Palaeoproterozoic evaporites in Fennoscandia: implications for seawater sulphate, the rise of atmospheric oxygen and local amplification of the δ13C excursion

This paper addresses global oxygenation and establishment of a marine sulphate reservoir in the Palaeoproterozoic. We report syn-depositional, marine, anhydrite-containing pseudomorphs after Ca-sulphates as widespread throughout the Tulomozero Formation in the SE Fennoscandian Shield, implying that surface waters were oxidized and a large SO marine reservoir was developed as early as 2100 Ma. The Ca-sulphates and associated magnesite and halite precipitated syn-depositionally from oxidized, evolved and modified seawater in coastal playa, sabkha and intertidal flat settings. ⁸⁷Sr/⁸⁶Sr and δ¹³C of associated ¹³C-rich stromatolitic dolostones were environmentally controlled with the highest ratios occurring in playa and sabkha carbonates. The results imply that the Palaeoproterozoic δ¹³C_carb excursion was amplified by 8‰ by local environmental factors and calls into question many observations of putative δ¹³C global signals reported previously from similar Palaeoproterozoic, evaporitic, dolostones. The local environmental amplification can explain a large regional and intercontinental δ¹³C discrepancy observed in synchronous carbonates.     

Dedolomitization and calcite cementation in the Middle Devonian Winnipegosis Formation in Central Saskatchewan,Canada

Limestone consisting of finely to medium crystalline calcite mosaics is present in the upper part of the Winnipegosis Formation on the east‐central margin of the Elk Point Basin where the overlying Prairie Evaporite deposits have been removed. This type of crystalline limestone is interpreted as dedolomite, based on petrographic observations. The δ¹⁸O and δ¹³C values of the Winnipegosis dedolomite vary from ?12·8‰ to ?11·9‰ VPDB (Vienna Pee Dee Belemnite) and from ?0·5‰ to +1·7‰ VPDB, respectively; both values are significantly lower than those for the corresponding dolomite. The ⁸⁷Sr/⁸⁶Sr ratios of the dedolomite are significantly higher, between 0·7082 and 0·7087. The spatial distribution and geochemical data of the Winnipegosis dedolomite suggest that dedolomitization was related to an influx of fresh groundwater and dissolution of the Prairie Evaporite anhydrite during the latest Mississippian to the Early Cretaceous when the basin was subjected to uplift and erosion. The Winnipegosis dedolomite displays a series of replacement fabrics showing progressive calcitization of dolomite, including the occurrence of dedolomite restricted along fractures and adjacent areas, dolomite patches ‘floating’ in the dedolomite masses and massive dedolomite with sparsely scattered dolomite relicts. However, the characteristic fabrics resulting from dedolomitization documented in the literature have not been observed in the Winnipegosis dedolomite. Coarsely to very coarsely crystalline, subhedral to euhedral calcite cement is restricted in the dedolomite. The petrographic features, isotopic compositions and homogenization temperatures, coupled with the burial history of the Winnipegosis Formation, constrain the precipitation of the calcite cement from a mixing of basinal brines and fresh groundwater during Late Cretaceous to Neogene time. The more negative C‐isotopic signatures of the calcite cement (?5·3‰ to ?2·3‰ VPDB) probably reflect a hydrocarbon‐derived carbon.     

Microcrystalline dolomite in a middle Permian volcanic lake: Insights on primary dolomite formation in a non-evaporitic environment

Lacustrine dolomite nucleation commonly occurs in modern and Neogene evaporitic alkaline lakes. As a result, ancient lacustrine microcrystalline dolomite has been conventionally interpreted to be formed in evaporitic environments. This study, however, suggests a non-evaporitic origin of dolomite precipitated in a volcanic–hydrothermal lake, where hydrothermal and volcanic processes interacted. The dolomite occurs in lacustrine fine-grained sedimentary rocks in the middle Permian Lucaogou Formation in the Santanghu intracontinental rift basin, north-west China. Dolostones are composed mainly of nano-sized to micron-sized dolomite with a euhedral to subhedral shape and a low degree of cation ordering, and are interlaminated and intercalated with tuffaceous shale. Non-dolomite minerals, including quartz, alkaline feldspars, smectite and magnesite mix with the dolomite in various proportions. The ⁸⁷Sr/⁸⁶Sr ratios (0.704528 to 0.705372, average = 0.705004) and δ²⁶Mg values (−0.89 to −0.24‰, average = −0.55‰) of dolostones are similar to those of mantle rocks, indicating that the precipitates mainly originated from fluids that migrated upward from the mantle and were subject to water–rock reactions at a great depth. The δ¹⁸O values (−3.1 to −22.7‰, average = −14.0‰) of the dolostones indicate hydrothermal influence. The trace and rare earth element concentrations suggest a saline, anoxic and volcanic–hydrothermally-influenced subaqueous environment. In this subaqueous environment of Lucaogou lake, locally high temperatures and a supply of abundant Mg²⁺ from a deep source induced by volcanic–hydrothermal activity formed favourable chemical conditions for direct precipitation of primary dolomite. This study's findings deepen the understanding of the origin and processes of lacustrine primary dolomite formation and provide an alternative possibility for environmental interpretations of ancient dolostones.     

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).     

Formation of lacustrine dolomite in the late Miocene marginal lakes of the East Mediterranean (Northern Israel)

The study focuses on the formation of lacustrine dolomite in late Miocene lakes, located at the East Mediterranean margins (Northern Israel). These lakes deposited the sediments of the Bira (Tortonian) and Gesher (Messinian) formations that comprise sequences of dolostone and limestone. Dolostones are bedded, consist of small‐sized (<7 μm), Ca‐rich (52 to 56 mol %) crystals with relatively low ordering degrees, and present evidence for replacement of CaCO₃ components. Limestones are comprised of a wackestone to mudstone matrix, freshwater macrofossils and intraclasts (mainly in the Bira Formation). Sodium concentrations and isotope compositions differ between limestones and dolostones: Na = ~100 to 150 ppm; ~1000 to 2000 ppm; δ¹⁸O = ?3·8 to ?1·6‰; ?2·0 to +4·3‰; δ¹³C = ?9·0 to ?3·4‰; ?7·8 to 0‰ (VPDB), respectively. These results indicate a climate‐related sedimentation during the Tortonian and early Messinian. Wet conditions and positive freshwater inflow into the carbonate lake led to calcite precipitation due to intense phytoplankton blooms (limestone formation). Dry conditions and enhanced evaporation led to precipitation of evaporitic CaCO₃ in a terminal lake, which caused an increased Mg/Ca ratio in the residual waters and penecontemporaneous dolomitization (dolostone formation). The alternating lithofacies pattern reveals eleven short‐term wet–dry climate‐cycles during the Tortonian and early Messinian. A shift in the environmental conditions under which dolomite formed is indicated by a temporal decrease in δ¹⁸O of dolostones and Na content of dolomite crystals. These variations point to decreasing evaporation degrees and/or an increased mixing with meteoric waters towards the late Messinian. A temporal decrease in δ¹³C of dolostones and limestones and appearance of microbial structures in close association with dolomite suggest that microbial activity had an important role in allowing dolomite formation during the Messinian. Microbial mediation was apparently the main process that enabled local growth of dolomite under wet conditions during the latest Messinian.     

Sedimentology,stable‐isotope geochemistry and palaeoenvironment of dolostones capping late Precambrian glacial sequences in Australia

Thin (<10 m), extensive dolostones conformably capping late Precambrian glaciogenic rocks in the Kimberley region and the Adelaide Geosyncline commonly comprise micritic dolomite apparently of ‘primary’ or early diagenetic origin. Their aphanitic texture, the presence of algal and cryptalgal lamination, tepee structures and intraclastic rocks, and the lack of saline evaporites or their pseudomorphs, suggest deposition mainly in supratidal to lagoonal environments under a seasonally evaporitic/humid climate. Less common oolitic or pelletal rocks and a finely laminated shaly dolostone facies also suggest peritidal to marine influences.

The ‘cap’ dolostones (omitting possible large erratics) have a δ¹⁸O mean of —6.4 ± 1.9% vs. PDB and a δ¹³C mean of —1.9 ± 2.1% vs. PDB. The oxygen mean is comparable to that determined for other late Precambrian ‘primary’ or early diagenetic dolostones not associated with glaciogenic rocks and presumably deposited under warm conditions. The carbon mean, in contrast, is lighter than that determined for other late Precambrian dolostones.

The sedimentological and oxygen‐isotope data are consistent with relatively high formation‐temperatures for the cap dolostones. Abrupt climatic warming at the close of late Precambrian glacial epochs is implied.     

Stable isotope geochemistry of magnesite from Holocene salt lake deposits,Taoudenni, Mali

Stable isotope data (δ¹⁸O, δ¹³C) were obtained for magnesite (MgCO₃) from Holocene salt lake deposits of the Taoudenni–Agorgott basin, Mali, in which it is the only carbonate mineral present. The deposits have a high glauberite content (Na₂Ca(SO₄)₂), representing a type of continental evaporite formation that is commonly magnesite‐bearing. Samples from seven different levels in a 5 m long sequence were analysed. δ¹⁸O_V‐PDB values are between +3.17 and +5.91‰, which is lower than might be expected for evaporitic environments, recording reduced ¹⁸O enrichment at high salinity. δ¹³C_V‐PDB values are between −1.32‰ and −4.79‰, showing an influence of carbon derived from the decomposition of organic matter rather than from exchange with atmospheric CO₂. Covariance between δ¹⁸O and δ¹³C is strong for the lower part of the sequence, recording coupled ¹⁸O and ¹³C enrichment as commonly observed for closed basins. Covariance is lacking for the upper part of the sequence, with only periodic massive magnesite deposition in a more shallow lake. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Genesis of island dolostones

Cenozoic ‘island dolostones’ are found on islands throughout the oceans of the world. Due to their geological youth and lack of deep burial, these dolostones provide an opportunity to resolve some of the mysteries surrounding the dolomite problem. In island dolostone bodies, which are of variable size and variable dolomitization, the petrographic and geochemical properties of the dolostones are characterized by geographic and stratigraphic variations. In the larger island‐wide dolostone bodies, like those found on Grand Cayman, there are progressive increases in mole %Ca (%Ca_mean: 53·9 to 57·6%), depletion of the heavier ¹⁸O and ¹³C isotopes (δ¹⁸O_mean: 3·6 to 2·1‰ _VPDB; δ¹³C_mean: 3·1 to 1·4‰ _VPDB), and changes from fabric‐retentive to fabric‐destructive fabrics and a decrease in the amount of dolomite cement from the coastal areas towards the centres of the islands, similar to the Little Bahama Bank. These changes define geographically concentric zones that parallel the coastlines and reflect geochemical modification of the dolomitizing fluid through water–rock interactions, mixing with meteoric water and the changes in the rate and flux of seawater as it flowed from coasts to island interiors. The pattern of dolomitization, however, is not consistent from island to island because geographic and stratigraphic variations, specific to each island, influenced groundwater flow pattern (for example, geometry and size of the islands; the porosity and permeability of the precursor limestone), the duration of the dolomitization reaction, and other factors. The geographic extent of dolomitization and variation in dolomite stoichiometry of island dolostones may be comparable to the reaction stages established in high‐temperature laboratory experiments.     

Calcitization/dedolomitization of Jurassic dolostones (Lebanon): results from petrographic and sequential geochemical analyses

Calcitized Jurassic dolostones from central Mount Lebanon (Kesrouane Formation) are discussed utilizing petrographic, mineralogical and geochemical data. In particular, two sequential extraction methods for both major/trace elements and stable isotope analyses provide results that support and refine conventional bulk analyses data. The new data demonstrate that the major dedolomitization phase of the investigated Jurassic carbonates occurred as a result of the migration of karst‐related meteoric waters (characterized by soil‐derived carbon, and estimated δ¹⁸O_V‐SMOW composition between ?7·2‰ and ?3·4‰) into previously dolomitized horizons within the limestone rock, during the final uplift and emergence of Mount Lebanon, after Palaeogene time. The study demonstrates that, in this case, the mechanisms of dedolomitization and their resulting fabrics are controlled primarily by the texture of the original dolomite rock. Pervasively dolomitized rocks, where the micritic matrix is entirely dolomitized, show calcitization mainly through dissolution/precipitation. By contrast, the rock textures that still include a considerable amount of limey micritic matrix – spared from dolomitization – are more prone to mole per mole and mimic replacement of the dolomite crystals by calcite.     

Dolomitization,gypsum calcitization and silicification in carbonate–evaporite shallow lacustrine deposits

This paper describes and interprets the mineral and facies assemblages that occur in carbonate–evaporite shallow lacustrine deposits, considering the importance of the processes pathway (i.e. dolomitization, gypsum calcitization and silicification). The Palaeogene deposits of the Deza Formation (Almazán Basin, central‐northern Spain) are selected as a case study to determine the variety of physicochemical processes taking place in carbonate–evaporite shallow lakes and their resulting diagenetic features. Dolostones are the predominant lithology and are composed mainly of dolomite with variable amounts of secondary calcite (5 to 50%), which mainly mimic lenticular gypsum (pseudomorphs). Five morphological types of dolomite crystal were identified as follows: dolomite tubes, dolomite cylinders, rhombohedral dolomite, spheroidal and quasi‐rhombohedral dolomite, and cocoon‐shaped dolomite. The dolomite cylinders and tubes are interpreted as the dolomitized cells of a widespread microbial community. The sequence of diagenetic processes started with growth of microlenticular interstitial gypsum in a calcareous mud deposited on the playa margin mudflats, and that sometimes included microbial sediments. Immediately following growth of gypsum, dolomite replaced the original calcite (or possibly aragonite) muds, the microbial community and the gypsum. Partial or total replacement of gypsum by dolomite was related mainly to the biomineralization of endolithic microbial communities on gypsum crystals. Later calcitization took place under vadose, subaerial exposure conditions. The development of calcrete in distal alluvial settings favoured the release of silica and subsequent silicification on the playa margin mudflats. Stable isotope compositions of calcite range from ?9·02 to ?5·83‰ δ¹³C_PDB and ?7·10 to 1·22‰ δ¹⁸O_PDB; for the dolomite, these values vary from ?8·93 to ?3·96‰ δ¹³C_PDB and ?5·53 to 2·4‰ δ¹⁸O_PDB. Quartz from the cherts has δ¹⁸O_SMOW values ranging from 27·1 to 31·1‰. Wide variation and relatively high δ¹⁸O_SMOW values for dolomite indicate evaporitic and closed hydrological conditions; increased influx of meteoric waters reigned during the formation of secondary calcite spar.     

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.     

Paragenesis of Cretaceous to Eocene carbonate reservoirs in the Ionian fold and thrust belt (Albania): relation between tectonism and fluid flow

ABSTRACT This paper examines the diagenetic history of dual (i.e. matrix and fracture) porosity reservoir lithologies in Cretaceous to Eocene carbonate turbidites of the Ionian fold and thrust belt, close to the oil‐producing centre of Fier–Ballsh (central Albania). The first major diagenetic event controlling reservoir quality was early cementation by isopachous and syntaxial low‐Mg calcite. These cements formed primarily around crinoid and rudist fragments, which acted as nucleation sites. In sediments in which these bioclasts are the major rock constituent, this cement can make up 30% of the rock volume, resulting in low effective porosity. In strata in which these bioclasts are mixed with reworkedmicrite, isopachous/syntaxial cements stabilized the framework, and matrixporosity is around 15%. The volumetric importance of these cements, their optical and luminescence character (distribution and dull orange luminescence) and stable isotopic signal (δ¹⁸O and δ¹³C averaging respectively; ?0·5‰ VPDB and +2‰ VPDB) all support a marine phreatic origin. Within these turbidites and debris flows, several generations of fractures alternated with episodes of cementation. A detailed reconstruction of this history was based on cross‐cutting relationships of fractures and compactional and layer‐parallel shortening (LPS) stylolites. The prefolding calcite veins possess orange cathodoluminescence similar to that of the host rock. Their stable isotope signatures (δ¹⁸O of ?3·86 to ?0·85‰ VPDB and δ¹³C of – 0·14 to + 2·98‰ VPDB) support a closed diagenetic rock‐buffered system. A similar closed system accounts for the selectively reopened and subsequently calcite‐cemented LPS stylolites (δ¹⁸O of ?1·81 to ?1·14‰ VPDB and δ¹³C of +1·52 to +2·56‰ VPDB). Within the prefolding veins, brecciated host rock fragments and complex textures such as crack and seal features resulted from hydraulic fracturing. They reflect expulsion of overpressured fluids within the footwall of the frontal thrusts. After folding and thrust sheet emplacement, some calcite veins are still rock buffered (δ¹⁸O of ?0·96 to +0·2‰ VPDB and δ¹³C of +0·79 to +1·37‰ VPDB), whereas others reflect external (i.e. extraformational) and thus large‐scale fluid fluxes. Some of these veins are linked to basement‐derived fluid circulation or originated from fluid flow along evaporitic décollement horizons (δ¹⁸O around +3·0‰ VPDB and δ¹³C around +1·5‰ VPDB). Others are related to the maturation of hydrocarbons in the system (δ¹⁸O around ?7·1‰ VPDB and δ¹³C around +9·3‰ VPDB). An open joint system reflecting an extensional stress regime developed during or after the final folding stage. This joint system enhanced vertical connectivity. This open joint network can be explained by the high palaeotopographical position and the folding of the reservoir analogue within the deformational front. The joint system is pre‐Burdigalian in age based upon a dated karstified discordance contact. Sediment‐filled karst cavity development is linked to meteoric water infiltration during emergence of some of the structures. Despite its sediment fill, the karst network is locally an important contributor to reservoir matrix porosity in otherwise tight lithologies. Development of secondary porosity along bed‐parallel and bed‐perpendicular (i.e. layer‐parallel shortening) stylolites is interpreted as a late‐stage diagenetic event associated with migration of acidic fluids during hydrocarbon maturation. Development of porosity along the LPS system enhanced the vertical reservoir connectivity.     

Multiple Dolomitization and Fluid Flow Events in the Precambrian Dengying Formation of Sichuan Basin,Southwestern China

The Precambrian Dengying Formation is a set of large-scale, extensively dolomitized, carbonate reservoirs occurring within the Sichuan Basin. Petrographic and geochemical studies reveal dolomitization was a direct result of precipitation by chemically distinct fluids occurring at different times and at different intensities. Based on this evidence, dolomitization and multiple fluid flow events are analyzed, and three types of fluid evolution models are proposed. Results of analysis show that Precambrian Dengying Formation carbonates were deposited in a restricted peritidal environment(630–542 Ma). A high temperature and high Mg~(2+) concentration seawater was a direct result of dolomitization for the micrite matrix, and for fibrous aragonite in primary pores. Geochemical evidence shows low δ~(18)O values of micritic dolomite varying from-1.29‰ to-4.52‰ PDB, abundant light rare earth elements(REEs), and low dolomite order degrees. Microbes and meteoric water significantly altered dolomite original chemical signatures, resulting in algal micritic dolomite and the fine-grained, granular, dolosparite dolomite having very negative δ~(18)O values. Finely crystalline cement dolomite(536.3–280 Ma) and coarsely crystalline cement dolomite have a higher crystallization degree and higher order degree. The diagenetic sequence and fluid inclusion evidence imply a linear correlation between their burial depth and homogenization temperatures, which closely resemble the temperature of generated hydrocarbon. Compared with finely crystalline dolomite, precipitation of coarsely crystalline dolomite was more affected by restricted basinal fluids. In addition, there is a trend toward a more negative δ~(18)O value, higher salinity, higher Fe and Mn concentrations, REE-rich. Two periods of hydrothermal fluids are identified, as the exceptionally high temperatures as opposed to the temperatures of burial history, in addition to the presence of high salinity fluid inclusions. The early hydrothermal fluid flow event was characterized by hot magnesium-and silicon-rich fluids, as demonstrated by the recrystallized matrix dolomite that is intimately associated with flint, opal, and microcrystalline quartz in intergranular or intercrystalline pores. This event was likely the result of a seafloor hydrothermal chimney eruption during Episode I of the Tongwan Movement(536.3±5.5 Ma). In contrast, later hydrothermal fluids, which caused precipitation of saddle dolomite, were characterized by high salinity(15–16.05 wt% NaCl equivalent) and homogenization temperatures(250 to 265°C), δ~(18)O values that were more enriched, and REE signatures. Geochemical data and the paragenetic sequence indicate that this hydrothermal fluid was related to extensive Permian large igneous province activity(360–280 Ma). This study demonstrates the presence of complicated dolomitization processes occurring during various paleoclimates, tectonic cycles, and basinal fluids flow; results are a useful reference for these dolomitized Precambrian carbonates reservoirs.     

Multistage dolomitization and distribution of dolomitized bodies in Early Jurassic carbonate platforms (Southern Alps,Italy)

The Early Jurassic dolomitized carbonates are a hydrocarbon exploration target in Northern Italy. Of these carbonates, the Liassic Albenza Formation platform and the overlying Sedrina Formation shelf were studied to define a pervasive dolomitization model and to shed light on dolomite distribution in the sub‐surface. Field work, as well as analyses of well cores, stable isotopes, trace elements and fluid inclusions, was carried out on the outcropping thrust belt and sub‐surface deformed foreland of the Southern Alps. Petrographic analyses showed a first, pervasive, replacement dolomitization phase (D1) followed by volumetrically less important dolomite cement precipitation phases (D2, D3 and D4). The δ¹⁸O values fall between ?8·2‰ and 0·1‰ Vienna‐Pee Dee Belemnite with the more depleted samples belonging to dolomite cement‐rich dolostones; the δ¹³C ranges from 2·6‰ to 3·7‰ Vienna‐Pee Dee Belemnite. Analysis of trace elements showed different Fe and Mn contents in the sub‐surface and outcropping dolostones, and a higher Fe in the younger dolomite cements. An increase in the precipitation temperature (up to 130 °C from fluid inclusion data) and a decrease in diagenetic fluid salinity (from sea water to brackish) are observed from the first pervasive replacement dolomite to the dolomite cement phases. Field observations indicate that, in the Albenza Formation, dolomitization was limited to palaeohighs or faulted platform margins in the Early Jurassic carbonates. The pervasive replacement phase is interpreted based on a ‘compaction model’; the formation fluids expelled from compacting basinal carbonates could have funnelled along faults into permeable palaeohighs. The high homogenization temperature of the dolomite cements and decreased salinities indicate precipitation at great depth with an influx of meteoric water. These data, along with the thermal history, suggest that the dolomite cements precipitated according to the ‘tectonic squeegee’ dolomitization model. The dolomite precipitation temperature was set against the thermal history of the carbonate platform to interpret the timing of dolomite precipitation. The dolomite precipitation temperatures (90 to 100 °C) were reached in the studied formations first in the thrust fold belt (Early Tertiary, 60 Ma), and then in the foreland succession during the Late Tertiary (10 Ma). This observation suggests that the dolomite precipitation fronts moved southwards over time, recording a ‘diagenetic wave’ linked to the migration of the orogenic system. Observations suggest that the porosity increased during the first phase of replacement dolomitization while the dolomite cementation phases partially occluded the pores. The distribution of porous dolomitized bodies is therefore linked to the ‘compaction dolomitization’ model.     

奥地利东阿尔卑斯山地区杂砂岩带中赋存于碳酸盐岩中的晶质菱镁矿床

奥地利东阿尔卑斯山地区Austroalpine杂砂岩带中的石炭纪Veitsch逆冲推覆体是"Veitsch型"晶质菱镁矿化的典型地区。几十年来,对其成因的解释一直是人们争论的焦点。为了解决这一长久以来的问题,本文对Veitsch推覆体的地质学、矿物学和地球化学制约条件进行了论述。菱镁矿仅仅存在于Veitsch推覆体之中,而其它推覆体中的碳酸盐岩岩层中则无菱镁矿。赋存于Veitsch推覆体中的碳酸盐岩石中的菱镁矿以不规则的岩株状、透镜状和层状产出。块状和厚层状的菱镁矿总是被白云岩包裹。在Veitsch推覆体中,沉积作用开始于晚维宪期的后造山的类磨拉石海相建造,并晚于内部基底带的变形和变质作用("Bretonic期")形成,该基底带位于现代的东阿尔卑斯山地区。沉积序列研究表明,演化从浅海大陆架开始,有时还穿插有高盐度的泻湖和透镜状生物礁,发展到海退的海岸线伴随有发育强烈的三角洲沉积的分支海湾和河流。由于成矿作用有好几个期次,所以对地球化学数据的解释相当复杂。 在Hohentauern／Sunk矿床中,石膏和硬石膏层在菱镁矿质沉积主岩中互层,其δ34S值分别为 17.6±0.2‰和 17.2±0.2‰,表现出石炭纪海水的特征。白云岩和菱镁矿的REE浓度要高于石灰质主岩。在Hohentauern／Sunk矿床中,球形白云岩中的白云岩球体和白云质基质     

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.     

Carbon isotope stratigraphy using carbonate cements in the Triassic Sherwood Sandstone Group: Corrib Field,west of Ireland

Carbon stable isotopes from carbonate minerals (mainly dolomite) from six wells from the Lower Triassic Sherwood Sandstones of the Corrib Gas Field, Slyne Basin, west of Ireland, allow stratigraphic correlation. The results also provide information on palaeoenvironmental change during the deposition of these continental redbed sedimentary rocks. The Triassic reservoir rocks have been buried to > 4000 m and heated to > 165 °C and now contain methane-rich gas. Although the oxygen isotopic signal has been at least partially reset during burial and heating, a primary carbon isotopic signal appears to have survived diagenesis. The carbon isotope ratio varies from − 3.2‰ to + 2.1‰. All six wells show similar stratigraphic changes when all the carbon isotope data are plotted relative to a major playa horizon. δ¹³C increases from about − 3‰ at the base of the Sherwood to about + 2‰ 170 m above the base. δ¹³C then decreases to about − 2‰ for the next 70 m and remains steady for the following 50 m. The top 20 m of the Sherwood contains carbonate with a δ¹³C values decreasing to about − 3‰. The occurrence of a stratigraphically-correlatable carbon isotope pattern implies that the primary evolution signal has been preserved. The change in δ¹³C correlates with indicators of aridity and biological stress such that the highest δ¹³C values are in sedimentary rocks deposited in a playa lake (arid times); these rocks contain the greatest quantity of dolomite cement. Conversely, the lowest δ¹³C values correspond to sedimentary rocks deposited from well-developed rivers (relatively humid times) from the lowest quantity of dolomite cement. The same carbon isotope evolution has been found in another well in the Slyne basin and in Belgium, suggesting that the palaeoenvironmental isotope signal in the Triassic sedimentary rocks of the Corrib Field may have a regional significance.     

Petrographic and geochemical evidence for the formation of primary, bacterially induced lacustrine dolomite: La Roda 'white earth' (Pliocene, central Spain)

Upper Pliocene dolomites (‘white earth’) from La Roda, Spain, offer a good opportunity to evaluate the process of dolomite formation in lakes. The relatively young nature of the deposits could allow a link between dolomites precipitated in modern lake systems and those present in older lacustrine formations. The La Roda Mg‐carbonates (dolomite unit) occur as a 3·5‐ to 4‐m‐thick package of poorly indurated, white, massive dolomite beds with interbedded thin deposits of porous carbonate displaying root and desiccation traces as well as local lenticular gypsum moulds. The massive dolomite beds consist mainly of loosely packed 1‐ to 2‐μm‐sized aggregates of dolomite crystals exhibiting poorly developed faces, which usually results in a subrounded morphology of the crystals. Minute rhombs of dolomite are sparse within the aggregates. Both knobbly textures and clumps of spherical bodies covering the crystal surfaces indicate that bacteria were involved in the formation of the dolomites. In addition, aggregates of euhedral dolomite crystals are usually present in some more clayey (sepiolite) interbeds. The thin porous carbonate (mostly dolomite) beds exhibit both euhedral and subrounded, bacterially induced dolomite crystals. The carbonate is mainly Ca‐dolomite (51–54 mol% CaCO₃), showing a low degree of ordering (degree of ordering ranges from 0·27 to 0·48). Calcite is present as a subordinate mineral in some samples. Sr, Mn and Fe contents show very low correlation coefficients with Mg/Ca ratios, whereas SiO₂ and K contents are highly correlated. δ¹⁸O‐ and δ¹³C‐values in dolomites range from ?3·07‰ to 5·40‰ PDB (mean=0·06, σ=1·75) and from ?6·34‰ to ?0·39‰ PDB (mean=?3·55, σ=1·33) respectively. Samples containing significant amounts of both dolomite and calcite do not in general show significant enrichment or depletion in ¹⁸O and ¹³C between the two minerals. The correlation coefficient between δ¹⁸O and δ¹³C for dolomite is extremely low and negative (r=?0·05), whereas it is higher and positive (r=0·47) for calcite. The lacustrine dolomite deposit from La Roda is interpreted mainly as a result of primary precipitation of dolomite in a shallow, hydrologically closed perennial lake. The lake was supplied by highly saturated HCO₃^?/CO₃^2? groundwater that leached dolomitic Mesozoic formations. Precipitation of dolomite from alkaline lake waters took place under a semi‐arid to arid climate. However, according to our isotopic data, strong evaporative conditions were not required for the formation of the La Roda dolomite. A significant contribution by bacteria to the formation of the dolomites is assumed in view of both petrographic and geochemical evidence.     

Multiple metasomatism in Sulu ultrahigh-P garnet peridotite constrained by petrological and geochemical investigations

The pre‐pilot hole (PP1) of the Chinese Continental Scientific Drilling Project (CCSD) recovered drill core samples from a 118 m‐thick section of peridotites located at Zhimafang in the southern Sulu UHP terrane, China. The peridotites consist of phlogopite‐bearing garnet lherzolite, harzburgite, wehrlite and dunite. Some peridotite layers contain magnesite and Ti‐clinohumite, and are characterized by LREE and LILE enrichment and HFSE depletion. Phlogopite (Phl) occurs in the peridotite matrix and is LILE‐enriched with low Zr/Hf ratios (0.19–0.60). Phlogopite shows a mantle signature in H and O isotopes (δ¹⁸O: +5.4‰ to +5.9‰, and δD: ?76‰ to ?91‰). Ti‐clinohumite (Ti‐Chu) is Nb and Ta‐enriched and has higher Ti and HREE concentrations than phlogopite. Magnesite (Mgs) occurs as megacrysts, as a matrix phase, and as veins (±Phl ± Ti‐Chu), and contains low REE^total contents (<0.3 ppm) with a flat REE pattern. The δ¹⁸O values (+5.5‰ to +8.0‰) of magnesite are in the range of primary carbonatite, but the δ¹³C values (?2.4‰ to ?3.4‰) are slightly more positive than those of the mantle and of primary carbonatite. Petrochemical data indicate that the Zhimafang peridotite was subjected to three episodes of metasomatism, listed in succession from oldest to youngest: (1) crystallization of phlogopite in the mantle caused by infiltration of K‐rich hydrous fluid/melt; (2) formation of Mgs and Mgs ± Phl ± Ti‐Chu veins possibly caused by infiltration of mantle‐derived carbonatitic melt with a hydrous silicate component; and (3) replacement of magnesite, garnet and diopside by dolomite and secondary hydrous phases caused by a crust‐related, CO₂‐bearing, aqueous fluid. Stable isotopic compositions of phlogopite and magnesite indicate metasomatic agents for events (1) and (2) are from an enriched mantle. Multiple metasomatism imposed on mantle peridotite of variable composition led to significant compositional heterogeneity at all scales within the Zhimafang peridotite.