Origin and diagenetic evolution of Ca–Mg–Fe carbonates in some coalfields of Japan

Carbonate concretions, lenses and bands in the Pleistocene, Palaeogene and Upper Triassic coalfields of Japan consist of various carbonate minerals with varied chemical compositions. Authigenic carbonates in freshwater sediments are siderite > calcite > ankerite > dolomite >> ferroan magnesite; in brackish water to marine sediments in the coal measures, calcite > dolomite > ankerite > siderite >> ferroan magnesite; and in the overlying marine deposits, calcite > dolomite >> siderite. Most carbonates were formed progressively during burial within a range of depths between the sediment-water interface and approximately 3 km. The mineral species and the chemical composition of the carbonates are controlled primarily by the initial sedimentary facies of the host sediments and secondarily by the diagenetic evolution of pore water during burial. Based on the regular sequence and burial depth of precipitation of authigenic carbonates in a specific sedimentary facies, three diagenetic stages of carbonates are proposed. Carbonates formed during Stage I (< 500 m) strongly reflect the initial sedimentary facies, e.g. low Ca-Mg siderite in freshwater sediments which are initially rich in iron derived from lateritic soil on the nearby landmass, and Mg calcite and dolomite in brackish-marine sediments whose pore waters abound in Ca²⁺ and Mg²⁺ originating in seawater and calcareous shells. Carbonates formed during Stage II (500–2000 m) include high Ca-Mg siderite, ankerite, Fe dolomite and Fe–Mg calcite in freshwater sediments. The assemblage of Stage II carbonates in brackish-marine sediments in the coal measures is similar to that in freshwater sediments. This suggests similar diagenetic environments owing to an effective migration and mixing of pore water due to the compaction of host sediments. Carbonates formed during Stage III (> 2000 m) are Fe calcite and extremely high Ca-Mg siderite; the latter is exclusively in marine mudstones. The supply of Ca is partly from the alteration of silicates in the sediments at elevated burial temperatures. After uplift, calcite with low Mg content precipitates from percolating groundwater and fills extensional cracks.     

Formation of bed‐scale spatial patterns in dolomite abundance during early dolomitization: Part I. Mechanisms and feedbacks revealed by reaction–transport modelling

Dolomites of varied ages exhibit metre‐scale nested patterns of lateral periodic variation in permeability and porosity and, by inference, dolomite abundance as most examples are 100% dolomite. Two‐dimensional reaction–transport modelling simulations of bed‐scale dolomitization were used to assess whether those patterns in dolomite abundance could form during near‐surface replacement dolomitization. Simulations used a 2 m high and 18 m long model domain, a low‐Mg calcite grainstone precursor and an evaporated Mississippian seawater brine (430 parts per thousand salinity) as the dolomitizing fluid. The domain was initially populated with random variations in porosity and/or grain size. Results reveal that spatial patterns in dolomite abundance emerge when there is as little as 1% dolomite formed, with similarities between the modelled patterns and outcrop‐documented patterns. The nested patterns include a near‐random component that constitutes ≤40% of the total variance, short‐range correlation ranging from 1·5 to 3·3 m and a longer‐range periodic trend with a wavelength up to 6·5 m. The emergence of pattern in dolomite abundance is the result of an autogenic self‐organizing phenomenon. It is triggered by variation in initial calcite reactive surface area that occurs due to the random heterogeneities in initial porosity and/or grain sizes. The pattern develops due to a combination of kinetic disequilibrium reactions (dolomite precipitation and calcite dissolution) and positive feedbacks between dolomite growth, calcite dissolution and fluid flow. Flow is around loci of higher dolomite, lower porosity and higher reactive surface areas, but through loci of lower dolomite, higher porosity and lower reactive surface areas. The resulting less porous/more dolomite and more porous/less dolomite structures at the metre‐scale arise from those localized interactions. This self‐organizing mechanism for pattern formation constitutes a new model for geochemical self‐organization during dolomitization and is the only self‐organization model that is proven applicable to the formation of metre‐scale patterns during early, near‐surface dolomitization.     

Saddle-Dolomite-Bearing Fracture Fillings and Records of Hot Brine Activity in the Jialingjiang Formation, Libixia Section, Hechuan Area of Chongqing City

Most vein minerals deposited in fractures of the Jialingjiang Formation from Libixia section,Hechan area include a large amount of saddle dolomite and accompanying celestite,calcite and fluorite.This study analyzed the nature,source,evolution of the fluids by plane-light petrography,fluid-inclusion methods,cathodoluminescence images,and stable isotopic compositions.The homogenization temperatures of two-phase aqueous fluid inclusions in dolomite range between100 and 270℃.Combined with theδ~(18)O data,it is suggested that the fluid responsible for the precipitation of fracture fillings haveδ~(18)O values between 10‰and 18‰(relative to SMOW).The saddle dolomite and the accompanying minerals were the result of activity of dense brines at elevated temperatures.Moreover,analysis shows that the fluid was derived from a mixture of marine-derived brine and deeper circulating flow.This fluid was enriched in Sr during diagenesis and formed celestite in fracture and for regional mineralization.Dissolution of saddle dolomite was attributed to the cooling of Mg/Ca-decreased fluids,which may relate to a leaching of gypsum to celestite in surrounding carbonates.     

Diagenesis of Ordovician carbonates from the north-east Michigan Basin, Manitoulin Island area, Ontario: evidence from petrography, stable isotopes and fluid inclusions

Middle to Late Ordovician subtidal carbonates in the Manitoulin Island area of Ontario are predominantly limestone in composition, but non-ferroan and ferroan dolomite is a common cement as well as a selective or locally pervasive replacement phase. Integration of field, petrographic, geochemical (δ¹³C, δ¹⁸O) and fluid inclusion data indicates that lithification of these carbonates occurred during burial diagenesis, with much of the alteration controlled by regional fracturing and hydrothermal influences. Aqueous (type 1) fluid inclusions in early calcite (pre-dolomite) and dolomite are saline (> 29 wt% NaCl eq.) solutions with Ca and/or Mg in excess of Na and display homogenization temperatures with modes of 95 and 101°C, respectively. These temperatures can be explained by significantly more burial than can be accounted for either by the available stratigraphic information or by an unusually high palaeogeothermal gradient, which also is not well supported. The fluid inclusion temperatures are interpreted to have resulted from hydrothermal fluids which circulated during the burial diagenesis of these strata. Type 1 inclusions in late (post-dolomite) calcite are less saline (<19 wt% NaCl eq.) and have a bimodal distribution of homogenization temperatures with a relatively well defined low temperature peak similar to those in early calcite and dolomite and a broad higher temperature grouping with a mode at 183°C. A small proportion of methane and light hydrocarbon-bearing fluid inclusions (type 2) are present in all stages of carbonate. Dolomitizing fluids were derived from burial compaction of argillaceous sediments in the more central parts of the Michigan Basin and the updip migration of these brines along fractures to the basin margin where the carbonates of the Manitoulin Island area were dolomitized. Alternatively, migration of dolomitizing brines downward from the overlying pervasively dolomitized Silurian sequence into fractures in the Ordovician carbonates may have occurred. Integration of the aqueous fluid inclusion data into the diagenetic history of these carbonates remains equivocal because most of the inclusions are secondary or indeterminate in origin. Nevertheless, high salinities resulting from interaction with evaporitic strata and hydrothermal effects are clearly implicated although the origin of the latter remains unclear. The alteration styles of the Ordovician carbonates in the Manitoulin area are similar to those of Ordovician hydrocarbon reservoirs described from other parts of the Michigan Basin. They indicate that fracture-related diagenesis occurred on a basin-wide scale and that hydrothermal effects were important.     

Direct physical evidence of dolomite recrystallization

The possibility of recrystallization is a long‐standing barrier to deciphering the genetic origin of dolomites. There is often uncertainty regarding whether or not characteristics of ancient dolomites are primary or the consequence of later recrystallization unrelated to the original dolomitization event. Results from 65 new high‐temperature dolomite synthesis experiments (1 m , 1·0 Mg/Ca ratio solutions at 218°C) demonstrate dolomite recrystallization affecting stoichiometry, cation ordering and nanometre‐scale surface texture. The data support a model of dolomitization that proceeds by a series of four unique phases of replacement and recrystallization, which occur by various dissolution–precipitation reactions. During the first phase (induction period), no dolomite forms despite favourable conditions. The second phase (replacement period) occurs when Ca‐rich dolomite products, with a low degree of cation ordering, rapidly replace calcite reactants. During the replacement period, dolomite stoichiometry and the degree of cation ordering remain constant, and all dolomite crystal surfaces are covered by nanometre‐scale growth mounds. The third phase (primary recrystallization period), which occurs in the experiments between 97% and 100% dolomite, is characterized by a reduced replacement rate but concurrent increases in dolomite stoichiometry and cation ordering. The end of the primary recrystallization period is marked by dolomite crystal growth surfaces that are covered by flat, laterally extensive layers. The fourth phase of the reaction (secondary recrystallization period) occurs when all calcite is consumed and is characterized by stoichiometric dolomite with layers as well as a continued increase in the degree of cation ordering with time. Inferences of recrystallization, in natural dolomite, based on cation order or stoichiometry of dolomite, usually depend on assumptions about the precursor dolomite subjected to recrystallization. If it is assumed that the experimental evidence presented here is applicable to natural, low‐temperature dolomites, then the presence of mounds is direct evidence of a lack of recrystallization and the presence of layers is direct evidence of recrystallization.     

四川盆地西部中二叠统白云岩/石的主要结构类型——兼论其与川东北上二叠统—三叠系白云岩/石的差异

白云岩/石的结构在白云岩成因研究中具有重要意义。四川盆地西部中二叠统栖霞组的白云岩具有与盆地东北部上二叠统长兴组-三叠系不同的结构:盆地西部中二叠统栖霞组除存在一部分斑状晶白云岩以外,总体上缺乏原始结构保存的白云岩,白云石具有特征的非平直晶面他形晶和鞍形晶,且晶体较大;盆地东北部上二叠统长兴组-三叠系非常发育原始结构保存的白云岩,结晶白云岩也以晶体较小的平直晶面自形晶-半自形晶为主。对碳酸盐岩中白云石含量的分布模式而言,盆地西部中二叠统栖霞组出现频率最高的是白云石含量40%~60%的过渡岩石类型,这是一种非经典的分布模式,而盆地东北部上二叠统长兴组-三叠系则缺乏这样的过渡岩石类型,出现频率最高的是白云石含量大于90%和小于10%的端元岩石类型,这是一种经典的分布模式。白云岩/石的结构特征的差异反映盆地西部中二叠统栖霞组白云岩较高的结晶温度、较低的流体Mg/Ca比值、较短的白云化作用持续时间和不彻底的回头白云化作用;盆地东北部上二叠统长兴组-三叠系则主要是相对低温的,高Mg/Ca比值海源流体的彻底白云化作用。     

Late Pleistocene mixing zone dolomitization, southeastern Barbados, West Indies

ABSTRACT Field, geochemical, and petrographic data for late Pleistocene dolomites from southeastern Barbados suggest that the dolomite precipitated in the zone of mixing between a coastal meteoric phreatic lens and normal marine waters. The dolomite is localized in packstones and wackestones from the algalAmphistegina fore-reef calcarenite facies. Stable isotopic evidence suggests that meteoric water dominated the diagenetic fluids responsible for dolomitization. Carbon isotopes in pure dolomite phases average about -15%₀ PDB. This light carbon is attributed to the influence of soil gas CO₂, and precludes substantial mixing with seawater. A narrow range of oxygen isotopic compositions coupled with a wide range of carbon compositions attest to the meteoric diagenetic overprint. Dolomitization likely occurred with as little as a five per cent admixture of seawater. Strontium compositions of the dolomites indicate probable replacement dolomitization of original unstable mineralogy. The dolomite is characterized by low sodium values. Low concentrations of divalent manganese and iron suggest oxidizing conditions at the time of dolomitization. A sequence of petrographic features suggests a progression of diagenetic fluids from more marine to more meteoric. Early marine diagenesis was followed by replacement dolomitization of skeletal grains and matrix. Limpid, euhedral dolomite cements precipitated in primary intra- and interparticle porosity subsequent to replacement dolomitization. As waters became progressively less saline, dolomite cements alternated with thin bands of syntaxial calcite cement. The final diagenetic phase precipitated was a blocky calcite spar cement, representing diagenesis in a fresh-water lens. This sequence of diagenetic features arose as the result of a single fall in eustatic sea-level following deposition. A stratigraphic-eustatic-diagenetic model constrains both the timing and rate of dolomitization in southeastern Barbados. Dolomitization initiated as sea-level began to fall immediately following the oxygen isotope stage 7–3 high stand, some 216 000 yr bp . Due to the rapidity of late Pleistocene glacio-eustasy, dolomitization (locally complete) is constrained to have occurred within about 5000 yr.     

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.     

Mineralogical and geochemical characterization of listwaenite from the Semail Ophiolite, Oman

The late Cretaceous-lower Tertiary hydrothermal alteration of serpentinized peridotite in the Semail ophiolite has formed two distinct types of listwaenite. Type I is characterized by the presence of calcite (Type IA) or dolomite (Type IB)+fuchsite±spinel. Type II is dominated by silicate minerals (quartz, chlorite, fuchsite)±calcite+dolomite±magnetite±apatite±plagioclase. Most listwaenites occur as veins along thrust fault zones within the ophiolite mélange. High Cr and Ni contents, abundant occurrence of Cr-spinel within a matrix of red-brown ferruginous carbonates within a micro-vein network of goethite, and the relics of mesh texture indicate an ultramafic protolith. Type I and II listwaenites represent different stages of hydrothermal alteration. The mineralogical and chemical distinctions of both types are the response to the extent of the reactions between the protoliths and the solutions leading to different stages of metasomatic replacement. The hydrothermal fluids involved in the formation of Type I listwaenite were enriched in Ca, Mg, and CO₂, whereas Type II listwaenite bodies were formed from a hydrothermal fluid enriched in SiO₂. REE and trace elements in both listwaenite types were extracted in part from adjoining peridotite. No Au anomaly in the study areas has been detected.     

Burial dolomitization and porosity development in a mixed carbonate-clastic sequence: an example from the Bowland Basin, northern England

Widespread dolomitization and leaching occur in the Asbian to Brigantian (Dinantian) sequence of the Bowland Basin. Within this mudrock-dominated succession, dolomite is developed in calcarenites and limestone breccia/conglomerates deposited in a carbonate slope environment (Pendleside Limestone) and also within graded quartz wackes deposited by density currents in a generally ‘starved’ basin environment (Pendleside Sandstone). The dolomitized intervals range in thickness from less than one metre to several tens of metres and have a stratabound nature. All stages of calcite cement pre-date dolomitization and calcite veins are dolomitized. Dolomite crystals replace neomorphic spar and may also contain insoluble residues that were concentrated along stylolites. Thus dolomitization was a late stage process within the carbonate diagenetic sequence. A late-stage diagenetic origin is also indicated within the sandstones, with dolomite post-dating the development of quartz overgrowths. Six main textural styles of dolomite are observed: (1) scattered; (2) mosaic; (3) subhedral to euhedral rhombic; (4) microcrystalline; (5) single crystal and (6) saddle. The style of dolomite developed is dependent on the host rock mineralogy, on whether it is space-filling or replacive and also on temperature. Chemically the dolomite varies from near stoichiometric compositions to ankeritic varieties containing up to 20 mole % FeCO₃. Generally the dolomites have isotopic compositions depleted in δ¹⁸O compared to the host limestone, with similar or lighter δ¹³C values. Initial dolomite was of the scattered type, but with progressive replacement of the host a mosaic dolostone with a sucrosic texture was produced. There was a general increase in the Fe and Mn content and reduction in δ¹⁸O ratio of the crystals during dolomitization. Leaching is restricted to partly dolomitized horizons, where calcite, feldspars, micas, clays and, to some extent, dolomite have been leached. This has produced biomouldic and vuggy secondary porosity within the carbonates, whereas in the sandstones honeycombed, corroded and floating grains associated with oversized pores occur. Porosity within both carbonates and sandstones is reduced by ferroan dolomite/ankerite cements. Field, petrographic and chemical characteristics indicate that dolomitizing solutions were predominantly derived from the enclosing mudrocks (Bowland Shales) during intermediate/deep burial. Fluid migration out of the mudrocks would have been sided by dehydration reactions and overpressure, the fluids migrating along the most permeable horizons—the coarse grained carbonates and sandstones that are now dolomitized and contain secondary porosity.     

Fluid–rock interactions associated with regional tectonics and basin evolution

An integrated approach consisting of fracture analysis, petrography, carbon, oxygen and strontium‐isotope analyses, as well as fluid‐inclusion micro‐thermometry, led to a better understanding of the evolution of fluid–rock interactions and diagenesis of the Upper Permian to Upper Triassic carbonates of the United Arab Emirates. The deposited carbonates were first marked by extensive early dolomitization. During progressive burial, the carbonates were affected by dolomite recrystallization as well as precipitation of vug and fracture‐filling dolomite, quartz and calcite cements. After considerable burial during the Middle Cretaceous, sub‐vertical north–south oriented fractures (F1) were cemented by dolomite derived from mesosaline to hypersaline fluids. Upon the Late Cretaceous maximum burial and ophiolite obduction, sub‐vertical east–west fractures (F2) were cemented by dolomite (Dc2) and saddle dolomite (Ds) derived from hot, highly saline fluids. Then, minor quartz cement has precipitated in fractures from hydrothermal brines. Fluid‐inclusion analyses of the various diagenetic phases imply the involvement of increasingly hot (200°C) saline brines (20 to 23% NaCl eq.). Through one‐dimensional burial history numerical modelling, the maximum temperatures reached by the studied rocks are estimated to be in the range of 160 to 200°C. Tectonically‐driven flux of hot fluids and associated diagenetic products are interpreted to have initiated during the Late Cretaceous maximum burial and lasted until the Oligocene–Miocene compressional tectonics and related uplift. The circulation of such hydrothermal brines led to partial dissolution of dolomites (Dc2 and Ds) and to precipitation of hydrothermal calcite C1 in new (mainly oriented north–south; F3) and pre‐existing, reactivated fractures. The integration of the obtained data confirms that the diagenetic evolution was controlled primarily by the interplay of the burial thermal evolution of the basin and the regional tectonic history. Hence, this contribution highlights the impacts of regional tectonics and basin history on diagenetic processes, which may subsequently affect reservoir properties.     

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).     

Multiphase partial and selective dolomitization of Carnian reef limestone (Transdanubian Range,Hungary)

Partially dolomitized carbonate successions provide a good opportunity to understand the commonly multistage process of dolomitization. Petrographic methods, fluid inclusion microthermometry and stable isotope measurements were applied to reconstruct the diagenetic evolution and dolomitization of a partially dolomitized Carnian reef limestone from the Transdanubian Range, Hungary. The diagenetic history began with reef diagenesis and formation of dolomite micro‐aggregates in microbial fabric elements; this was followed by the development of euhedral porphyrotopic dolomite crystals through overgrowths around the previously formed dolomite micro‐aggregates during the earliest burial stage. Increasing burial resulted in the extension of the dolomite patches via formation of finely crystalline replacement dolomite. From the Late Norian, when the Carnian reef carbonates reached the depth of 1·0 to 1·8 km, the diagenetic evolution continued in an intermediate to deep‐burial setting. Contemporaneously, an extensional regime was established, leading to fracturing. The progressive burial resulted in the recrystallization of the pre‐existing dolomite with increasing temperature, while saddle dolomite cement was precipitated in fractures. In connection with the Alpine Orogeny, intense denudation took place during the Late Cretaceous, accompanied by fracturing. Similar tectonically controlled denudation and fracturing occurred in several stages during the Cenozoic. As a result of these processes, the studied Carnian carbonates were raised to a near‐surface position or became subaerially exposed, leading to dedolomitization of the last dolomite phase and precipitation of calcite cement in cavities and fractures. This study revealed that by investigating partially and selectively dolomitized rock types, it is possible to document and understand those stages of the multiple dolomitization process which can barely be detected in the completely dolomitized rock bodies. Recognition of the dolomitization phases could provide the basis for the analysis of their relations with the depositional, diagenetic and tectonic processes, and stages of basin evolution.     

羌塘盆地中央隆起带南侧隆额尼-昂达尔错布曲组古油藏白云岩稀土元素特征及成因意义

以系统的岩石学及沉积相分析为基础,深入探讨了隆额尼—昂达尔错古油藏白云岩及其伴生灰岩的稀土元素地球化学特征,认为该区灰岩及白云岩∑REE仍受沉积相带及沉积过程的控制,且具∑REE较低的总体特征,白云岩中HREE比LREE更具贫化的特点,这些特征均系淡水淋漓作用的结果;灰岩及白云岩在配分模式上,均为相对平坦的页岩配分模式。其中灰岩在配分模式上,在∑REE较高的情况下表现出起伏较大的特点,而白云岩在∑REE较低的情况下,表现出较为平坦的特征,白云岩化过程中稀土元素有贫化和均一的趋势;灰岩与白云岩相比,灰岩δEu值较高,而白云岩δCe较高,反映出灰岩形成于水体较深的还原环境,而白云岩形成于古地理相对高点的氧化环境。该区白云岩为混合水交代成因。     

Genesis of Dolomite from Ma55–Ma510 Sub-members of the Ordovician Majiagou Formation in the Jingxi Area in the Ordos Basin

We clarified three stages of dolomitization and secondary changes by studying the petrology and geochemistry characteristics of dolomite from the Ma55–Ma510 sub-members of the Ordovician Majiagou Formation in the Jingxi area in the Ordos Basin: (1) Syngenetic microbial dolomitization is characterized by formation of dolomite with a mainly micrite structure and horse tooth-shape dolomite cements. (2) Seepage reflux dolomitization during the penecontemporaneous period superposed adjustment functions such as recrystallization and stabilization in the middle-deep burial stage, forming dolomites mainly consisting of micro crystal and powder crystal structure. (3) Powder dolomite, fine dolomite, and medium-coarse crystalline dolomite formed in pores and fractures in the middle-deep burial stage. The secondary concussive transgression-regression under a regressive background is an important condition for the occurrence of many stages of dolomitization in the study area. The basin was an occlusive epicontinental sea environment in the Ma5 member of the Ordovician Majiagou Formation sedimentary period. In the sediments, sulfate content was high, which is conducive to the preservation of microbial activity and microbial dolomitization. Micritic dolomite formed by microbial dolomitization provides good migration pathways for seepage reflux dolomitization. Affected by evaporation seawater with increased Mg/Ca ratio, seepage reflux dolomitization was widely developed and formed large-scale dolomite, and underwater uplifts and slopes are favorable areas for dolomite. In the middle-deep burial stage, dolomitizing fluid in the stratum recrystallized or stabilized the previous dolomite and formed a small amount of euhedral dolomite in the pores and fractures.     

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.     

Formation of low‐magnesium calcite at cold seeps in an aragonite sea

This study investigates the conditions of occurrence and petrographic characteristics of low‐Mg calcite (LMC) from cold seeps of the Gulf of Mexico at a water depth of 2340 m. Such LMC mineral phases should precipitate in calcite seas rather than today's aragonite sea. The ¹³C‐depleted carbonates formed as a consequence of anaerobic oxidation of hydrocarbons in shallow subsurface cold seep environments. The occurrence of LMC may result from brine fluid flows. Brines are relatively Ca²⁺‐enriched and Mg²⁺‐depleted (Mg/Ca mole ratio <0.7) relative to seawater, where the Mg/Ca mole ratio is ~5, which drives high‐Mg calcite and aragonite precipitation. The dissolution of aragonitic mollusk shells, grains and cements was observed. Aerobic oxidation of hydrocarbons and H₂S is the most likely mechanism to explain carbonate dissolution. These findings have important implications for understanding the occurrence of LMC in deep water marine settings and consequently their counterparts in the geological record.     

The interaction of tectonics,climate and eustasy in controlling dolomitization: A case study of Cenomanian–Turonian,shallow marine carbonates of the Iberian Basin

During the Cretaceous, high global sea-level and low latitudinal temperature variations led to the growth of epeiric carbonate platforms. Platform-scale dolomitization of these platforms is not common, reflecting the low Mg/Ca ratio of seawater and a humid climate. This study describes the processes governing pervasive dolomitization of a land-attached carbonate platform within the Iberian Basin. Dolomite is planar to sub-planar with a geochemical signature consistent with dolomitization from penesaline seawater. Dolomitization was most pervasive during a 1 Myr period in the middle Cenomanian, by repeated reflux of seawater from brine pools formed on the top of a southward-prograding carbonate platform. Tilting and structural reorganization in the Upper Cenomanian led to a reversal in polarity of the platform, and dolomitization was restarted by the northward reflux of seawater. Rising relative sea-level and oceanic acidification led to back-stepping of the platform such that the supply of dolomitizing fluids was cut off. In the Lower Turonian, pervasively dolomitized rudist rudstone facies in the south of the study area indicate that dolomitization restarted, either penecontemporaneously or later, from highly evaporated Campanian–Maastrichtian seawater. A systematic increase in dolomite crystal size up-section ties broadly, but not entirely, to stratigraphy. It is possible that these textural differences reflect changes in fluid chemistry, limestone permeability or precursor rock texture. However, the lack of stratigraphic conformance, and the preservation of the earliest-formed dolomite only in the oldest sediments, could indicate a progressive recrystallization of early-formed dolomite through repeated reflux of brines. As such, the succession appears to preserve a fossilized record of dolomite recrystallization through time during the Cenomanian–Turonian. The results of this study therefore provide a record of the progressive dolomitization of a carbonate platform and demonstrate the important interplay of climate and basin-scale tectonics on dolomite distribution and crystallinity.     

Microbially influenced formation of Mg‐calcite and Ca‐dolomite in the presence of exopolymeric substances produced by sulphate‐reducing bacteria

Some species of sulphate‐reducing bacteria (SRB) are known to mediate the formation of dolomite and Mg‐calcite. However, their exact role in the mineralization process remains elusive. Here, we present the result of a laboratory experiment that was designed to test whether formation of carbonate minerals by SRB can occur in the absence of living cells, through passive mineralization of their exopolymeric substances (EPS). SRB capable of mediating dolomite were cultivated in the laboratory, allowing them to secrete EPS. Microbial activity within the cultures was subsequently inhibited with antibiotics. Only after this step, Ca²⁺ and Mg²⁺ were added to the solution and carbonate minerals could form. Mg‐calcite and disordered Ca‐dolomite precipitated in association with EPS. The mol.% of Mg²⁺ in the crystals increased with longer incubation times. This result demonstrates that organic compounds produced by SRB can mediate the formation of Ca‐Mg carbonates in the absence of an active metabolism.     

Calcium-isotope fractionation in selected modern and ancient marine carbonates

The calcium-isotope composition (δ^44/42Ca) was analyzed in modern, Cretaceous and Carboniferous marine skeletal carbonates as well as in bioclasts, non-skeletal components, and diagenetic cements of Cretaceous and Carboniferous limestones. In order to gain insight in Ca²⁺_aq-CaCO₃-isotope fractionation mechanisms in marine carbonates, splits of samples were analyzed for Sr, Mg, Fe, and Mn concentrations and for their oxygen and carbon isotopic composition. Biological carbonates generally have lower δ^44/42Ca values than inorganic marine cements, and there appears to be no fractionation between seawater and marine inorganic calcite. A kinetic isotope effect related to precipitation rate is considered to control the overall discrimination against ⁴⁴Ca in biological carbonates when compared to inorganic precipitates. This is supported by a well-defined correlation of the δ^44/42Ca values with Sr concentrations in Cretaceous limestones that contain biological carbonates at various stages of marine diagenetic alteration. No significant temperature dependence of Ca-isotope fractionation was found in shells of Cretaceous rudist bivalves that have recorded large seasonal temperature variations as derived from δ¹⁸O values and Mg concentrations. The reconstruction of secular variations in the δ^44/42Ca value of seawater from well preserved skeletal calcite is compromised by a broad range of variation found in both modern and Cretaceous biological carbonates, independent of chemical composition or mineralogy. Despite these variations that may be due to still unidentified biological fractionation mechanisms, the δ^44/42Ca values of Cretaceous skeletal calcite suggest that the δ^44/42Ca value of Cretaceous seawater was 0.3-0.4‰ lower than that of the modern ocean.