐free part of the system were probably transformed through sabkha and reflux diagenetic processes into calcian varieties, and exhibit δ¹³C values of ca +3‰. Major shifts of δ¹³C values strictly follow the lateral migration of facies and thus mark transgressions and regressions.     

Multistage hydrothermal dolomites in the Middle Devonian (Givetian) carbonates from the Guilin area, South China

Pervasive dolomites occur preferentially in the stromatoporoid biostromal (or reefal) facies in the basal Devonian (Givetian) carbonate rocks in the Guilin area, South China. The amount of dolomites, however, decreases sharply in the overlying Frasnian carbonate rocks. Dolostones are dominated by replacement dolomites with minor dolomite cements. Replacement dolomites include: (1) fine to medium, planar‐e floating dolomite rhombs (Rd1); (2) medium to coarse, planar‐s patchy/mosaic dolomites (Rd2); and (3) medium to very coarse non‐planar anhedral mosaic dolomites (Rd3). They post‐date early submarine cements and overlap with stylolites. Two types of dolomite cements were identified: planar coarse euhedral dolomite cements (Cd1) and non‐planar (saddle) dolomite cements (Cd2); they post‐date replacement dolomites and predate late‐stage calcite cements that line mouldic vugs and fractures. The replacement dolomites have δ¹⁸O values from ?13·7 to ?9·7‰ VPDB, δ¹³C values from ?2·7 to + 1·5‰ VPDB and ⁸⁷Sr/⁸⁶Sr ratios from 0·7082 to 0·7114. Fluid inclusion data of Rd3 dolomites yield homogenization temperatures (T_h) of 136–149 °C and salinities of 7·2–11·2 wt% NaCl equivalent. These data suggest that the replacive dolomitization could have occurred from slightly modified sea water and/or saline basinal fluids at relatively high temperatures, probably related to hydrothermal activities during the latest Givetian–middle Fammenian and Early Carboniferous times. Compared with replacement dolomites, Cd2 cements yield lower δ¹⁸O values (?14·2 to ?9·3‰ VPDB), lower δ¹³C values (?3·0 to ?0·7‰ VPDB), higher ⁸⁷Sr/⁸⁶Sr ratios (≈ 0·7100) and higher T_h values (171–209 °C), which correspond to trapping temperatures (T_r) between 260 and 300 °C after pressure corrections. These data suggest that the dolomite cements precipitated from higher temperature hydrothermal fluids, derived from underlying siliciclastic deposits, and were associated with more intense hydrothermal events during Permian–Early Triassic time, when the host dolostones were deeply buried. The petrographic similarities between some replacement dolomites and Cd2 dolomite cements and the partial overlap in ⁸⁷Sr/⁸⁶Sr and δ¹⁸O values suggest neomorphism of early formed replacement dolomites that were exposed to later dolomitizing fluids. However, the dolomitization was finally stopped through invasion of meteoric water as a result of basin uplift induced by the Indosinian Orogeny from the early Middle Triassic, as indicated by the decrease in salinities in the dolomite cements in veins (5·1–0·4 wt% NaCl equivalent). Calcite cements generally yield the lowest δ¹⁸O values (?18·5 to ?14·3‰ VPDB), variable δ¹³C values (?11·3 to ?1·2‰ VPDB) and high T_h values (145–170 °C) and low salinities (0–0·2 wt% NaCl equivalent), indicating an origin of high‐temperature, dilute fluids recharged by meteoric water in the course of basin uplift during the Indosinian Orogeny. Faults were probably important conduits that channelled dolomitizing fluids from the deeply buried siliciclastic sediments into the basal carbonates, leading to intense dolomitization (i.e. Rd3, Cd1 and Cd2).     

Recrystallization of dolomite: evidence from the Monterey Formation (Miocene), California

Dolomites from the upper calcareous-siliceous member of the Miocene Monterey Formation exposed west of Santa Barbara, California, were analysed for geochemical, isotopic and crystallographic variation. The data clearly document the progressive recrystallization of dolomite during burial diagenesis in marine pore fluids. Recrystallization is recognized by the following compositional and crystallographic variations. Dolomites have decreasing δ¹⁸O and δ¹³C compositions, decreasing Sr contents and increasing Mg contents with increasing burial depths and temperatures from east to west in the study area. δ¹⁸O values vary from 5·3‰ in the east to − 5·5‰ PDB in the west and are interpreted to reflect the greater extent and higher temperature of dolomite recrystallization in the west. δ¹³C values correlate with δ¹⁸O and decrease from 13·6‰ in the east to − 8·7‰ PDB in the west. Sr concentrations correlate positively with δ¹⁸O values and decrease from a mean of 750 ppm in the east to a mean of 250 ppm in the west. Mol% MgCO₃ values inversely correlate with δ¹⁸O values and increase from a minimum of 41·0 in the east to a maximum of 51·4 in the west. Rietveld refinements of powder X-ray diffraction data indicate that the more recrystallized dolomites have more contracted unit cells and increased cation ordering. The fraction of the Ca sites in the dolomites that are occupied by Ca atoms increases slightly with the approach to stoichiometry. The fraction of the Mg sites occupied by Mg atoms strongly correlates with mol% MgCO₃. Even in early diagenetic, non-stoichiometric dolomites, there is little substitution of Mg in Ca sites. During recrystallization, the amount of Mg substituting for Ca in Ca sites decreases even further. Most of the disorder in the least recrystallized, non-stoichiometric dolomites is related to substitution of excess Ca on Mg sites.     

Microtextural Characteristics and Origin of Dolomites in the Tepearasi Formation, SW of Beysehir-Konya, Turkey

The Tepearasi Formation of the autochthonous Geyikdagi Group in the Central Tauride Belt, SE of Beysehir, is Dogger in age and consists dominantly of massive limestones and greyish dolomites occurring within the middle to upper sections. The total thickness of the dolomitic levels ranges from 100-300 m and laterally extends 500-700 m. Three types of dolomite were distinguished through petrographic analyses: homogeneous, mottled (saddle-crystalline) and joint-filling dolomite, which were interpreted to have formed in two different stages, early diagenetic and late diagenetic. The homogeneous dolomite of the early diagenetic stage is light-coloured and monotonous-textured and shows the form of a dolosparite mosaic. The mottled dolomite formed in the late diagenetic stage is light- to dark-coloured and coarsely granular idiomorphic. The other type of late diagenetic dolomite, described as the joint-filling type, presents a crystal growth pattern from the joint walls towards the centre of the joint space. I     

Activity of Silica-Rich Hydrothermal Fluid and Its Impact on Deep Dolomite Reservoirs in the Sichuan Basin, Southern China

Well-developed dissolution pores occur in the dolomites of the Sinian Dengying Formation, which is an important oil and gas reservoir layer in the Sichuan Basin and adjacent areas in southern China. The pores are often filled with quartz, and some dolomites have been metasomatically altered to siliceous chert. Few studies have documented the characteristics, source or origin of silica-rich fluids and their effects on the dolomite reservoir. The peak homogenisation temperatures(T_h) of fluid inclusions in pore-filling quartz are between 150℃ and 190℃, with an average of 173.7℃. Gases in the inclusions are mainly composed of CO_2, CH_4 and N_2. Compared with host dolomite, pore-filling quartz and metasomatic chert contain higher amounts of Cr, Co, Mo, W and Fe, with average concentrations of 461.58, 3.99, 5.05, 31.43 and 6666.83 ppm in quartz and 308.98, 0.99, 1.04, 13.81 and 4703.50 ppm in chert, respectively. Strontium levels are lower than that in the host dolomite, with average concentrations in quartz and chert of 4.81 and 11.06 ppm, respectively. Rare earth element compositions in quartz and chert display positive Eu anomalies with a maximum δEu of 5.72. The δD_(SMOW) values of hydrogen isotopes in water from quartz inclusions vary from-85.1‰ to-53.1‰ with an average of-64.3‰, whereas the δ~(18)O_(SMOW) values range from 7.2‰ to 8.5‰ with an average of 8.2‰. The average ~(87)Sr/~(86)Sr ratios in quartz and chert are 0.711586 and 0.709917, respectively, which are higher than that in the host dolomite. The fluid inclusions, elemental and isotopic compositions demonstrate that the formation of quartz and chert was related to silica-rich hydrothermal fluid and that the fluid was the deep circulation of meteoric water along basement faults. Interactions with silica-rich hydrothermal fluids resulted in densification of dolomite reservoirs in the Dengying Formation through quartz precipitation and siliceous metasomatism. However, it increased the resistance of the host dolomite to compaction, improving the ability to maintain reservoir spaces during deep burial. Evidence for silica-rich hydrothermal activity is common in the Yangtze Platform and Tarim Basin and its influence on deep dolomite reservoirs should be thoroughly considered.     

Characteristics and Dolomitization of Upper Cambrian to Lower Ordovician Dolomite from Outcrop in Keping Uplift, Western Tarim Basin, Northwest China

Late Cambrian to Early Ordovician sedimentary rocks in the western Tarim Basin, Northwest China, are composed of shallow-marine platform carbonates. The Keping Uplift is located in the northwest region of this basin. On the basis of petrographic and geochemical features, four matrix replacement dolomites and one type of cement dolomite are identified. Matrix replacement dolomites include (1) micritic dolomites (MD1); (2) fine–coarse euhedral floating dolomites (MD2); (3) fine–coarse euhedral dolomites (MD3); and (4) medium–very coarse anhedral mosaic dolomites (MD4). Dolomite cement occurs in minor amounts as coarse saddle dolomite cement (CD1) that mostly fills vugs and fractures in the matrix dolomites. These matrix dolomites have δ18O values of ?9.7‰ to ?3.0‰ VPDB (Vienna Pee Dee Belemnite); δ13C values of ?0.8‰ to 3.5‰ VPDB; 87Sr/86Sr ratios of 0.708516 to 0.709643; Sr concentrations of 50 to 257 ppm; Fe contents of 425 to 16878 ppm; and Mn contents of 28 to 144 ppm. Petrographic and geochemical data suggest that the matrix replacement dolomites were likely formed by normal and evaporative seawater in early stages prior to chemical compaction at shallow burial depths. Compared with matrix dolomites, dolomite cement yields lower δ18O values (?12.9‰ to ?9.1‰ VPDB); slightly lower δ13C values (?1.6‰–0.6‰ VPDB); higher 87Sr/86Sr ratios (0.709165–0.709764); and high homogenization temperature (Th) values (98°C–225°C) and salinities (6 wt%–24 wt% NaCl equivalent). Limited data from dolomite cement shows a low Sr concentration (58.6 ppm) and high Fe and Mn contents (1233 and 1250 ppm, respectively). These data imply that the dolomite cement precipitated from higher temperature hydrothermal salinity fluids. These fluids could be related to widespread igneous activities in the Tarim Basin occurring during Permian time when the host dolostones were deeply buried. Faults likely acted as important conduits that channeled dolomitizing fluids from the underlying strata into the basal carbonates, leading to intense dolomitization. Therefore, dolomitization, in the Keping Uplift area is likely related to evaporated seawater via seepage reflux in addition to burial processes and hydrothermal fluids.     

Basin‐scale thermal and fluid flow histories revealed by carbonate clumped isotopes (Δ47) – Middle Jurassic carbonates of the Paris Basin depocentre

The reconstruction of past diagenetic conditions in sedimentary basins is often under‐constrained. This results from both the analytical challenge of performing the required analyses on the minute sample amounts available from diagenetic mineral phases and the lack of tracers for some of the diagenetic parameters. The carbonate clumped isotope thermometry (Δ₄₇) opens new perspectives for unravelling the temperatures of diagenetic phases together with the source of their parent fluids, two parameters that are otherwise impossible to constrain in the absence of exploitable fluid inclusions. Here is reported the study of a large number of sedimentary and diagenetic carbonate phases (from Middle Jurassic reservoirs of the Paris Basin depocentre) by combining detailed petrographic observations with a large number of Δ₄₇ data (n  > 45) on a well‐documented paragenetic sequence, including calcite and dolomite burial cements. The data reveal carbonate crystallization at temperatures between 29°C and 98°C from fluids with δ ¹⁸O_water values between −7‰ and +2‰, in response to the progressive burial and uplift of the Paris Basin, throughout 165 Myr of basin evolution. Coupled with the time–temperature evolution previously estimated from thermal maturity modelling, these temperatures allow determining the timing of four successive cementation episodes. The overall data set indicates a history of complex water mixing with a significant contribution of hypersaline waters from the Triassic aquifers migrated upward along faults during the Cretaceous subsidence of the basin. Subsequent large‐scale infiltrations of meteoric waters induced a dilution of these pre‐existing brines in response to the Paris Basin uplift in the Tertiary. Overall, the data presented here allow proposing an integrated approach to characterize the cementation events affecting the studied carbonate reservoir units, based on temperature, oxygen isotope composition and salinity of the parent fluids as well as on petrographic grounds.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.     

Early and pervasive dolomitization by near-normal marine fluids: New lessons from an Eocene evaporative setting in Qatar

The upper Palaeocene–lower Eocene Umm er Radhuma Formation in the subsurface of Qatar is dominated by subtidal carbonate depositional packages overlain by bedded evaporites. In Saudi Arabia and Kuwait, peritidal carbonate depositional sequences with intercalated evaporites and carbonates in Umm er Radhuma have been previously interpreted to have been dolomitized via downward reflux of hypersaline brines. Here, textural, mineralogical and geochemical data from three research cores in Qatar are presented which, in contrast, are more consistent with dolomitization by near-normal marine fluids. Petrographic relationships support a paragenetic sequence whereby dolomitization occurred prior to the formation of all other diagenetic mineral phases, including chert, pyrite, palygorskite, gypsum, calcite and chalcedony, which suggests that dolomitization occurred very early. The dolomites occur as finely crystalline mimetic dolomites, relatively coarse planar-e dolomites, and coarser nonplanar dolomites, all of which are near-stoichiometric (50.3 mol% MgCO₃) and well-ordered (0.73). The dolomite stable isotope values (range −2.5‰ to +1‰; mean δ¹⁸O = −0.52‰) and trace element concentrations (Sr = 40 to 150 ppm and Na = 100 to 600 ppm) are compatible with dolomitization by near-normal seawater or mesohaline fluids. Comparisons between δ¹⁸O values from Umm er Radhuma dolomite and the overlying Rus Formation gypsum further suggest that dolomitization did not occur in fluids related to Rus evaporites. This study provides an example of early dolomitization of evaporite-related carbonates by near-normal seawater rather than by refluxing hypersaline brines from overlying bedded evaporites. Further, it adds to recent work suggesting that dolomitization by near-normal marine fluids in evaporite-associated settings may be more widespread than previously recognized.     

Petrographic and Geochemicial Characteristics of the K?z?loren Formation (Upper Triassic-Lower Jurassic) in the Akp?nar (Konya, Turkey) Area

This paper describes the occurrence of dolomite and the mechanism of dolomitization of the Upper Triassic-Lower Jurassic K?z?loren Formation in the autochthonous Bolkardag? unit of the middle Taurus Mountains in south western Turkey. Dolomites were analyzed for geochemical, isotopic and crystallographic variation. Dolomites occur as a replacement of precursor carbonate and cement. The dolomite crystals range from <10 to ~1000 μm existing as both replacements and cements. Sr concentrations range between 84 and 156 ppm, and the molar Sr/Ca ratios of dolomitizing fluids are estimated to range between 0.0066 to 0.013 ratios. Dolomites are Ca-rich (with average CaCO3 and MgCO3 equal to 56.43 and 43.57 mol%, respectively) and they are non-stoichiometric, with an average Sr=116 ppm, Na=286 ppm, Mn=81 ppm, Fe=1329 ppm, and δ18O and δ13C ranges from –0.6‰ to –6.1‰ Pee Dee Belemnite [PDB], and +1.2 to +3.9‰ PDB. The North American Shale Composition [NASC]-normalized rare earth element (REE) values of the both limestone and dolomite sample groups show very similar REE patterns characterized by small positive Eu (mean=1.32 and mean=1.42, respectively) and slightly or considerably negative Ce (mean=0.61 and mean=0.72, respectively) anomalies and a clear depletion in all REE species. The K?z?loren Formation dolomites have been formed as early diagenetic from mixing zone fluids at the tidal-subtidal environment and at the late diagenetic from basinal brines at the shallow-deep burial depths.     

Massive dolomitization of a late Miocene carbonate platform: a case of mixed evaporative brines with meteoric water,Nijar, Spain

Late Miocene platform carbonates from Nijar, Spain, have been extensively dolomitized. Limestones are present in the most landward parts of the platform, in stratigraphically lower units and topographically highest outcrops, suggesting that dolomitizing fluids were derived from the adjacent Nijar Basin. The dolomite crystals range from <10 to ≈100 μm existing as both replacements and cements. Na, Cl and SO₄ concentrations in the dolomites range from 200 to 1700 p.p.m., 250–650 p.p.m., and 600–7000 p.p.m., respectively, comparable with other Tertiary and modern brine dolomite values, and also overlapping values from mixing-zone dolomites. Sr concentrations range between 50 and 300 p.p.m., and the molar Sr/Ca ratios of dolomitizing fluids are estimated to range between 7× seawater brine to freshwater ratios. The δ¹⁸O and δ¹³C of the dolomites range from ?1·0 to +4·2‰ PDB, and ?4·0 to +2·0‰ PDB, respectively. ⁸⁷Sr/⁸⁶Sr values (0·70899–0·70928) of the dolomites range from late Miocene seawater to values greater than modern seawater. Mixtures of freshwater with seawater and evaporative brines probably precipitated the Nijar dolomites. Modelled covariations of molar Sr/Ca vs. δ¹⁸O and Na/Ca vs. δ¹⁸O from these mixtures are consistent with those of the proposed Nijar dolomitizing fluids. Complete or partial dolomite recrystallization is ruled out by well preserved CL zoning, nonstoichiometry and quantitative water–rock interaction modelling of covariations of Na vs. Sr and δ¹⁸O vs. δ¹³C. The possibility of multiple dolomitization events induced by evaporative brines, seawater and freshwater, respectively, is consistent with mineral-mineral mixing modelling. The basin-derived dolomitizing brines probably mixed with freshwater in the Nijar Basin or mixed with fresh groundwater in the platform, and were genetically related either to deposition of the Yesares gypsum or the Feos gypsum. Dolomitization occurred during either the middle Messinian or the early upper Messinian. Nijar dolomitization models may be applicable to dolomitization of other late Miocene platform carbonates of the western Mediterranean. Moreover, the Nijar models may offer an analogue for more ancient evaporite-absent platform carbonates fringing evaporite basins.     

Origin and migration of palaeofluids in the Upper Visean of the Campine Basin, northern Belgium

Upper Visean limestones in the Campine Basin of northern Belgium are intensively fractured. The largest and most common fractures are cemented by non-ferroan, dull brown-orange luminescent blocky calcite. First melting temperatures of fluid inclusions in these calcites are around -57°C, suggesting that precipitation of the cements occurred from NaCl-CaCl₂-MgCl₂ fluids. The final melting temperatures (T_m^ice) are between -5 and -33°C. The broad range in the T_m^ice data can be explained by the mixing of high salinity fluids with meteoric waters, but other hypotheses may also be valid. Homogenization temperatures from blocky calcite cements in the shelf limestones are interpreted to have formed between 45 and 75°C. In carbonates which were deposited close to and at the shelf margin, precipitation temperatures were possibly in the range 70-85°C and 72-93°C, respectively. On the shelf, the calcites have a δ¹⁸O around -9.3‰ PDB and they are interpreted to have grown in a fluid with a δ¹⁸O between −3.5 and +1.0‰ SMOW. At the shelf margin, blocky calcites (δ¹⁸O∼ - 13.5‰ PDB) could have precipitated from a fluid with a δ¹⁸O betweenn -4.0 and -1.1‰ SMOW. The highest oxygen isotopic compositions are comparable to those of Late Carboniferous marine fluids (δ¹⁸O= - 1‰ SMOW). The lowest values are more positive than a previously reported composition for Carboniferous meteoric waters (δ¹⁸O= -7‰ SMOW). Precipitation is likely to have occurred in marine-derived fluids, which mixed with meteoric waters sourced from near the Brabant Massif. Fluids with a similar negative oxygen isotopic composition and high salinity are actually present in Palaeozoic formations. The higher temperature range in the limestones near the shelf margin is explained by the upward migration of fluids from the ‘basinal’ area along fractures and faults into the shelf.     

Multiple-step recrystallization within massive ancient dolomite units: an example from the Dinantian of Belgium

South of the Caledonian Brabant-Wales Massif a more than 200 m thick Tournaisian to Lower Visean replacive dolomite unit can be followed for several hundred kilometres from the Boulonnais (France) to Aachen (Germany). Field observations, of features such as karst cavities occurring at the top of the Lower Visean dolomite which are filled by Lower Visean crinoidal limestone, indicate that dolomitization and karstification took place during the Early Visean. This early development of the dolomite is in agreement with the presence of stylolites cutting the dolomite fabric. The minor element composition of the majority of the dolomites remains almost uniform throughout the entire studied area. Values for Fe, Mn, Na and Sr are normally in the range 700–4700 ppm, 15–400 ppm, 80–300 ppm and 50–200 ppm, respectively. The δ¹³C values (range-0.72 to +5.31%_o) mainly reflect the carbon isotopic composition of the precursor limestones. The δ¹⁸O values, in contrast, are highly variable: ranging from-19.15 to +0.85%_o. This rather large range of δ¹⁸O values is explained by multiple-step re-equilibration/recrystallization during progressive burial and subsequent uplift of the dolomites. These processes are also responsible for the high ⁸⁷Sr/⁸⁶Sr values of the dolomites which range from about 0.7088 to 0.7098. They are distinctly more radiogenic than Lower Visean marine carbonates (0.7076–0.7078). Correlation, however, of δ¹⁸O values or ⁸⁷Sr/⁸⁶Sr ratios with dolomite and/or cathodoluminescenec (CL) textures has not been very successful. This suggests that recrystallization may remain unrecognized if only petrographic techniques are used. Nevertheless, certain CL textures can be related to specific interactions with the ambient recrystallizing fluids.     

Origin of dolomitization on the Barbwire Terrace, Canning Basin, Western Australia

A thick, areally extensive subsurface sequence of Upper Devonian carbonates occurs on the Barbwire Terrace in the Canning Basin of Western Australia. It is a platform sequence in which most of the shallow water lithologies have been thoroughly dolomitized. Slightly deeper water marls have remained as limestones. The major, regional dolomite type in the sequence is not restricted to peritidal lithologies and forms large thicknesses of dolomite (up to 600 m) with no primary calcite. A small volume of evaporitic, supratidal dolomite is present at one location. This dolomite is derived from highly saline fluids developed in an arid supratidal environment. Replacement dolomite of the regional dolomite type has a xenotopic form, with undulose extinction, and irregular crystal boundaries. In addition, saddle dolomite cements appear to have precipitated contemporaneously with the major phase of replacement dolomite. This suggests the regional dolomite type was precipitated at slightly elevated temperatures. Dolomitized stylolites and cements appear to indicate that dolomitization occurred after cementation and pressure solution. Geochemically, the synsedimentary supratidal and regional dolomite types are quite distinctive. Supratidal dolomites have δ18O values which are significantly higher (δ18O=?2 to +1‰ (PDB)) than the regional dolomite type (δ18O=?9 to ?2‰ (PDB)). Assuming the lowest δ18O values for the sabkha dolomite represent replacement in marine waters, the oxygen isotopic composition for Upper Devonian Canning Basin marine dolomite would be around δ18O=?2‰ (PDB). The petrographic and geochemical characteristics of the regional dolomite type support a burial diagenetic origin. However, sources of magnesium in current burial dolomitization models appear insufficient to account for the large volume of dolomite on the Barbwire Terrace. Therefore, it is suggested that dolomitization may have taken place in a near-surface environment with a major recrystallization event superimposed during burial diagenesis.     

Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

Using strain birefringence in diamond to estimate the remnant pressure on an inclusion

Abstract

The Upper Triassic Chang 8 Member, the eighth member of the Yanchang Formation, is a key reservoir interval in the Jiyuan area of the Ordos Basin. The reservoir quality of the Chang 8 Member tight sandstones is extremely heterogeneous owing to the widespread distribution of carbonate cements. The carbonate cements commonly develop near sandstone–mudstone interfaces and gradually decrease away from the interfaces to the centres of the sand bodies. However, the content of carbonate cements (≤6%) has a positive correlation with the visual porosity in the Chang 8 Member sandstone, revealing that the carbonate cements contribute to the compaction resistance and the residual primary pores of reservoirs during the diagenetic process. Three main types of carbonate cement are identified: type I (calcite), type II (calcite and ferrocalcite), and type III (dolomite and ankerite). The type I calcite is characterised by enriched δ¹³C (mean –3.41‰) and δ¹⁸O (mean –15.17‰) values compared with the type II (mean δ¹³C?=?–7.33‰, δ¹⁸O?=?–18.90‰) and type III (mean δ¹³C?=?–10.0‰, δ¹⁸O?=?–20.2‰) cements. Furthermore, the mean δ¹⁸O value (–4.7‰) of the type I pore fluids is 1.5‰ and 0.9‰ lower than the type II (mean –3.2‰) and type III (mean –3.8‰) pore fluids, respectively. This indicates that the evolving pore fluids experienced some relative strong water–rock interactions that provided the original materials (e.g. Ca²⁺, Fe³⁺, and Mg²⁺) for the carbonate cements during the diagenetic process. The highly saline lake water directly provided the primary material for the type I calcite precipitation, which also provided the material necessary for the precipitation of the type II and type III carbonate cements, causing enriched δ¹⁸O values of the pore fluids during the precipitation of the type II and type III carbonate cements. Although the earlier dissolved pores were filled with ferrocalcite, dolomite and ankerite in the middle–late diagenetic stages, some residual pores and fractures remained to become the potential reservoir storage spaces for the oil and gas exploration in the Jiyuan area.     

Dolomitization of the Waulsortian Limestone (Lower Carboniferous) in the Irish Midlands

The Waulsortian Limestone (Lower Carboniferous) of the southern Irish Midlands is dolomitized pervasively over a much larger region than previous studies have documented. This study indicates a complex, multistage, multiple fluid history for regional dolomitization. Partially and completely dolomitized sections of Waulsortian Limestones are characterized by finely crystalline (0·01–0·3 mm) planar dolomite. Planar replacive dolomite is commonly followed by coarse (≥0·5 mm) nonplanar replacive dolomite, and pervasive void‐filling saddle dolomite cement is frequently associated with Zn–Pb mineralization. Planar dolomite has average δ¹⁸O and δ¹³C values (‰ PDB) of –4·8 and 3·9 respectively. These are lower oxygen and slightly higher carbon isotope values than averages for marine limestones in the Waulsortian (δ¹⁸O=–2·2, δ¹³C=3·7). Mean C and O isotope values of planar replacive dolomite are also distinct from those of nonplanar and saddle dolomite cement (–7·0 and 3·3; –7·4 and 2·4 respectively). Fluid inclusions indicate a complex history involving at least three chemically and thermally distinct fluids during dolomite cementation. The petrography and geochemistry of planar dolomites are consistent with an early diagenetic origin, possibly in equilibrium with modified Carboniferous sea water. Where the Waulsortian was exposed to hydrothermal fluids (70–280 °C), planar dolomite underwent a neomorphic recrystallization to a coarser crystalline, planar and nonplanar dolomite characterized by lower δ¹⁸O values. Void‐filling dolomite cement is isotopically similar to nonplanar, replacive dolomite and reflects a similar origin from hydrothermal fluids. This history of multiple stages of dolomitization is significantly more complex than earlier models proposed for the Irish Midlands and provides a framework upon which to test competing models of regional vs. localized fluid flow.     

Traces of brine and hydrocarbon migration in carbon,oxygen, and sulfur isotopic compositions of reservoir rocks in the Talakan petroleum field,Southwestern Yakutia

Dolomites from the productive Osa horizon (upper subformation of the Lower Cambrian Bilir Formation) in the Talakan petroleum field show a prominent 1–2‰ decrease in δ¹⁸O (from 23–24 to 21–22‰), which presumably marks a zone of relatively high water/rock ratios. Productive boreholes are characterized by moderate δ³⁴S values (from 25.1 to 30.6‰) and negative correlation between δ³⁴S in anhydrite and δ¹⁸O in associated dolomite, which points to a partial sulfate reduction during catagenesis. In nonproductive borehole, δ³⁴S values increase significantly (from 31.4 to 35.6‰) and show positive correlation with δ¹⁸O in dolomite. Rocks recovered by nonproductive borehole possibly recrystallized during early diagenesis, and, correspondingly lost their permeability and capacity to form pores. Limestones and dolomites of the Osa horizon have a carbon isotopic composition within the range of normal marine carbonates (δ¹³C = 0 ± 1 ‰), which does not indicate a significant role of organic matter in postsedimentary recrystallization of carbonate sediments. A positive δ¹³C excursion up to 4.5‰ recorded in the lower subformation of the Bilir Formation presumably occurred at the sedimentation stage under conditions of high rates of bioproductivity and organic matter burial in sediments.     

Geology and Isotope Geochemistry of the Yinchanggou-Qiluogou Pb-Zn Deposit, Sichuan Province, Southwest China

The Yinchanggou-Qiluogou Pb-Zn deposit,located in the western Yangtze Block,southwest China,is hosted by the Upper Sinian Dengying Formation dolostone.Ore bodies occur in the Qiluogou anticline and the NS-and NNW-trending faults.Sulfide ores mainly consist of sphalerite,pyrite,galena and calcite,with subordinate dolomite and quartz.Seventeen ore bodies have been discovered to date and they have a combined 1.0 million tons of sulfide ores with average grades of 2.27wt%Zn and 6.89wt%Pb.The δD_(H2O-SMOW) and δ~(18)O_(H2O-SMOW) values of fluid inclusions in quartz and calcite samples range from-68.9‰ to-48.7‰ and 7.3‰ to 15.9‰,respectively,suggesting that H_2O in the hydrothermal fluids sourced from metamorphic water.Calcite samples have δ~(13)C_(PDB) values ranging from-6.2‰ to-4.1‰ and δ~(18)O_(SMOW) values ranging from 15.1‰ to 17.4‰,indicating C and O in the hydrothermal fluids likely derived from a mixed source of metamorphic fluids and the host carbonates.The δ~(34)S_(CDT) values of sulfide minerals range from 5.5‰ to 20.3‰,suggesting that thermal chemical reduction of sulfate minerals in evaporates were the most probable source of S in the hydrothermal fluids.The ~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb and ~(208)Pb/~(204)Pb ratios of sulfide minerals fall in the range of 18.11 to 18.40,15.66 to 15.76 and 38.25 to 38.88,respectively.The Pb isotopic data of the studied deposit plot near the upper crust Pb evolution curve and overlap with the age-corrected Proterozoic basement rocks and the Upper Sinian Dengying Formation hosting dolostone.This indicates that the Pb originated from a mixed source of the basement metamorphic rocks and the ore-hosting carbonate rocks.The ore geology and C-H-O-S-Pb isotopic data suggest that the YinchanggouQiluogou deposit is an unusual carbonate-hosted,strata-bound and epigenetic deposit that derived ore-forming materials from a mixed source of the underlying Porterozoic basements and the Sinian hosting carbonates.     

Petrography and geochemistry of early-stage, fine- and medium-crystalline dolomites in the Middle Devonian Presqu'ile Barrier at Pine Point, Canada

The petrography and geochemistry of fine- and medium-crystalline dolomites of the Middle Devonian Presqu’ile barrier at Pine Point (Western Canada Sedimentary Basin) are different from those of previously published coarse-crystalline and saddle dolomites that are associated with late-stage hydrothermal fluids. Fine-crystalline dolomite consists of subhedral to euhedral crystals, ranging from 5 to 25 μm (mean 8 μm). The dolomite interbedded with evaporitic anhydrites that occur in the back-barrier facies in the Elk Point Basin. Fine-crystalline dolomite has δ¹⁸Ο values between ?1·6 to –3·8‰ PDB and ⁸⁷Sr/⁸⁶Sr ratios from 0·7079–0·7081, consistent with derivation from Middle Devonian seawater. Its Sr concentrations (55–225 p.p.m., mean 105 p.p.m.) follow a similar trend to modern Little Bahama seawater dolomites. Its rare earth element (REE) patterns are similar to those of the limestone precursors. These data suggest that this fine-crystalline dolomite formed from Middle Devonian seawater at or just below the sea floor. Medium-crystalline dolomite in the Presqu’ile barrier is composed of anhedral to subhedral crystals (150–250 μm, mean 200 μm), some of which have clear rims toward the pore centres. This dolomite occurs mostly in the southern lower part of the barrier. Medium-crystalline dolomite has δ¹⁸O values between ?3·7 to ?9·4‰ PDB (mean ?5·9‰ PDB) and ⁸⁷Sr/⁸⁶Sr ratios from 0·7081–0·7087 (mean 0·7084); Sr concentrations from 30 to 79 p.p.m. (mean 50 p.p.m.) and Mn content from 50 to 253 p.p.m. (mean 161 p.p.m.); and negative Ce anomalies compared with those of marine limestones. The medium-crystalline dolomite may have formed either (1) during shallow burial at slightly elevated temperatures (35–40 °C) from fluids derived from burial compaction, or, more likely (2) soon after deposition of the precursor sediments by Middle Devonian seawater derived from the Elk Point Basin. These results indicate that dolomitization in the Middle Devonian Presqu’ile barrier occurred in at least two stages during evolution of the Western Canada Sedimentary Basin. The geochemistry of earlier formed dolomites may have been modified if the earlier formed dolomites were porous and permeable and water/rock ratios were large during neomorphism.