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.     

Dolomitization of the Devonian Swan Hills Formation, Rosevear Field, Alberta, Canada

The Swan Hills Formation (Middle-Upper Devonian) of the Western Canada Basin is host to several NW-SE-trending gas fields developed in massive replacement dolostone. One of these, the Rosevear Field, contains two major dolostone trends along opposing margins of a marine channel that penetrates into a platform-reef complex. Dolostones consist predominantly of branching and bulbous strdmatoporoid floatstones and rudstones with well-developed moldic and vuggy porosity. Replacement dolomite is coarsely crystalline (100-600 μm), inclusion-rich, composed of euhedral through anhedral crystals and has a blotchy to homogeneous red cathodoluminescence. Geochemically, replacement dolomite is characterized by (i) nearly stoichiometric composition (50.1-51.1 mol% CaCO₃), (ii) negative δ¹⁸O values (mean=-7.5‰, PDB) and (iii) variable ⁸⁷Sr/⁸⁶Sr ratios ranging from values similar to Late Devonian-Early Mississippian seawater (～0.7082) to radiogenic compositions comparable to saddle dolomite cements (>0.7100). Dolomitization began after widespread precipitation of early, equant calcite spar and after the onset of pressure solution, implying that replacement dolomite formed in a burial environment. Oxygen isotope data suggest that dolomite formed at 35-75°C, temperatures reached during burial in Late Devonian through Jurassic time, at minimum depths of 450 m. The linear NW-SE orientation of most dolomite fields in the Swan Hills Formation is suggestive of fault control on fluid circulation. Two models are proposed for fault-controlled circulation of dolomitizing fluids at the Rosevear Field. In the first, compaction-driven, updip fluid migration occurred in response to basin tilting commencing in the Late Palaeozoic. Deep basinal fluids migrating updip were focused into channel-margin sediments along fault conduits. The second model calls upon fault-controlled convective circulation of (i) warm Devonian-Mississippian seawater or (ii) Middle Devonian residual evaporitic brines. The overlap in ⁸⁷Sr/⁸⁶Sr and δ¹⁸O compositions, and similar cathodoluminescence properties between replacement and saddle dolomites provide evidence for neomorphism of some replacement dolomite. Quantitative modelling of Sr and O isotopes and Sr abundances suggests partial equilibration of some replacement dolomite with hot radiogenic brines derived during deep burial of the Swan Hills Formation in the Late Cretaceous-Palaeocene. Interaction of replacement dolomite with deep brines led to enrichment in ⁸⁷Sr while leaving δ¹⁸O similar to pre-neomorphism values.     

Syn-sedimentary hydrothermal dolomites in a lacustrine rift basin: Petrographic and geochemical evidence from the lower Cretaceous Erlian Basin,Northern China

Dolomites occur extensively in the lower Cretaceous along syn-sedimentary fault zones of the Baiyinchagan Sag, westernmost Erlian Basin, within a predominantly fluvial–lacustrine sedimentary sequence. Four types of dolomite are identified, associated with hydrothermal minerals such as natrolite, analcime and Fe-bearing magnesite. The finely-crystalline dolomites consist of anhedral to subhedral crystals (2 to 10 μm), evenly commixed with terrigenous sediments that occur either as matrix-supporting grains (Fd1) or as massive argillaceous dolostone (Fd2). Medium-crystalline (Md) dolomites are composed of subhedral to euhedral crystals aggregates (50 to 250 μm) and occur in syn-sedimentary deformation laminae/bands. Coarse-crystalline (Cd) dolomites consist of non-planar crystals (mean size >1 mm), and occur as fracture infills cross-cutting the other dolomite types. The Fd1, Md and Cd dolomites have similar values of δ¹⁸O (−20·5 to −11·0‰ Vienna PeeDee Belemnite) and δ¹³C (+1·4 to +4·5‰ Vienna PeeDee Belemnite), but Fd2 dolomites are isotopically distinct (δ¹⁸O −8·5 to −2·3‰ Vienna PeeDee Belemnite; δ¹³C +1·4 to +8·6‰ Vienna PeeDee Belemnite). Samples define three groups which differ in light rare-earth elements versus high rare-earth elements enrichment/depletion and significance of Tb, Yb and Dy anomalies. Medium-crystalline dolomites have signatures that indicate formation from brines at very high temperature, with salinities of 11·8 to 23·2 eq. wt. % NaCl and T_h values of 167 to 283°C. The calculated temperatures of Fd1 and Cd dolomites extend to slightly lower values (141 to 282°C), while Fd2 dolomites are distinctly cooler (81 to 124°C). These results suggest that the dolomites formed from hydrothermal fluid during and/or penecontemporaneous with sediment deposition. Faults and fractures bounding the basin were important conduits through which high-temperature Mg-rich fluids discharged, driven by an abnormally high heat flux associated with local volcanism. It is thought that differing amounts of cooling and degassing of these hydrothermal fluids, and of mixing with lake waters, facilitated the precipitation of dolomite and associated minerals, and resulted in the petrographic and geochemical differences between the dolomites.     

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).     

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.     

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.     

Dolomitization of the Middle Devonian Winnipegosis carbonates in south-central Saskatchewan, Canada

The Middle Devonian Winnipegosis carbonate unit in south‐central Saskatchewan is partially to completely dolomitized. Two major types of replacive dolomite are distinguished. Microcrystalline to finely crystalline dolomite (type 1) displays nonplanar‐a to planar‐s textures, mimetically replaces the precursor limestone, accounts for about four‐fifths of dolomite phases volumetrically, and mainly occurs in the Winnipegosis mounds and the Lower Winnipegosis Member directly underlying the mounds. Medium crystalline dolomite (type 2) shows planar‐s to planar‐e textures, commonly occurs in the Lower Winnipegosis and Brightholme members, and decreases upward in abundance. The ⁸⁷Sr/⁸⁶Sr ratios of type 1 dolomite (0·70795 to 0·70807) fall within the estimated Sr‐isotopic range for Middle Devonian marine carbonates. Stratigraphic, petrographic and geochemical data constrain the formation of type 1 dolomite to hypersaline sea water in a near‐surface environment, after marine cementation and sub‐aerial diagenesis and prior to precipitation of the Middle Devonian Leofnard salts. Movement of dolomitizing fluids could be driven by density differences and elevation head. The shift to lower δ¹⁸O values of type 1 dolomite [?7·4 to ?5·1‰ Vienna Pee Dee Belemnite (VPDB)] is interpreted as the result of recrystallization at elevated temperatures during burial. Type 2 dolomite has higher ⁸⁷Sr/⁸⁶Sr ratios (0·70809–0·70928), suggesting that the dolomite probably formed from basinal fluids with an increased richness in the radiogenic Sr isotope. In type 2 dolomite, Sr²⁺ concentrations are lower, and Fe²⁺ and Mn²⁺ concentrations are higher, compared with the associated limestone and type 1 dolomite. Type 2 dolomite is interpreted as having been formed from upward‐migrating basinal fluids during latest Devonian and Carboniferous period.     

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.     

Fracturing and fluid migration during Palaeogene compression and Neogene extension in the Catalan Coastal Ranges, Spain

The Catalan Coastal Ranges (NE part of the Eastern Iberian Margin) correspond to a system of grabens formed at the north-western margin of the Valencia Trough. Extensional activity in the Catalan Coastal Ranges occurred at least from early to late Miocene and reactivated earlier transpressive faults related to the Palaeogene compression. In the central part of the Catalan Coastal Ranges, tectonic micro and macrostructures (faults, joints, stylolites) are well developed in the Mesozoic (mainly Cretaceous) limestones as well as in the Miocene graben fill deposits. In these rocks, seven generations of fractures, which formed during different tectonic phases, have been distinguished. Type 1–4 fractures affect only the Cretaceous limestones, type 5 and 6 fractures the Cretaceous and Miocene deposits, and type 7 fractures only the Miocene sediments. The fractures are filled with calcites, and locally with an internal sediment or a dolomite cement. The Cretaceous host-rock has an average δ¹⁸O value of –4·3‰ PDB (Peedee Belemnite), an average δ¹³C value of +0·6‰ PDB, a ⁸⁷Sr/⁸⁶Sr ratio of 0·70741, up to 5630 p.p.m. of Mg²⁺, up to 2615 p.p.m. of Sr²⁺, and up to 1560 p.p.m. of Fe²⁺. Type 2 fractures are related to Palaeogene compression. The calcite cement filling this type of fracture has an average δ¹⁸O value of –8·2‰ PDB, an average δ¹³C value of –0·6‰ PDB, a ⁸⁷Sr/⁸⁶Sr ratio of 0·70714, up to 4560 p.p.m. of Mg²⁺, up to 3275 p.p.m. of Sr²⁺, and up to 3540 p.p.m. of Fe²⁺. These results indicate a fluid characterized by a high rock–fluid interaction approaching a closed system equilibrium. Type 5 fractures are related to the syn-rift stage. The calcite cement filling this type of fracture has an average δ¹⁸O value of –6·9‰ PDB, an average δ¹³C value of –4·3‰ PDB, a ⁸⁷Sr/⁸⁶Sr ratio of 0·70787, up to 5375 p.p.m. of Mg²⁺, up to 1750 p.p.m. of Sr²⁺ and up to 2855 p.p.m. of Fe²⁺. These results indicate a fluid characterized by a low rock–fluid interaction and an open hydrogeological system. The cements filling the compressional fractures are characterized by undulose extinction, subgrain formation and deformed mechanical twin planes indicating formation under stressed conditions. In contrast, cements filling extensional fractures are characterized by translucent crystals with uniform extinction, indicating free growth not subjected to stress.     

Dolomitization of Quaternary reef limestone, Aitutaki, Cook Islands

Six holes were drilled to depths of 30–69 m in the shallow lagoon of Aitutaki in the southern Cook Islands. One hole encountered pervasively dolomitized reef limestones at 36 m subbottom depth, which extended to the base of the drilled section at 69·3 m. This hole was drilled near the inner edge of the present barrier reef flat on the flank of a seismically defined subsurface ridge. Both the morphology and biofacies indicate that this ridge may represent an outer reef crest. Mineralogy, porosity and cementation change in concert downhole through three zones. Zone 1, 0–9 m, is composed of primary skeletal aragonite and calcite with minor void-filling aragonite and magnesian calcite cement of marine phreatic origin. Zone 2, 9–36 m, is composed of replacement calcite and calcite cement infilling intergranular, intragranular, mouldic and vuggy porosity. Stable isotopes (mean δ¹⁸O=—5·4‰ PDB for carbonate; δD =—50‰ SMOW for fluid inclusions) support the petrographic evidence indicating that sparry calcite cements formed in predominantly freshwater. Carbon isotope values of —4·0 to —11·0‰ for calcite indicate that organic matter and seawater were the sources of carbon. Zone 3, 36–69·3 m, is composed of replacement dolostone, consisting of protodolomite with, on average, 7 mol% excess CaCO₃ and broad and weak ordering X-ray reflections at 2·41 and 2·54 A. The fine-scale replacement of skeletal grains and freshwater void-filling cements by dolomite did not significantly reduce porosity. Stable isotopes (mean δ¹⁸O=+2·6‰₀ PDB for dolomite; maximum δD =—27‰ SMOW for fluid inclusions) and chemical composition indicate that the dolomite probably formed from seawater, although formation in the lower part of a mixed freshwater-seawater zone, with up to 40% freshwater contribution, cannot be completely ruled out. The carbon (δ¹³C=2·7‰) and magnesium were derived from seawater. Low-temperature hydrothermal iron hydroxides and associated transition metals occur in void space in several narrow stratigraphic intervals in the limestone section that was replaced by dolomite. The entire section of dolomite is also enriched in these transition metals. The metals dispersed throughout the dolostone section were introduced at the time of dolomitization by a different and later episode of hydrothermal circulation than the one(s) that produced the localized deposits near the base of the section. The primary reef framework is considered to have been deposited during several highstands of sea level. Following partial to local recrystallization of the limestone, a single episode of dolomitization occurred. Both tidal and thermal pumping drove large quantities of seawater through the porous rocks and perhaps maintained a wide mixing zone. However, the isotopic, geochemical and petrographic data do not clearly indicate the extent of seawater mixing.     

Fault-controlled dolomitization at Swan Hills Simonette oil field (Devonian), deep basin west-central Alberta, Canada

The partly dolomitized Swan Hills Formation (Middle‐Upper Devonian) in the Simonette oil field of west‐central Alberta underwent a complex diagenetic history, which occurred in environments ranging from near surface to deep (>2500 m) burial. Five petrographically and geochemically distinct dolomites that include both cementing and replacive varieties post‐date stylolites in limestones (depths >500 m). These include early planar varieties and later saddle dolomites. Fluid inclusion data from saddle dolomite cements (T_h=137–190 °C) suggest that some precipitated at burial temperatures higher than the temperatures indicated by reflectance data (T_peak=160 °C). Thus, at least some dolomitizing fluids were ‘hydrothermal’. Fluorescence microscopy identified three populations of primary hydrocarbon‐bearing fluid inclusions and confirms that saddle dolomitization overlapped with Upper Cretaceous oil migration. The source of early dolomitizing fluids probably was Devonian or Mississippian seawater that was mixed with a more ⁸⁷Sr‐rich fluid. Fabric‐destructive and fabric‐preserving dolostones are over 35 m thick in the Swan Hills buildup and basal platform adjacent to faults, thinning to less than 10 cm thick in the buildup between 5 and 8 km away from the faults. This ‘plume‐like’ geometry suggests that early and late dolomitization events were fault controlled. Late diagenetic fluids were, in part, derived from the crystalline basement or Palaeozoic siliciclastic aquifers, based on ⁸⁷Sr/⁸⁶Sr values up to 0·7370 from saddle dolomite, calcite and sphalerite cements, and ²⁰⁶Pb/²⁰⁴Pb of 22·86 from galena samples. Flow of dolomitizing and mineralizing fluids occurred during burial greater than 500 m, both vertically along reactivated faults and laterally in the buildup along units that retained primary and/or secondary porosity.     

Dolomitization by hypersaline reflux into dense groundwaters as revealed by vertical trends in strontium and oxygen isotopes: Upper Muschelkalk,Switzerland

The Trigonodus Dolomit is the dolomitized portion of the homoclinal ramp sediments of the Middle Triassic Upper Muschelkalk in the south‐east Central European Basin. Various dolomitizing mechanisms, followed by recrystallization, have been previously invoked to explain the low δ¹⁸O, high ⁸⁷Sr/⁸⁶Sr, extensive spatial distribution and early nature of the replacive matrix dolomites. This study re‐evaluates the origin, timing and characteristics of the dolomitizing fluids by examining petrographic and isotopic trends in the Trigonodus Dolomit at 11 boreholes in northern Switzerland. In each borehole the ca 30 m thick unit displays the same vertical trends with increasing depth: crystal size increase, change from anhedral to euhedral textures, ultraviolet‐fluorescence decrease, δ¹⁸O_VPDB decrease from ?1·0‰ at the top to ?6·7‰ at the base and an ⁸⁷Sr/⁸⁶Sr increase from 0·7080 at the top to 0·7117 at the base. Thus, dolomites at the top of the unit record isotopic values similar to Middle Triassic seawater (δ¹⁸O_VSMOW = 0‰; ⁸⁷Sr/⁸⁶Sr = 0·70775) while dolomites at the base record values similar to meteoric groundwaters from the nearby Vindelician High (δ¹⁸O_VSMOW = ?4·0‰; ⁸⁷Sr/⁸⁶Sr = >0·712). According to water–rock interaction modelling, a single dolomitizing or recrystallizing fluid cannot have produced the observed isotopic trends. Instead, the combined isotopic, geochemical and petrographic data can be explained by dolomitization via seepage‐reflux of hypersaline brines into dense, horizontally‐advecting groundwaters that already had negative δ¹⁸O and high ⁸⁷Sr/⁸⁶Sr values. Evidence for the early groundwaters is found in meteoric calcite cements that preceded dolomitization and in fully recrystallized dolomites with isotopic characteristics identical to the groundwaters following matrix dolomitization. This study demonstrates that early groundwaters can play a decisive role in the formation and recrystallization of massive dolomites and that the isotopic and textural signatures of pre‐existing groundwaters can be preserved during seepage‐reflux dolomitization in low‐angle carbonate ramps.     

Rare earth element geochemistry of dolomites in the Middle Devonian Presqu'ile barrier, Western Canada Sedimentary Basin: implications for fluid-rock ratios during dolomitization

Rare earth elements (REE) were determined in fine, medium and coarse crystalline replacement dolomites, and for saddle dolomite cements from the Middle Devonian Presqu'ile barrier from Pine Point and the subsurface of the Northwest Territories and north-eastern British Columbia. REE patterns of the fine crystalline dolomite are similar to those of Middle Devonian limestones from the Presqu'ile barrier. Fine crystalline dolomite occurs in the back-barrier facies and may represent penecontemporaneous dolomitization at, or just below, the sea floor. Medium crystalline dolomite is widespread in the lower southern and lower central barrier. Medium crystalline dolomite is slightly depleted in heavy REE compared with Devonian marine limestones and fine crystalline dolomite, and has negative Ce and Eu anomalies. Medium crystalline dolomites replaced pre-existing limestones or were recrystallized from earlier fine crystalline dolomites. During these processes, the REE patterns of their precursors were modified. Late stage, coarse crystalline replacement dolomite and saddle dolomite cements occur together in the upper barrier and have similar geochemical signatures. Coarse crystalline dolomites have negative Eu anomalies, and those from the Pine Point area also have positive La anomalies. Saddle dolomites are enriched in light REE and have positive La anomalies. The REE patterns of coarse crystalline dolomite and saddle dolomite differ from those of marine limestones and fine and medium crystalline dolomites, suggesting that different diagenetic fluids were responsible for these later dolomites. Although massive dolomitization requires relatively large volumes of fluids in order to provide the necessary amounts of Mg^2-. dolomitization and subsequent recrystallization may not necessarily modify the REE signatures of the precursor limestones because of the low concentrations of REE in most natural fluids. Thus, relative fluid-rock ratios during diagenesis may be estimated from REE patterns in the diagenetic and precursor minerals. Fine crystalline dolomites retain the REE patterns of their limestone precursors. In the medium and coarse crystalline dolomites the precursor REE patterns were apparently altered by large volumes of fluids involved during dolomitization. This study suggests that REE compositions of dolomites and their limestone precursors may provide important information about the relative amounts of fluids involved during diagenetic processes, such as dolomitization.     

塔里木盆地塔北、塔中地区寒武系—奥陶系碳酸盐岩中鞍形白云石胶结物特征

通过对塔里木盆地中、北部地区寒武系—奥陶系碳酸盐岩的研究,发现鞍形白云石胶结物发育比较普遍,常见于孔洞或裂缝之中,乳白色,晶体粗大,晶面弯曲或呈阶梯状,镜下波状消光,晶体内部常见微裂缝,常与热液矿物共生。本文对28个鞍形白云石样品进行了碳、氧、锶同位素测试,结果显示鞍形白云石的δ~(13)C和δ~(18)O值分别介于-2.446‰～0.686‰和-9.101‰～-5.117‰之间,~(87)Sr/~(86)Sr值介于0.708 6～0.710 2之间;流体包裹体测温分析表明,鞍形白云石中气—液两相包裹体的均一温度(T_h)介于121～159.5℃之间,但集中分布在135～145℃之间;根据最后冰融点温度(T_m)求得的白云岩化流体盐度介于21.3%～23.1%之间。这些数据表明,该类型白云石形成于热卤水(盐度是海水的5～8倍)之中。塔里木盆地鞍形白云石与世界范围内其它盆地的鞍形白云石的碳、氧同位素特征基本相似,但其~(87)Sr/~(86)Sr值相对偏低。导致这一现象的原因可能是鞍形白云石形成于来自深部的岩浆热液流体之中,这些流体伴随岩浆侵位或通过切穿基底的深大断裂及其与之相连的次级断裂系统从深部直接进入碳酸盐岩地层中,未经过碎屑岩输导层的长时间运移,所以导致其中形成的鞍形白云石~(87)Sr/~(86)Sr值偏低。     

Early diagenetic recrystallization of Holocene (<3000 years old) peritidal dolomites, Ambergris Cay, Belize

Three peritidal carbonate crusts and associated intercrust sediments (total thickness of ～30cm; aged <3000 years BP) on Ambergris Cay, Belize, contain 32–100% calcian dolomite (δx=72·5% dolomite) ranging in composition from 40 to 46 mol% MgCO₃ (δx=43·3). Dolomite replaced high Mg calcite foraminiferal muds penecontemporaneously with sedimentation, forming partially dolomitized sediments and lithified crusts. Dolomitization probably occurred in normal to moderately evaporated seawater and is apparently continuing at the present. Detailed scanning electron microscope analysis shows a linear increase in mean dolomite crystal size with depth; 0·4 μm near the top of the section to 1·0 μm near the base of the dolomitized section. This size increase is not accompanied by any significant decrease in porosity. Crystal size distributions appear to be log-normal and become increasingly broad and flat with depth. Rietveld X-ray pattern-fitting structure refinements indicate increasing Ca and Mg concentrations on their respective sites (cation ordering) as a function of increasing depth. Most of the ordering occurs within the first 15 cm of the surface. Stoichiometry does not increase with depth indicating no relationship between the Ca/Mg ratio and cation ordering. Strong geochemical trends were observed down-section in the dolomite, including: (1) increasing Mn content (44 to 274 ppm), and (2) decreasing δ¹³C values (?0·9 to ?5·5‰ PDB). Oxygen isotope values range from δ¹⁸O = 1·3‰ PDB in the upper part of the section to 2·6‰ PDB in the lower part of the section and are interpreted to represent two distinct groups of values rather than a continuous trend. Down-section dolomite crystal size increase and shapes of crystal size distributions are consistent with recrystallization via a surface energy-driven dissolution-reprecipitation process (Ostwald ripening). The observed trends in carbon isotopes and Mn content probably result from geochemical re-equilibration during recrystallization and reflect reducing conditions and an isotopically light, organically derived, carbon source. Oxygen isotope compositions probably reflect relict original dolomite values and are a result of decreasing evaporation due to rising sea level.     

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.     

Epigenetic dolomitization of the Přaídolí formation (Upper Silurian), the Barrandian basin,Czech Republic: implications for burial history of Lower Paleozoic strata

Stratabound epigenetic dolomite occurs in carbonate facies of the Barrandian basin (Silurian and Devonian), Czech Republic. The most intense dolomitization is developed in bioclastic calcarenites within the transition between micritic limestone and shaledominated Přídolí and Lochkov formations deposited on a carbonate slope. Medium-crystalline (100–400 μm), inclusion-rich, xenotopic matrix dolomite (δ ¹⁸O=−4.64 to −3.40‰ PDB;δ ¹³C=+1.05 to +1.85‰ PDB) which selectively replaced most of the bioclastic precursor is volumetrically the most important dolomite type. Coarse crystalline saddle dolomite (δ ¹⁸O=−8.04 to −5.14‰ PDB;δ ¹⁸C=+0.49 to +1.49 PDB) which precipitated in fractures and vugs within the matrix dolomite represents a later diagenetic dolomitization event. In some vugs, saddle dolomite coprecipitated with petroleum inclusion-rich authigenic quartz crystals and minor sulfides which, in turn, were post-dated by semisolid asphaltic bitumen. The interpretation of the dolomitization remains equivocal. Massive xenotopic dolomite, although generally characteristic of a deeper burial setting, may have been formed by a recrystallization of an earlier, possibly shallow burial dolomite. Deeper burial recrystallization by reactive basinal pore fluids that presumably migrated through the more permeable upper portion of the Přídolí sequence appears as a viable explanation for this dolomitization overprint. Saddle dolomite cement of the matrix dolomite is interpreted as the last dolomitization event that occurred during deep burial at the depth of the oil window zone. The presence of saddle dolomite, the fluid inclusion composition of associated quartz crystals, and vitrinite paleogeothermometry of adjacent sediments imply diagenetic burial temperatures as high as 160°C. Although high geothermal gradients in the past or the involvement of hydrothermally influenced basinal fluids can account for these elevated temperatures, burial heating beneath approximately 3-km-thick sedimentary overburden of presumably post-Givetian strata, no longer preserved in the basin, appears to be the most likely interpretation. This interpretaion may imply that the magnitude of post-Variscan erosion in the Barrandian area was substantially greater than previously thought.     

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.     

A basement-interacted fluid in the N81 deposit, Pine Point Pb-Zn District, Canada: Sr isotopic analyses of single dolomite crystals

The Mississippi Valley-type Pb-Zn deposits of the Pine Point district (Northwest Territories, Canada) are located close to the eastern edge of the present day Western Canadian Sedimentary Basin. The deposits are thought to have formed as the result of basin-wide fluid flow in the Presqu’ile Barrier, the host to the ore deposits. A laser ablation multi-collector inductively coupled plasma mass spectrometric study of ⁸⁷Sr/⁸⁶Sr ratios of ore-related dolomites from the N81 deposit at Pine Point indicates that at least two sources of Sr were present in the mineralizing system. One fluid has a range in Sr isotopic values from 0.07073 to 0.71200 and is interpreted to be derived from Middle Devonian seawater that interacted with clastic units in the basin. The second fluid has higher Sr isotopic values (up to 0.71520), similar to those found in some Canadian Shield brines, and is interpreted to represent an evaporated seawater-derived brine which has interacted with crystalline basement rocks. Reactivation of old structures in the basement may have provided a pathway for cross-formation fluid flow to the site of mineralization. The data suggest that the stratigraphic location of the Pine Point District, near the interface between the Western Canadian Sedimentary Basin and its basement, may have exerted a fundamental control on the formation of these deposits.     

Formation,diagenesis and palaeoenvironmental significance of upper Ediacaran fibrous dolomite cements

Neoproterozoic marine dolomite cements represent reliable, albeit complex, archives of their palaeoenvironment. Petrological and high-resolution geochemical data from well-preserved fibrous dolomite and pyrite in the upper Ediacaran (ca 551·1 to 548·0 Ma) Dengying Formation in south-west China are presented and discussed here. The aim of this research is to reconstruct the redox state of late Ediacaran shallow seawater and porewater in the Sichuan Basin using early marine diagenetic fabrics. Based on crystalline texture and axis, four basic types of fibrous dolomite cements formed penecontemporaneously in a microbialite reef setting at the platform margin: (i) bladed dolomites (replacement from a high-Mg calcite precursor); (ii) fascicular fast dolomites (replacement from an aragonitic precursor); (iii) fascicular slow dolomites; and (iv) radial slow dolomites. The latter two fabrics are considered direct marine porewater precipitates due to their length-slow character, cathodoluminescent zonation, and enriched copper and cobalt concentrations. Marine cements yield rare earth element and yttrium patterns comparable to modern seawater and represent a refined set of archive data relative to previously published bulk dolostones. Redox-sensitive elements and cathodoluminescence indicate that the fascicular fast dolomites formed in suboxic seawater, while fascicular slow and radial slow dolomites formed in euxinic marine porewaters. Microbial sulphate reduction during the formation of fascicular slow and radial slow dolomites is recognized by nanometre-scale spheroidal ankerite and sulphur-containing dolomite, and intergrown pyrite grains with U-shaped δ³⁴S transects. Data shown here suggest predominantly suboxic shallow late Ediacaran seawater and euxinic marine porewaters, with microbial activity promoting the direct precipitation of dolomite.