Sedimentology of the Cretaceous Maha Sarakham evaporites in the Khorat Plateau of northeastern Thailand

Evaporites of the Cretaceous to early Tertiary Maha Sarakham Formation on the Khorat Plateau of southeast Asia (Thailand and Laos) are composed of three depositional members that each include evaporitic successions, each overlain by non-marine clastic red beds, and are present in both the Khorat and the Sakon Nakhon sub-basins. These two basins are presently separated by the northwest-trending Phu Phan anticline. The thickness of the formation averages 250 m but is up to 1.1 km thick in some areas. In both basins it thickens towards the basin centre suggesting differential basin subsidence preceding or during sedimentation. The stratigraphy, lithological character and mineralogy of the evaporites and clastics are identical in both basins suggesting that they were probably connected during deposition. Evaporites include thick successions of halite, anhydrite and a considerable accumulation of potassic minerals (sylvite and carnallite) but contain some tachyhydrite, and minor amounts of borates. During the deposition of halite the basin was subjected to repeated inflow of fresher marine water that resulted in the formation of anhydrite marker beds. Sedimentary facies and textures of both halite and anhydrite suggest deposition in a shallow saline-pan environment. Many halite beds, however, contain a curious `sieve-like' fabric marked by skeletal anhydrite outlines of gypsum precursor crystals and are the product of early diagenetic replacement by halite of primary shallow-water gypsum. The δ³⁴S isotopic values obtained from different types of anhydrite interbedded with halite range from 14.3‰ to 17.0‰ (CDT), suggesting a marine origin for this sulphate. Bromine concentration in the halite of the Lower Member begins around 70 ppm and systematically increases upward to 400 ppm below the potash-rich zone, also suggesting evaporation of largely marine waters. In the Middle Member the initial concentration of bromine in halite is 200 ppm, rising to 450 ppm in the upper part of this member. The bromine concentration in the Upper Member exhibits uniform upward increase and ranges from 200 to 300 ppm. The presence of tachyhydrite in association with the potassic salts was probably the result of: (1) the large volumes of halite replacement of gypsum, on a bed by bed basis, releasing calcium back into the restricted waters of the basin; and (2) early hydrothermal input of calcium chloride-rich waters. The borates associated with potash-rich beds likely resulted from erosion and influx of water from surrounding granitic terrains; however, hydrothermal influx is also possible. Interbedded with the evaporites are non-marine red beds that are also evaporative, with displacive anhydrite nodules and beds and considerable amounts of displacive halite. The δ³⁴S isotopic values of this anhydrite have non-marine values, ranging from 6.4‰ to 10.9‰ (CDT). These data indicate that the Khorat and Sakhon Nakhon basins underwent periods of marine influx due to relative world sea-level rise but were sporadically isolated from the world ocean.     

Neogene evaporites in desert volcanic environments: Atacama Desert, northern Chile

The Upper Miocene and Pliocene evaporite deposits of the Atacama Desert of northern Chile (Hilaricos and Soledad Formations) are among the few non‐marine evaporites in which aridity not only formed the deposits, but has also preserved them almost unaltered under near‐surface conditions. These deposits are largely composed of displacive Ca sulphate and halite together with minor amounts of glauberite, thenardite and polyhalite. However, at the base and top of these deposits, there are also beds of gypsum crystal pseudomorphs that originally formed as free‐growth forms within shallow brine bodies, rather than as displacive sediments. The halite is present as interstitial cement, displacive cubes and shallow‐water, bottom‐growth chevron crusts. Most of the calcium sulphate is presently anhydrite, pseudomorphous after gypsum, that was the primary depositional sulphate mineral. The secondary anhydrite formed under early diagenetic conditions after slight burial (some metres) resulting from the effect of strongly evolved pore brines. The anhydrite has been preserved without rehydration during late diagenetic and exhumation stages on account of the arid environment of the Atacama Desert. Both the Hilaricos and the Soledad Formations contain geochemical markers indicating that these Neogene evaporites had a largely non‐marine origin. Bromine content in the halite is very low (few p.p.m.), indicating neither a sedimentological relation with sea water nor the likelihood of direct recycling of prior marine halites. Moreover, the δ³⁴S of sulphates (+4·5‰ to +9‰) also reflects a non‐marine origin, with a strong volcanic influence, although some recycling of Mesozoic marine sulphates cannot be ruled out. δ³⁴S of dissolved sulphate from hot springs and streams in the area commonly displays positive values (+2‰ to +10‰). Leaching of oxidized sulphur and chlorine compounds from volcanoes and epithermal ore bodies, very common in the associated drainage areas, have been the main contribution to the accumulation of evaporites. The sedimentary and diagenetic evolution of the Hilaricos and Soledad evaporites (based on lithofacies analysis) provides information about the palaeohydrological conditions in the Central Depression of northern Chile during the Neogene. In addition, the diagenesis and exhumation history of these evaporites confirms the persistence of strongly arid conditions from Late Miocene until the present. A final phase of tectonism took place permitting the internal drainage to change and open to the sea, resulting in dissolution and removal of a significant portion of these deposits. Despite the extensive dissolution, the remaining evaporites have undergone little late exhumational hydration.     

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

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

Dolomitization of the Capitan Formation forereef facies (Permian, west Texas and New Mexico): seepage reflux revisited

Abstract Interpretation of seepage reflux dolomitization is commonly restricted to intervals containing evaporites even though several workers have modelled reflux of mesosaline brines. This study looked at the partially dolomitized forereef facies of the Capitan Formation to test the extent of reflux dolomitization and evaluate the possible role of the near‐backreef mesosaline carbonate lagoon as an alternative source of dolomitizing fluids. The Capitan Formation forereef facies ranges from 10% to 90% dolomite. Most of the dolomite is fabric preserving and formed during early burial after marine cementation, before and/or during evaporite cementation and before stylolitization. Within the forereef facies, dolomite follows depositional units, with debris‐flow and grain‐flow deposits the most dolomitized and turbidity‐current deposits the least. The amount of dolomite increases with stratigraphic age and decreases downslope. Within the reef facies, dolomite is restricted to haloes around fractures and primary cavities except where the reef facies lacks marine cements and, in contrast, is completely dolomitized. This dolomite distribution supports dolomitization by sinking fluids. Oxygen isotopic values for fabric‐preserving dolomite (δ¹⁸O = 0·9 ± 1·0‰, N = 101) support dolomitization by sea water to isotopically enriched sea water. These values are closer to the near‐backreef dolomite (δ¹⁸O = 2·1 ± 0·7‰, N = 48) than the hypersaline backreef dolomite (δ¹⁸O = 3·6 ± 0·9‰, N = 11). Therefore, the fabric‐preserving dolomite is consistent with dolomitization during seepage reflux of mainly mesosaline brines derived from the near‐backreef carbonate lagoon. The occurrence of mesosaline brine reflux in the Capitan Formation has important implications for dolomitization in forereef facies and elsewhere. First, any area with a restricted carbonate lagoon may be dolomitized by refluxing brines even if there are no evaporite facies present. Secondly, such brines may travel significant distances vertically provided permeable pathways (such as fractures) are present. Therefore, the absence of immediately overlying evaporite or restricted facies is not sufficient cause to eliminate reflux dolomitization from consideration.     

Changes in carbon and oxygen isotope composition during limestone diagenesis

The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ¹³C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ¹⁸O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ¹⁸O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ¹³C ? 6-8‰.     

Palaeoproterozoic magnesite: lithological and isotopic evidence for playa/sabkha environments

Magnesite forms a series of 1‐ to 15‐m‐thick beds within the ≈2·0 Ga (Palaeoproterozoic) Tulomozerskaya Formation, NW Fennoscandian Shield, Russia. Drillcore material together with natural exposures reveal that the 680‐m‐thick formation is composed of a stromatolite–dolomite–‘red bed’ sequence formed in a complex combination of shallow‐marine and non‐marine, evaporitic environments. Dolomite‐collapse breccia, stromatolitic and micritic dolostones and sparry allochemical dolostones are the principal rocks hosting the magnesite beds. All dolomite lithologies are marked by δ¹³C values from +7·1‰ to +11·6‰ (V‐PDB) and δ¹⁸O ranging from 17·4‰ to 26·3‰ (V‐SMOW). Magnesite occurs in different forms: finely laminated micritic; stromatolitic magnesite; and structureless micritic, crystalline and coarsely crystalline magnesite. All varieties exhibit anomalously high δ¹³C values ranging from +9·0‰ to +11·6‰ and δ¹⁸O values of 20·0–25·7‰. Laminated and structureless micritic magnesite forms as a secondary phase replacing dolomite during early diagenesis, and replaced dolomite before the major phase of burial. Crystalline and coarsely crystalline magnesite replacing micritic magnesite formed late in the diagenetic/metamorphic history. Magnesite apparently precipitated from sea water‐derived brine, diluted by meteoric fluids. Magnesitization was accomplished under evaporitic conditions (sabkha to playa lake environment) proposed to be similar to the Coorong or Lake Walyungup coastal playa magnesite. Magnesite and host dolostones formed in evaporative and partly restricted environments; consequently, extremely high δ¹³C values reflect a combined contribution from both global and local carbon reservoirs. A ¹³C‐rich global carbon reservoir (δ¹³C at around +5‰) is related to the perturbation of the carbon cycle at 2·0 Ga, whereas the local enhancement in ¹³C (up to +12‰) is associated with evaporative and restricted environments with high bioproductivity.     

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.     

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.     

Replacement of evaporites within the Permian Park City Formation, Bighorn Basin, Wyoming, USA

The Permian Park City Formation consists of cyclically bedded subtidal to supratidal carbonates, cherts and siltstones. Early diagenesis of Park City Formation carbonates occurred under the influence of waters ranging from evaporative brines to dilute meteoric solutions and resulted in evaporite emplacement (syndepositional nodules and cements), as well as dolomitization, silicification and leaching of carbonate grains. Major differences are seen, however, in the diagenetic patterns of subsurface and surface sections of Park City Formation rocks. Subsurface samples are characterized by extensively preserved evaporite crystals and nodules, and preserve evidence of significant silicification (chert, chalcedony and megaquartz) and minor calcitization of evaporites. In outcrop sections, the evaporites are more poorly preserved, and have been replaced by silica and calcite and also leached. The resultant mouldic porosity is filled with widespread, very coarse, blocky calcite spar. These replacements appear to be multistage phenomena. Field and petrographic evidence indicates that silicification involved direct replacement of evaporites and occurred during the early stages of burial prior to hydrocarbon migration. Siliceous sponge spicules provided a major source of silica, and the fluids involved in replacement were probably a mixture of marine and meteoric waters. A second period of replacement and minor calcitization is inferred to have occurred during deep burial (under the influence of thermochemical sulphate reduction), although the presence of hydrocarbons probably retarded most other diagenetic reactions during this time interval. The major period of evaporite diagenesis, however, occurred during late stage uplift. The late stage replacement and pore-filling calcites have δ¹³C values ranging from 0·5 to -25·3%, and δ¹⁸O values of -16·1 to -24·3₀ (PDB), reflecting extensive modification by meteoric water. Vigorous groundwater flow, associated with mid-Tertiary block faulting, led to migration of meteoric fluids through the porous carbonates to depths of several kilometres. These waters reacted with the in situ hydrocarbon-rich pore fluids and evaporite minerals, and precipitated calcite cements. The Tosi Chert appears to have been an even more open system to fluid migration during its burial and has undergone a much more complex diagenetic history, as evidenced by multiple episodes of silicification, calcitization (ferroan and non-ferroan), and hydrocarbon emplacement. The multistage replacement processes described here do not appear to be restricted to the Permian of Wyoming. Similarly complex patterns of alteration have been noted in the Permian of west Texas, New Mexico, Greenland and other areas, as well as in strata of other ages. Thus, multistage evaporite dissolution and replacement may well be the norm rather than the exception in the geological record.     

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.     

Evolution of late Triassic rift basin evaporites (Passaic Formation): Newark Basin, Eastern North America

The Passaic Formation of the late Triassic Newark Supergroup is 2700 m thick and was deposited in series of wide, deep to shallow lacustrine environments in the Newark rift basin (eastern North America). The Passaic Formation can be divided into lower, middle, and upper sections based on depositional structures, composition and the distribution and morphology of its evaporites. Evaporites formed as a result of syndiagenetic cementation and/or displacive processes. Evaporitive minerals now include gypsum and anhydrite, although other mineral species, such as glauberite, may have originally existed. Most of the evaporites of the Passaic Formation occur within massive red mudstone and siltstone lithologies in the form of diffuse cements, void-fillings, euhedral crystals, crystal clusters and nodules. These evaporites grew displacively within the fine siliciclastic matrix as a result of changes in the hydrochemical regimes of the rift basin. A well-developed upward increase in the amount of evaporite material is present in the Passaic Formation. This resulted from: (1) long-term, progressive increase in aridity, and (2) significant increase in evaporation surface area of the basin during its tectonic evolution. A nonmarine source for the evaporites is evident from the isotopic data. Sulphate δ³⁴S ranges from 11%. to 3.3%. CDT, while δ¹⁸O ranges from + 15.1%. to + 20.9%. SMOW, indicating derivation from early diagenetic oxidation of organic sulphur and pyrite within the organic-rich, lacustrine deposits. The ⁸⁷Sr/⁸⁶Sr ratios in sulphate are radiogenic (average 0.71211), showing the interaction of basin waters with detrital components and that the Newark Basin was isolated from the world ocean. Most of the original evaporites show evidence of diagenetic change to polycrystalline and polymineralic pseudomorphs now filled with recrystallized coarse-grained anhydrite (1–3 mm size) and low-temperature albite. Homogenization temperatures of fluid inclusions within the coarse-grained anhydrite indicate crystallization temperatures for anhydrite in the range of 150° to 280°C. Such elevated temperatures resulted from circulation of hot water in the basin. Later exhumation of these rocks caused partial to total replacement of anhydrite by gypsum in the upper part of the section. The resulting increase in volume due to hydration of anhydrite at shallow depths also emplaced non-evaporative satin-spar veins (fibrous gypsum) along bedding planes and in fractures. While the local geology of the Newark rift basin controlled the distribution of facies, the sedimentological development of the Passaic Formation evaporites resulted from the world-wide climatic aridity that prevailed during the late Triassic. because the Newark Basin sequence was only covered with about 3 km of sedimentary overburden that correspond to about 100°C and hence suggests that evaporites have experienced alteration by hot fluids. 5 As the Triassic marks the greatest evaporite formation world-wide and profound sense of parched continentality throughout the world existed before the final break-up of the Pangea, the Passaic Formation evaporites are an example of the influence of these palaeoclimatic conditions at the eastern margin of North America.     

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.     

Physical and chemical growth conditions of Ordovician organogenic deep-water dolomite concretions: implications for the δ18O of Early Palaeozoic sea water

The estimated depth of formation of authigenic dolomite concretions in the Middle Ordovician Cloridorme Formation, Quebec, ranges from < 1 m to 150–200 m below sea floor (mbsf) (mostly between < 1 and 25 mbsf), based on centre‐to‐margin variations in minus‐cement porosity (80–90% to 45–75%). Formation depths are > 350 mbsf (25–17% porosity) in the Lower Ordovician Levis Formation. Outward‐decreasing δ¹³C_VPDB values (10·2–0·8‰) suggest precipitation in the methane generation zone with an increasing contribution of light carbonate derived by advection from thermocatalytic reactions at depth. Anomalously low δ¹⁸O_VPDB values (centre‐to‐margin variations of ?0·4 to ?7·5‰) give reasonable temperatures for the concretion centres only if the δ¹⁸O of Ordovician sea water was negative (?6‰) and the bottom water was warm (> 15 °C). The 3–5‰ lower values for the concretion margins compared with the centres can be explained if, in addition, volcanic‐ash alteration, organic‐matter decomposition and/or advection of ¹⁸O‐depleted water lowered the δ¹⁸O of the pore water further by 2·0–4·0‰ during the first 25–200 m of burial. Reasonable growth temperatures for the margins of 17–20 °C are compatible with a lowering of the isotopic ratios by 1 to < 1·3‰ as a temperature effect. The systematic concentric isotope zonation of the concretions suggests that the well‐ordered near‐stoichiometric dolomite is a primary feature and not the result of recrystallization. Diagenetic dolomite beds of the Cloridorme Formation appear to have formed by coalescence of concretions, as shown by randomly sampled traverses that indicate formation at different subsurface depths. Growth of the Cloridorme dolomites was probably limited by calcium availability, at least 50% of which was derived from connate water, and the remainder by diffusion from sea water. Dolomite precipitation was favoured over calcite by very high sedimentation rates, the abundance of marine organic matter in the host sediment and a correspondingly thin sulphate reduction zone. Deep‐seated concretion growth in the Levis Formation required either internal sources for the participating ions (carbonate dissolution event) or porewater advection along faults.     

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.     

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

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

Formation of 18O-depleted dolomite within a marine evaporitic sequence, Triassic Reichenhall Formation, Austria

Dark grey, bituminous dolostones interbedded with marine-derived anhydrite horizons occur in the Triassic Reichenhall Formation of western Austria. Fossils are rare and indicate a hostile, hypersaline depositional environment. The dolomites are finely crystalline, fairly stoichiometric, well ordered and non-ferroan. Closely spaced samples (94 in total) of individual dolomite units have been analysed for their carbon and oxygen isotopic composition. The data indicate surprisingly low δ¹⁸O values (-5.7 to -2.1%₀ PDB), whereas the δ¹³C values are comparable to the contemporary Triassic seawater (+0.2 to +2.6%₀ PDB). Sedimentological evidence, including (i) lack of any evidence for extensive dissolution, (ii) distinct oxygen and carbon isotope ratios of individual dolomite units, (iii) covariance of carbon and oxygen isotopes within some dolomite layers and (iv) inclusions of celestite in dolomite, indicates a nearly closed system after early diagenesis. Combining this information with water-rock interaction calculations suggests that the lightest oxygen isotope compositions are the result of freshwater influx into the basin during very early dolomite formation. A secondary factor may be dolomite recrystallization at elevated temperatures during burial.     

泰国—老挝呵叻高原钾盐矿床研究现状及展望

泰国—老挝境内的呵叻高原马哈萨拉堪组钾盐矿床是世界上最大的钾盐矿床之一。综合研究表明,马哈萨拉堪组赋钾蒸发岩形成于晚白垩世,其成盐物质来自海水。该含盐建造很可能形成于陆相环境中,为"海源陆相"沉积。在蒸发岩沉积过程中及沉积后,一直伴随着水—岩(盐)作用的发生,钾盐沉积之后往往受到该作用的改造。溢晶石的出现是该地区"异常"蒸发岩的表现特征之一,它的形成很可能与海水的变质作用有关,但其形成机制尚未得到合理解释。兰坪—思茅盆地勐野井组与呵叻高原马哈萨拉堪组联系密切且具有共同之处,但二者在时代、成盐期次对比等问题上存在较大争议。最后,针对今后该地区钾盐研究提出了一些新的研究思路与方法。     

Depositional environments and facies of the Late Triassic Abu Ruweis Formation, Jordan

The Abu Ruweis Formation is composed of carbonates, evaporites, and mudstones, with some locally developed pelletic, oolitic and stromatolitic limestones. The lateral persistence of bedding, the purity of the evaporite rocks, the alternating arrangement of marine carbonates and evaporites indicates periodic deposition in subaqueous conditions (salina). Petrographic investigations, X-ray diffraction analysis as well as chemical analysis have shown that the outcropping evaporite beds are mainly composed of secondary gypsum, with rare anhydrite relics. Five microfacies of gypsum were recognized according to their fabrics: porphyroblastic and granoblastic gypsum showing polarization texture, gypsum pseudomorph after anhydrite laths, and satin spar gypsum. The textures they display indicate a hydration origin of precursor anhydrite, which is in turn rehydrated from primary gypsum. Some of these anhydrites were formed as a result of replacement processes of the carbonate sediments associated with the evaporites, as evidenced from the textural relationships of the carbonate and sulfate minerals. The O¹⁸ content ranges from 1.45 to 8.38% PDB and the C¹³ content ranges from −1.52 to 4.73% PDB. Trace elements analysis has shown that the Abu Ruweis dolomites are rich in strontium (up to 600 ppm), and sodium (up to 835 ppm). The isotope composition and trace elements content, as well as the petrographic characteristics point to a penecontemporaneous hypersaline dolomitization origin for the Abu Ruweis dolomites. The evaporites were deposited during a regressive lowstand systems tract, whereas the carbonates were deposited under shallow water marine conditions during a highstand systems tract. The Abu Ruweis succession represents a relatively stable arid climate within a rapidly subsiding basin. Restricted conditions were provided by the development of beach barriers.     

Halite saltern in the Canning Basin, Western Australia: a sedimentological analysis of drill core from the Ordovician-Silurian Mallowa Salt

The Late Ordovician-Early Silurian Mallowa Salt of the Carribuddy Group, Canning Basin, north-west Australia, is the largest halite deposit known in Australia, attaining thicknesses of 800 m or more within an area of approximately 200 000 km². Study of 675 m of drill core from BHP-Utah Minerals’ Brooke No. 1 well in the Willara Sub-basin indicates that the Mallowa Salt accumulated within a saltern (dominantly subaqueous evaporite water body) that was subject to recurrent freshening, desiccation and exposure. Textures and bromine signatures imply a shallow water to ephemeral hypersaline environment typified by increasing salinity and shallowing into evaporitic mudflat conditions toward the top of halite-mudstone cycles (Type 2) and the less common dolomite/anhydrite-halite-mudstone cycles (Type 1). The borate mineral priceite occurs in the capping mudstones of some cycles, reinforcing the idea of an increasing continental influence toward the top of mudstone-capped halite cycles. The rock salt in both Type 1 and Type 2 cycles typically comprises a mosaic of large, randomly orientated, interlocking halite crystals that formed during early diagenesis. It only partially preserves a primary sedimentary fabric of vertically elongate crystals, some with remnant aligned chevrons. Intraformational hiati, halite karst tubes and solution pits attest to episodic dissolution. Stacked Type 2 cycles dominate; occasional major recharges of less saline, perhaps marine, waters in the same area produced Type I cycles. The envisaged saltern conditions were comparable in many ways to those prevailing during the deposition of halite cycles of the Permian Salado Formation in New Mexico and the Permian San Andres Formation of the Palo Duro Basin area in Texas. However, in the Canning Basin the cycles are characterized by a much lower proportion of anhydrite, implying perhaps a greater degree of continental restriction to the basin. The moderately high level of bromine in the Mallowa Salt (156·5 ± 43·5 ppm Br for primary halite, 146·1 ± 54·7 ppm Br for secondary halite) accords with evolved continental brines, although highly evaporative minerals such as polyhalite and magnesite are absent. The bromine levels suggest little or no dissolution/reprecipitation of primary halite and yet, paradoxically, there is little preservation of the primary depositional fabric. The preservation of early halite cements and replacement textures supports the idea of an early shutdown of brine flow paths, probably at burial depths of no more than a few metres, and the resultant preservation of primary bromine values in the secondary halite.     

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.