Differentiation of environments of dolomite formation, Lower Cretaceous of Central Tunisia

Combined field, sedimentological, mineralogical, isotopic and geochemical study of the Lower Cretaceous dolomites of Central Tunisia has demonstrated considerable diversity in origin. Environments of dolomite formation include deep phreatic, karst, lacustrine and evaporitic sabkha. All four groups of dolomite are composed of non-stoichiometric and/or disordered crystals which are more or less rich in calcium and in iron. Petrographic fabrics are of three types: replacement, recrystallization and cementation. These three fabrics are proposed among the various criteria for the different environments of dolomitization. Average isotope (δ¹⁸ O and δ¹³ C) contents for these four dolomite groups range from ?10·5 to +0·4%_o (PDB) and ?3·9 to + 3·7%_o respectively. The distribution of strontium is related both to the degree of recrystallization and to the palaeosalinity. Ferrous iron, also very common, is regarded as an indicator of relatively deep reducing conditions, mainly in meteoric groundwaters. Sodium distribution is related to inclusions within the dolomite, its distribution being relatively constant in all four groups; it cannot be regarded as a reliable criterion for palaeosalinity of dolomitizing fluids. This study confirms that dolomitization may occur under widely different palaeoenvironments, either at the surface or during burial. With the exception of the sabkha environment, dolomitizing fluids seem to have been essentially meteoric.     

Tectonically driven dolomitization of Cambrian to Lower Ordovician carbonates of the Quruqtagh area,north‐eastern flank of Tarim Basin,north‐west China

Dolomites occur extensively in Cambrian to Lower Ordovician carbonates in the Tienshan orogen of the Quruqtagh area, north‐east Tarim Basin, where thick (up to 1 km), dark grey lenticular limestones of semi‐pelagic to pelagic origin are prominent. The dolomites generally occur as beige, anastomosed geobodies that cross‐cut well‐stratified limestones. Based on detailed field investigations and petrographic examination, three types of matrix dolomite are identified: fine crystalline planar‐e (Md1), fine to medium crystalline planar‐s (e) (Md2) and fine to coarse crystalline non‐planar‐a (Md3) dolomites. One type of cement dolomite, the non‐planar saddle dolomite (Cd), is also common. The preferential occurrence of Md1 along low‐amplitude stylolites points to a causal link to pressure dissolution by which minor Mg ions were probably released for replacive dolomitization during shallow burial compaction. Type Md2, Md3 and Cd dolomites, commonly co‐occurring within the fractured zones, have large overlaps in isotopic composition with that of host limestone, implying that dolomitizing fluids inherited their composition from remnant pore fluids or were buffered by the formation water of host limestones through water–rock interaction. However, the lower δ¹⁸O and higher ⁸⁷Sr/⁸⁶Sr ratios of these dolomites also suggest more intense fluid–rock interaction at elevated temperature and inputs of Mg and radiogenic Sr from the host limestones with more argillaceous matter and possibly underlying Neoproterozoic siliciclastic strata. Secondary tensional faults and fractures within a compressional tectonic regime were probably important conduits through which higher‐temperature Mg‐rich fluids that had been expelled from depth were driven by enhanced tectonic compression and heating during block overthrusting, forming irregular networks of dolomitized bodies enclosed within the host limestones. This scenario probably took place during the Late Hercynian orogeny, as the Tarim block collided with Tienshan island arc system to the north and north‐east. Subsequent downward recharges of meteoric fluids into the dolomitizing aquifer probably terminated dolomitization as a result of final closure of the South Tienshan Ocean (or Palaeo‐Asian Ocean) and significant tectonic uplift of the Tienshan orogen. This study demonstrates the constructive role of notably tensional (or transtensional) faulting/fracturing in channelling fluids upward as a result of intense tectonic compression and heating along overthrust planes on the convergent plate margin; however, a relatively short‐lived, low fluid flux may have limited the dolomitization exclusively within the fractured/faulted limestones in the overthrust sheets.     

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.     

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

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

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.     

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).     

四川盆地东北部晚二叠世-早三叠世白云岩与同期海水锶同位素组成的对比研究

在四川盆地东北部14条野外剖面和地下钻井的二叠系长兴组、三叠系飞仙关组和嘉陵江组石灰岩和白云岩岩石学研究的基础上,对其中189个不同类型的碳酸盐样品(包括代表海水的石灰岩样品和在不同成岩阶段形成的各种白云岩样品)进行了锶同位素组成和相应的MgO、CaO和Mn、Sr元素分析,获得了系统的晚二叠-早三叠世海水的锶同位素组成数据并建立了相应演化曲线.在此基础上,对不同地层组/段和不同类型白云岩的锶同位素组成与同期海水锶同位素组成进行了对照研究,取得了如下主要认识:(1)川东北晚二叠-早三叠世白云岩的锶同位素组成与同期海水具有类似的演化趋势,结合白云岩的低锰、高锶特征,说明白云化流体与海水存在显著的亲缘关系,与铝硅酸盐地层无关;(2)白云岩的锶同位素组成与同期海水存在差别,各地层组/段白云岩的87Sr/86Sr比值都不同程度地高于同期海水,但从下往上,即从长兴组、飞2+3段、嘉2段到嘉4段,这种差值逐渐缩小,嘉4段白云岩的锶同位素组成已和同期海水基本一致;(3)川东北长兴组、飞2+3段白云岩形成的时间显著晚于同层石灰岩,白云化流体为时间上更晚的海源流体,但嘉2、嘉4段白云岩的形成时间仅略晚于同层石灰岩,白云化流体来源于非常近同期的蒸发浓缩的高Mg/Ca比值海水,一些嘉4段的白云岩的白云化流体就是同期海水,因而这些白云岩是同生或准同生的;(4)如果把白云化的时间看作白云岩的形成时间,则违背地层叠置原理是川东北长兴组和飞仙关组结晶白云岩的主要特征之一,其形成机制可用非同期海源流体的隐伏回流-对流模式来解释,嘉陵江组白云岩形成机制可用活跃回流-萨布哈模式来解释.白云岩和代表同期海水的石灰岩锶同位素组成的对比为解决白云化流体与海水之间的时间关系提供一种新的研究途径.     

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.     

Evidence for high temperature and 18O‐enriched fluids in the Arab‐D of the Ghawar Field,Saudi Arabia

Using the clumped isotope method, the temperature of dolomite and calcite formation and the oxygen isotopic composition (δ¹⁸O_w) of the diagenetic fluids have been determined in a core taken from the Arab‐D of the Ghawar field, the largest oil reservoir in the world. These analyses show that while the dolomites and limestones throughout the major zones of the reservoir recrystallized at temperatures between ca 80°C and 100°C, the carbonates near the top of the reservoir formed at significantly lower temperatures (20 to 30°C). Although the δ¹⁸O values of the diagenetic fluids show large variations ranging from ca <0‰ to ca +8‰, the variations exhibit consistent downhole changes, with the highest values being associated with the portion of the reservoir with the highest permeability and porosity. Within the limestones, dolomites and dolomites associated with the zone of high permeability, there are statistically significant different trends between the δ¹⁸O_w values and recrystallization temperature. These relationships have different intercepts suggesting that fluids with varying δ¹⁸O_w values were involved in the formation of dolomite and limestone compared to the formation of dolomite associated with the zone of high permeability. These new data obtained using the clumped isotope technique show how dolomitization and recrystallization by deep‐seated brines with elevated δ¹⁸O_w values influence the δ¹⁸O values of carbonates, possibly leading to erroneous interpretations unless temperatures can be adequately constrained.     

Origin and modification of Cambrian dolomites (Red Heart Dolomite and Arthur Creek Formation), Georgina Basin, central Australia

The Early to Middle Cambrian Red Heart Dolomite and lower Arthur Creek Formation of the southern portion of the Georgina Basin, Australia, is an entirely dolomitized succession of shallow-water evaporitic mudflat and deeper-water subtidal lithologies. Three types of dolomite have been identified and are interpreted as: (1) syndepositional dolomite; (2) regional replacement dolomite; and (3) void-filling dolomite (cement). Syndepositional dolomite, derived from saline pore fluids developed in a sabkha environment, is a minor dolomite type with very fine crystal mosaics and has a mottled, non-zoned cathodoluminescence. The widespread regional replacement dolomite ranges from fine- to medium-crystalline forming mainly planar-s and non-planar-a crystal mosaics, and displays blotchy, mottled, non-zoned cathodoluminescence. Void-filling dolomite commonly forms planar-s to planar-e, medium to very coarse crystal mosaics. Rare non-planar-c, very coarsely crystalline saddle dolomite also exists. Void-filling dolomite has a successively zoned cathodoluminescence pattern from non-, to brightly, to dully luminescent. Geochemically, the syndepositional dolomite has δ¹⁸O (PDB) values ranging between ? 5.3 and ? 8.6%_o. Regional replacement dolomites exhibit a wide range of δ¹⁸O values from ? 3.3 to ? 10.9%_o whereas void-filling dolomite has δ¹⁸O values ranging from ? 10.8 to ? 14.3%_o. All three dolomite types have similar δ¹³C (PDB) values, in the range between +1.7 and ?1.7%_o. Three initial dolomitization episodes are interpreted: (1) a sabkha stage, forming the syndepositional dolomite and dolomitizing the evaporitic mudflat lithologies; (2) a brine-reflux stage, replacing the subtidal lithologies; and (3) a burial stage, forming the void-filling dolomite type. Final dolomite stabilization occurred during burial, at elevated temperatures, in the presence of basinal fluids, resulting in progressive recrystallization and stabilization of the earlier-formed syndepositional and replacement dolomites. Both textural and geochemical evolution should be taken into account when studying the origin of dolomites, based on their present geochemical composition. Sulphates are represented by very fine-crystalline syndepositional anhydrite in association with the syndepositional dolomite, and coarse to very coarse anhydrite cement. Evaportic mudflat (sabkha) and burial environments are inferred for the origin of the former and the latter anhydrite types, respectively. Evaporite dissolution breccias, indicative of the former presence of evaporites, are common throughout the succession.     

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.     

Dolomitization by penesaline sea water in Early Jurassic peritidal platform carbonates, Gibraltar, western Mediterranean

Peritidal carbonates of the Lower Jurassic (Liassic) Gibraltar Limestone Formation, which form the main mass of the Rock of Gibraltar, are replaced by fine and medium crystalline dolomites. Replacement occurs as massive bedded or laminated dolomites in the lower 100 m of an ≈460‐m‐thick platform succession. The fine crystalline dolomite has δ¹⁸Ο values either similar to, or slightly higher than, those expected from Early Jurassic marine dolomite, and δ¹³C values together with ⁸⁷Sr/⁸⁶Sr ratios that overlap with sea‐water values for that time, indicating that the dolomitizing fluid was Early Jurassic sea water. Absence of massive evaporitic minerals and/or evaporite solution‐collapse breccias in these carbonate rocks indicates that the salinity of sea water during dolomitization was below that of gypsum precipitation. The occurrence of peritidal facies, a restricted microbiota and rare gypsum pseudomorphs are also consistent with penesaline conditions (salinity 72–199‰). The medium crystalline dolomite has some δ¹⁸Ο and δ¹³C values and ⁸⁷Sr/⁸⁶Sr ratios similar to those of Early Jurassic marine dolomites, which indicates that ambient sea water was again a likely dolomitizing fluid. However, the spread of δ¹⁸Ο, δ¹³C and ⁸⁷Sr/⁸⁶Sr values indicates that dolomitization occurred at slightly increased temperatures as a result of shallow (≈500 m) burial or that dolomitization was multistage. These data support the hypothesis that penesaline sea water can produce massive dolomitization in thick peritidal carbonates in the absence of evaporite precipitation. Taking earlier models into consideration, it appears that replacement dolomites can be produced by sea water or modified sea water with a wide range of salinities (normal, penesaline to hypersaline), provided that there is a driving mechanism for fluid migration. The Gibraltar dolomites confirm other reports of significant Early Jurassic dolomitization in the western Tethys carbonate platforms.     

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.     

The Origin of Paleokarst in the Huanglong Formation of the Eastern Sichuan Basin: Evidence from δ13C, δ18O and 87Sr/86Sr

Karst rocks from the Huanglong Formation exposed at the margin of the Eastern Sichuan Basin can be divided into four types:slightly corroded, moderately corroded porous, intensely corroded brecciated and intensely corroded and replaced secondary calcic karstic rocks. The carbon, oxygen and strontium isotope compositions of the various karst rocks are analyzed systematically and compared to rocks without karst corrosion. The results indicate that(1) the Huanglong Formation in the eastern Sichuan Basin was a restricted bay supplied and controlled by freshwater in which mudmicrite and mud-dolomicrite exhibit low δ13C and δ18O values and high 87Sr/86 Sr ratios;(2) all types of karstic rocks in the paleokarst reservoirs of the Huanglong Formation in the research area are affected by atmospheric freshwater with the δ13C and δ18O values and 87Sr/86 Sr ratios in the original formation approaching those of atmospheric freshwater, which reflects ancient hydrological conditions, fluid properties, isotopic source and the fractionation effect;(3) the intensely corroded and replaced secondary limestone is affected by a variety of diagenetic fluids, often reflected by δ13C and δ18O values, while the 87Sr/86 Sr ratios exhibit the strong degree of the corrosion;(4) after comparing the 87Sr/86 Sr ratios of each type of karst rock, the diagenetic fluids are determined to be mainly atmospheric freshwater, and depending on the strength of corrosion, and the low 87Sr/86 Sr ratio fluids in the layer will participate in the karst process. The carbon, oxygen, and strontium isotopes of different karstic reservoirs can provide meaningful geochemical information for forecasting and evaluating the development and distribution rules of the Huanglong Formation at the margin of the eastern Sichuan Basin in time and space.     

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.     

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

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

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.     

Deducing the source and composition of rare earth mineralising fluids in carbonatites: insights from isotopic (C,O, <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) data from Kangankunde,Malawi

Carbonatites host some of the largest and highest grade rare earth element (REE) deposits but the composition and source of their REE-mineralising fluids remains enigmatic. Using C, O and ⁸⁷Sr/⁸⁶Sr isotope data together with major and trace element compositions for the REE-rich Kangankunde carbonatite (Malawi), we show that the commonly observed, dark brown, Fe-rich carbonatite that hosts REE minerals in many carbonatites is decoupled from the REE mineral assemblage. REE-rich ferroan dolomite carbonatites, containing 8–15 wt% REE₂O₃, comprise assemblages of monazite-(Ce), strontianite and baryte forming hexagonal pseudomorphs after probable burbankite. The ⁸⁷Sr/⁸⁶Sr values (0.70302–0.70307) affirm a carbonatitic origin for these pseudomorph-forming fluids. Carbon and oxygen isotope ratios of strontianite, representing the REE mineral assemblage, indicate equilibrium between these assemblages and a carbonatite-derived, deuteric fluid between 250 and 400 °C (δ¹⁸O + 3 to + 5‰_VSMOW and δ¹³C ? 3.5 to ? 3.2‰_VPDB). In contrast, dolomite in the same samples has similar δ¹³C values but much higher δ¹⁸O, corresponding to increasing degrees of exchange with low-temperature fluids (< 125 °C), causing exsolution of Fe oxides resulting in the dark colour of these rocks. REE-rich quartz rocks, which occur outside of the intrusion, have similar δ¹⁸O and ⁸⁷Sr/⁸⁶Sr to those of the main complex, indicating both are carbonatite-derived and, locally, REE mineralisation can extend up to 1.5 km away from the intrusion. Early, REE-poor apatite-bearing dolomite carbonatite (beforsite: δ¹⁸O + 7.7 to + 10.3‰ and δ¹³C ?5.2 to ?6.0‰; ⁸⁷Sr/⁸⁶Sr 0.70296–0.70298) is not directly linked with the REE mineralisation.     

Milankovitch cyclicity in Purbeck peritidal limestones of the Prebetic (Berriasian, southern Spain)

Peritidal carbonate rocks (Purbeck facies) of the uppermost Portlandian to Berriasian in the type section of the Sierra del Pozo Formation in the Prebetic Zone, southern Spain, are divisible into 141 shallowing upward cycles averaging 2 m in thickness. The subtidal facies in these cycles consist of micritic or marly limestones with dasycladacean algae and lituolids; the intertidal facies are micritic limestones containing birdseyes and miliolids; the supratidal facies comprise laminated algal limestones, the tops of which display desiccation cracks and rhizocretions, or more locally palaeosols, calcretes, or palaeokarst surfaces. A statistical study, using power spectra of the Fast Fourier Transform, demonstrates that the periodicity of these cycles is in the Milankovitch frequency band. Most sedimentary cycles correspond to the obliquity cycles; eccentricity and precession cycles have also been recognized. Using a Fischer plot, third-order tectono-eustatic cycles are recognized, which can be correlated with the eustatic curve of the Exxon chart. The shallowing upward sequences are characterized by a distinctive pattern of geochemical parameters. Carbon and oxygen isotopic (δ¹³C and δ¹⁸O) variations, calcium and magnesium carbonate contents and the abundance of organic matter and trace elements (Mn and Sr) all have predictable patterns of distribution within the sequences. The Sr content of the subtidal facies is relatively high whereas the δ¹³C and δ¹⁸O ratios are quite low; in the intertidal facies the Sr and Mn levels fall concomitantly with a rise in δ¹³C and δ¹⁸O. The highest δ¹³C and δ¹⁸O values occur in the lower part of the supratidal facies, whereas in the upper part of δ values and Sr contents drop sharply. Cyclic variations in evaporation and in meteoric water influence, determined from oxygen isotopic composition, reveal that the cyclicity of the beds containing the most limestones (supratidal) and those with the most marls (subtidal) is related to climatic changes. The coldest periods are those represented by supratidal deposits, when the sea level was at its lowest. During the warmest periods, when the overall sea level was higher, subtidal deposits accumulated in the region. A genetic model is proposed, according to which the asymmetrical sedimentary cycles occur in response to glacio-eustatic changes with a periodicity similar to that of Plio-Pleistocene sea-level variations, but with a much lower range due to the smaller extent of polar ice caps during the Early Cretaceous. The glacio-eustatic changes involved a rapid sea-level rise and a slow sea-level fall.     

The geometry and petrogenesis of hydrothermal dolomites at Navan, Ireland

The dolomites at Navan, Ireland, formed in Courceyan peritidal and shallow-shelf limestones. The dolomite body has a plume-like geometry, cross-cutting both lithological boundaries and diagenetic barriers generated by sea-floor cementation and emergence. The dolomitizing fluids rose parallel to major faults to diffuse laterally through the succession, controlled by variations in permeability that reflect both facies variation on deposition and pre-dolomitization diagenesis. Cathodoluminescent zones reveal three principal stages of dolomite emplacement, separated by dissolution surfaces, with each stage reflecting several changes in the character of dolomitizing solutions. The predominance of dull zones indicates burial rather than surface conditions. The dolomites formed some time after burial in response to an areally limited hydrothermally-driven flow. Isotope values (σ¹⁸O of — 6σ6 to — 10.4%_δ and σ¹³C of — 0σ2 to +2σ5%_δ PDB), and fluid inclusion data, suggest that these fluids had compositions similar to those of Carboniferous seawater. However, these became hotter with time, with temperature increasing from 60 to 160δC. The Navan dolomites are closely associated with Europe's largest zinc-lead deposit. The distribution of the ores follows the same trend as that of the dolomites and paragenetic relationships indicate that dolomitization and mineralization were temporally and genetically related.