Nodular chert from the Arbuckle Group, Slick Hills, SW Oklahoma: a combined field, petrographic and isotopic study

Nodular chert from the middle and upper Arbuckle Group (Early Ordovician) in the Slick Hills, SW Oklahoma, was formed by selective replacement of grainstones, burrow fillings, algal structures, and evaporite nodules. Chert nodules are dominantly microquartz with minor fibrous quartz (both quartzine and chalcedony), megaquartz, and microflamboyant quartz. Lepisphere textures of an opal-CT precursor are preserved in many (especially in finely-crystalline) chert nodules. The δ¹⁸O values of microquartz chert range from +23.4 to + 28.8^0/00 (SMOW), significantly lower than those of Cenozoic and Mesozoic microquartz chert formed both in the deep sea and from near-surface sea water. The δ¹⁸O values of chert decrease with increasing quartz crystal size. Silicification in the Arbuckle Group occurred during early diagenesis, with the timing constrained by the relative temporal relationships among silicification, burial compaction, and early dolomite stabilization. Silica for initial chert nucleation may have been derived from both dissolution of sponge spicules and silica-enriched sea water. Chert nucleation appears to have been controlled by the porosity, permeability, and organic matter content of precursor sediments. This conclusion is based on the fact that chert selectively replaced both porous grainstones and burrows and algal structures enriched in organic matter. Growth of chert probably occurred by a maturation process from opal-A(?), to opal-CT, to quartz, as indicated by the presence of opal-CT precursor textures in many chert nodules. Although field and petrographic evidence argues for an early marine origin for chert in the Arbuckle Group, the light δ¹⁸O values are inconsistent with this origin. Meteoric resetting of the δ¹⁸O values of the chert during exposure of the carbonate platform best explains the light δ¹⁸O values because: (i) the δ¹⁸O values of chert nodules decrease with decreasing δ¹⁸O values of host limestones, and (ii) chert nodules from early dolomite, which underwent more extensive meteoric modification than associated limestones, have lighter δ¹⁸O values than chert nodules from limestones. Increasing recrystallization of chert nodules by meteoric water resulted in progressive ¹⁸O depletion and (quartz) crystal enlargement.     

Origin of spheroidal chert nodules, Drunka Formation (Lower Eocene), Egypt

Chert nodules of the Drunka Formation (Lower Eocene) are mostly spherical, have diameters from 40 to 120 cm, are quasi-uniformly spaced 2–3 m apart in the plane of bedding, have concentric internal structure and, except for rare small (<6 cm) solid chert nodules, are less than 85% chertified. Nodules formed after moderate alteration of limestone by meteoric water (δ¹⁸O_calcite = –4 to –8‰) at shallow (<100 m) burial depths; more extensive alteration of limestone (δ¹⁸O = –10 to –16‰) by meteoric water followed nodule growth. Chertification was by low-temperature meteoric water (δ¹⁸O_quartz = +18‰ in margins to +22‰ in nuclei) at shallow burial depths. Meteoric water may have invaded the Drunka Formation in association with shelf progradation during the Early Eocene, or during the development of a Middle Eocene unconformity. Replacement of carbonate mud by microcrystalline quartz was the dominant chertification process, but fossils were replaced in part by fine-grained equant megaquartz, quartzine and chalcedony; the last of these occurs in places as beekite. Opal A-secreting marine organisms are the inferred source of silica, but none are preserved. There is no compelling evidence of an opal-CT precursor, so quartz may have formed by direct precipitation. Self-organization processes of enigmatic character established the spacing pattern of the nodules and also the Liesegang-banded internal structure of the chert nodules. Nodules grew chiefly by diffusive supply of silica, although one locality has elongate nodules that grew when there was some porewater advection. Chertification patterns and δ¹⁸O values of both calcite and quartz indicate that nodule growth was complex and variable. Some nodules probably grew from the centre outwards. Many nodules, however, initially grew simultaneously across the entire nodule, but late-stage growth was predominantly at the outer margins or at selective internal sites.     

Early and pervasive dolomitization by near-normal marine fluids: New lessons from an Eocene evaporative setting in Qatar

The upper Palaeocene–lower Eocene Umm er Radhuma Formation in the subsurface of Qatar is dominated by subtidal carbonate depositional packages overlain by bedded evaporites. In Saudi Arabia and Kuwait, peritidal carbonate depositional sequences with intercalated evaporites and carbonates in Umm er Radhuma have been previously interpreted to have been dolomitized via downward reflux of hypersaline brines. Here, textural, mineralogical and geochemical data from three research cores in Qatar are presented which, in contrast, are more consistent with dolomitization by near-normal marine fluids. Petrographic relationships support a paragenetic sequence whereby dolomitization occurred prior to the formation of all other diagenetic mineral phases, including chert, pyrite, palygorskite, gypsum, calcite and chalcedony, which suggests that dolomitization occurred very early. The dolomites occur as finely crystalline mimetic dolomites, relatively coarse planar-e dolomites, and coarser nonplanar dolomites, all of which are near-stoichiometric (50.3 mol% MgCO₃) and well-ordered (0.73). The dolomite stable isotope values (range −2.5‰ to +1‰; mean δ¹⁸O = −0.52‰) and trace element concentrations (Sr = 40 to 150 ppm and Na = 100 to 600 ppm) are compatible with dolomitization by near-normal seawater or mesohaline fluids. Comparisons between δ¹⁸O values from Umm er Radhuma dolomite and the overlying Rus Formation gypsum further suggest that dolomitization did not occur in fluids related to Rus evaporites. This study provides an example of early dolomitization of evaporite-related carbonates by near-normal seawater rather than by refluxing hypersaline brines from overlying bedded evaporites. Further, it adds to recent work suggesting that dolomitization by near-normal marine fluids in evaporite-associated settings may be more widespread than previously recognized.     

Diagenesis of spiculites and carbonates in a Permian temperate ramp succession – Tempelfjorden Group,Spitsbergen, Arctic Norway

This paper explores little investigated diagenesis of spicule‐dominated sediments, based on Permian spiculites and cool‐water carbonates of the Tempelfjorden Group in central Spitsbergen. Field observations, petrography, stable isotope geochemistry, and mineralogical and chemical analyses reveal that the strata have been subjected to multistage diagenesis as the result of silica phase transitions at medium burial depths and deep‐burial overprinting. The growth of silica concretions occurred during the opal‐A/opal‐CT conversion and was controlled by the content and distribution of clay and spicules in the sediment, resulting in a variety of megascopic silica fabrics. Opal‐CT was subsequently dissolved, and all silica is now in a stable quartz stage. Petrographically, the rocks are characterized by a variety of chalcedony and quartz cements which perfectly preserve precursor textures. Most cements precipitated from silica‐oversaturated fluids, and their shapes reflect the silica saturation state and geometry of the pore space. Some microquartz and cryptoquartz also formed by a solid–solid inversion (recrystallization) of chalcedony. The cements have δ ¹⁸O values between +30‰ and +20‰ Standard Mean Ocean Water and display a systematic depletion in ¹⁸O from the first to the last crystallized, interpreted to reflect a gradual increase in temperature during burial. The precipitation of quartz cements started in the Middle Triassic when the strata passed the 19°C isotherm at burial depths of ca 600 m, and was completed in the mid‐Cretaceous, 2·3 km beneath the sea floor at temperatures of 75°C. Late diagenetic overprinting of the chert includes fracturing, brecciation and cementation with carbonate cements having δ ¹⁸O values between +2‰ and −30‰ Pee Dee Belemnite and δ ¹³C values between +4‰ and −14‰ Pee Dee Belemnite; they are linked to hot solutions introduced during Cretaceous volcanism or Palaeogene tectonism. This study illustrates the diagenetic pathway during burial of spicule‐rich sediments in a closed system and thereby provides a baseline for studies of more complexly altered chert deposits.     

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.     

Origin and migration of palaeofluids in the Upper Visean of the Campine Basin, northern Belgium

Upper Visean limestones in the Campine Basin of northern Belgium are intensively fractured. The largest and most common fractures are cemented by non-ferroan, dull brown-orange luminescent blocky calcite. First melting temperatures of fluid inclusions in these calcites are around -57°C, suggesting that precipitation of the cements occurred from NaCl-CaCl₂-MgCl₂ fluids. The final melting temperatures (T_m^ice) are between -5 and -33°C. The broad range in the T_m^ice data can be explained by the mixing of high salinity fluids with meteoric waters, but other hypotheses may also be valid. Homogenization temperatures from blocky calcite cements in the shelf limestones are interpreted to have formed between 45 and 75°C. In carbonates which were deposited close to and at the shelf margin, precipitation temperatures were possibly in the range 70-85°C and 72-93°C, respectively. On the shelf, the calcites have a δ¹⁸O around -9.3‰ PDB and they are interpreted to have grown in a fluid with a δ¹⁸O between −3.5 and +1.0‰ SMOW. At the shelf margin, blocky calcites (δ¹⁸O∼ - 13.5‰ PDB) could have precipitated from a fluid with a δ¹⁸O betweenn -4.0 and -1.1‰ SMOW. The highest oxygen isotopic compositions are comparable to those of Late Carboniferous marine fluids (δ¹⁸O= - 1‰ SMOW). The lowest values are more positive than a previously reported composition for Carboniferous meteoric waters (δ¹⁸O= -7‰ SMOW). Precipitation is likely to have occurred in marine-derived fluids, which mixed with meteoric waters sourced from near the Brabant Massif. Fluids with a similar negative oxygen isotopic composition and high salinity are actually present in Palaeozoic formations. The higher temperature range in the limestones near the shelf margin is explained by the upward migration of fluids from the ‘basinal’ area along fractures and faults into the shelf.     

Alluvial-fan-carbonate facies with evaporites, Eocene Guarga Formation, Southern Pyrenees, Spain

Continental carbonates of the basal part of the Guarga Formation, Upper Eocene, have been studied in the field and in the laboratory. Both geographic pattern and vertical sequences served as a basis for sedimentary models. The pattern reveals that carbonate deposition was greater in the western part of the Tremp-Graus Basin than in the eastern part. Studies of slabs and thin sections suggest high energy deposition in the eastern part of the basin and low energy deposition in the western part. Gross lithology, petrography, and faunal/floral associations indicate sedimentary environments which include calcimorphic palaeosoils, caliche nodule zones, solid caliche nodule zones, caliche crusts, fluvial carbonates, paludal carbonates, and pond/lake carbonates. Distribution pattern of the carbonate bodies and lithologies seem to be controlled by alluvial-fan processes. They are typical fining-upward sequences in the sense of Collinson (1978) which furthermore can be assigned to a channel-bound group and a succession independent of fluvial channels. Referring to fan-physiography the sequences can be subdivided into fluvial proximal interchannel, fluvial distal interchannel, lacustrine distal interchannel, nearshore lacustrine-paludine, and lacustrine offshore carbonate facies. The two last categories are distal alluvial plain and/or fan-edge associations. The presence of especially charophyte oogonia adjacent to pseudomorphs of lenticular gypsum in the lacustrine carbonates of the western Tremp-Graus Basin indicates that their depositional environment was that of shallow lakes with alternating salinities. Diagenetic alterations consist of three major phenomena: (a) general cementation of the carbonates by low-Mg calcite, (b) pseudomorphs of lenticular gypsum, and (c) silification. The relationship of gypsum and silica diagenesis to the regional distribution of lacustrine carbonates suggests early diagenetic processes for their formation. Gypsum pseudomorphs are small and are found to be replaced by Fe-calcite throughout the whole area, or are large and replaced preferentially by silica in the west only. There is experimental evidence (Cody, 1979) that distribution of gypsum morphology and crystal sizes can be related to increased salinities and increased organic production in the west. Chert-gypsum fabrics from that area resemble the ‘silex nectique’ of Cayeux (1929). The occurrence of this noteworthy type of chert together with length-slow chalcedony is an indication of relatively early silification of the gypsum. It is suggested that the sediments containing the silicified lenticular gypsum hosted brines of partly marine origin which alternately became brackish or fresh. An attempt was made to check the influence of evaporation during carbonate deposition by determining the stable isotope composition of the carbonates and of the chert. The data show no distinct variations with respect to the presumed palaeoenvironments. The ranges in the carbonates (δ¹³C ? 5,0 to ?7,9; δ¹⁸ O ?4,5 to ?7,7) fit among the data given in the literature. The values derived from chert (δ¹⁸O 26,9 to 31 SMOW) support a concept of alternating salinities. Distribution of carbonate lithofacies indicate a systematic change in sedimentation from fluvial/ephemeral to permanent lacustrine from east to west. Diagenetic alterations suggest an increase of salinities of pore waters in the same direction. In addition the lacustrine limestones in the west were due to frequent changes in pore-water salinity. Similar sequences lacking subtidal and/or lagoonal fossil associations but including pseudomorphs of carbonate and chert after lenticular gypsum were described from the Lower Purbeckian of Dorset (West, 1964, 1975, 1979), and from the Tertiary of the Paris Basin (Fontes, 1968). Guarga limestone environments of especially the western Tremp-Graus Basin probably resembled the modern semi-arid ephemeral saline lakes in Australia (Burne, Bauld & De Dekker, 1980). Gypsum precipitation in these environments can be compared to the one in modern sabkhas from the Mediterranean coast of Egypt (West, Ali & Hilmy, 1979; Ali West & Hilmy, 1980).     

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.     

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.     

Origin of quartz geodes from Laño and Tubilla del Agua sections (middle–upper Campanian,Basque‐Cantabrian Basin,northern Spain): isotopic differences during diagenetic processes

Quartz geodes and nodular chert have been found within middle–upper Campanian carbonate sediments from the Laño and Tubilla del Agua sections of the Basque‐Cantabrian Basin, northern Spain. The morphology of geodes together with the presence of anhydrite laths included in megaquartz crystals and spherulitic fibrous quartz (quartzine‐lutecite), suggest an origin from previous anhydrite nodules. The anhydrite nodules at Laño were produced by the percolation of marine brines, during a period corresponding to a sedimentary gap, with δ³⁴S and δ¹⁸O mean values of 18.8‰ and 13.6‰ respectively, consistent with Upper Cretaceous seawater sulphate values. Higher δ³⁴S and δ¹⁸O mean values of 21.2‰ and 21.8‰ recorded in the Tubilla del Agua section are interpreted as being due to a partial bacterial sulphate reduction process in a more restricted marine environment. The idea that sulphates may have originated from the leaching of previously deposited Keuper sulphate evaporites with subsequent precipitation as anhydrite, is rejected because the δ³⁴S, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values of anhydrite laths observed at both the Tubilla del Agua and Laño sections suggest an origin from younger marine brines. Later calcite replacement and precipitation of geode‐filling calcite is recorded in both sections, with δ¹³C and δ¹⁸O values indicating the participation of meteoric waters. Synsedimentary activity of the Peñacerrada diapir, which lies close to the Laño section, played a significant role in the local shallowing of the basin and the formation of quartz geodes. In contrast, eustatic shallowing of the inner marine series of the Tubilla del Agua section led to the generation of morphologically similar quartz geodes. Copyright © 2002 John Wiley & Sons, Ltd.     

Evaporative systems and diagenetic patterns in the Calatayud Basin (Miocene,central Spain)

This paper concerns the evaporite units, depositional systems, cyclicity, diagenetic products and anhydritization patterns of the Calatayud Basin (nonmarine, Miocene, central Spain). In outcrop, the sulphate minerals of these shallow lacustrine evaporites consist of primary and secondary gypsum, the latter originating from the replacement of anhydrite and glauberite. In the evaporative systems of this basin, gypsiferous marshes of low salinity can be distinguished from central, saline lakes of higher salinity. In the gypsiferous marsh facies, the dominant, massive, bioturbated gypsum was partly replaced by synsedimentary chert nodules and siliceous crusts. In the saline lake facies, either cycles of gypsiferous lutite‐laminated gypsarenite or irregular alternations of laminated gypsum, nodular and banded glauberite, thenardite and nodular anhydrite precipitated. Early replacement of part of the glauberite by anhydrite also occurred. Episodes of subaerial exposure are represented by: (1) pedogenic carbonates (with nodular magnesite) and gypsiferous crusts composed of poikilitic crystals; and (2) nodular anhydrite, which formed in a sabkha. Additionally, meganodular anhydrite occurs, which presumably precipitated from ascending, highly saline solutions. The timing of anhydritization was mainly controlled by the salinity of the pore solutions, and occurred from the onset of deposition to moderate burial. Locally, a thick (>200 m) sequence of gypsum cycles developed, which was probably controlled by climatic variation. A trend of upward‐decreasing salinity is deduced from the base to the top of the evaporite succession.     

Depositional environments and diagenesis in Lake Parakeelya: a Cambrian alkaline playa from the Officer Basin, South Australia

Laminated and desiccated siliceous dolostones, dolomitic mudstones and dolomitic sandstones in the Cambrian Parakeelya Alkali Member of the Observatory Hill Formation accumulated in an alkaline playa. Four facies are recognized (from lake centre to lake edge): lake, saline mudflat, dry mudflat and sandflat facies. The facies occur in cycles. Cycles of tens of metres thickness record the gradual expansion and contraction of the playa. Superimposed smaller cycles of tens of centimetres thickness record minor oscillations in the position of the strandline in a shallow lake. The dominance of saline mudflat, dry mudflat and sandflat facies indicates that the lake was rimmed by broad flat areas with negligible relief. The high δ¹⁸O values of primary and penecontemporaneous diagenetic carbonates of +24 to +28‰ (SMOW) indicate strong evaporation of ground and surface waters within the lake system. Calcite pseudomorphs of the sodium carbonate minerals trona and shortite have δ¹⁸O values between + 19 and + 22.5‰, and contain fluid inclusions with variable salinites and homogenization temperatures up to around 110°C. This suggests that the euhedral alkaline evaporites were dissolved by heated waters; calcite pseudomorphs then precipitated from a mixed solution formed by the interaction of these incoming fluids with the relatively saline interstitial brines. The sodium bicarbonate solutions formed by dissolution of the evaporites would have been dispersed by the basinal brines so that despite the closed drainage, further groundwater concentration did not take place.     

Diagenetic alterations of the upper Jurassic scleractinian corals,Hanifa Formation,Jabal Al-Abakkayn,central Saudi Arabia

During diagenetic stages, the aragonitic skeletons and the inter/intra-corallite cement of the upper Jurassic corals of Hanifa Formation either dissolved or subjected to diagenetic alterations including cementation, micritization, recrystallization, silicification, dolomitization and dedolomitization. The proposed sequence of diagenetic stages is as follows: early marine diagenesis, early meteoric and mixing zone diagenesis, late meteoric diagenesis, and shallow burial diagenesis. Each stage is characterized by certain diagenetic processes. The source of sulfate solutions for dedolomitization in the studied corals is the dissolved anhydrite deposits of the Arab–Hith Formations, sometime before their erosion. A possible source of silica, needed for the formation of chert and chalcedony, is the sponge spicules dispersed in many carbonates of the Hanifa Formation.     

Participation of fresh water in chert diagenesis: evidence from oxygen isotopes and boron α-track mapping

Sedimentary chert breccias are the product of two stages of silicification: one which produced ‘fragments’, the other, during which the ‘matrix’ crystallized. Fragments and matrix of twenty-five breccias from the Senonian Mishash Formation in Southern Israel were separated and analysed for δ¹⁸O in quartz. The matrix is significantly depleted in ¹⁸O in comparison with fragments (δ¹⁸O of fragments ranges between +29.4 and +34.7‰, for matrix the range is +21.1–32.6‰). Boron has been mapped in the same rocks using the ¹⁰B(n, α)⁷Li reaction and α-track etching. Fragments are significantly enriched in boron in comparison to the matrix. The correspondence between boron maps and rock texture is perfect. These results when combined with Steinitz's (1977) report of evaporites and evaporite ghosts in the same rocks are interpreted as indicating two different environments of chert diagenesis: a first, normal marine to hypersaline stage during which the microquartz in fragments crystallized, and a second stage of matrix chertification which in most cases occurred when fresh water was interacting with the crystallizing sediment. These conclusions are corroborated by isotopic analysis of carbonates which coexist with the cherts, as well as stratigraphical and palaeontological analysis.     

Evaluation of bulk carbonate δ13C data from Triassic hemipelagites and the initial composition of carbonate mud

Bulk carbonate samples of hemipelagic limestone–marl alternations from the Middle and Upper Triassic of Italy are analysed for their isotopic compositions. Middle Triassic samples are representative of the Livinallongo Formation of the Dolomites, while Upper Triassic hemipelagites were sampled in the Pignola 2 section, within the Calcari con Selce Formation of the Southern Apennines in Southern Italy. Triassic hemipelagites occur either as nodular limestones with chert nodules or as plane‐bedded limestone–marl alternations which are locally silicified. In the Middle Triassic Livinallongo Formation, diagenetic alteration primarily affected the stable isotopic composition of sediment surrounding carbonate nodules, whereas the latter show almost pristine compositions. Diagenesis lowered the carbon and oxygen isotope values of bulk carbonate and introduced a strong correlation between δ¹³C and δ¹⁸O values. In the Middle Triassic successions of the Dolomites, bulk carbonate of nodular limestone facies is most commonly unaltered, whereas carbonate of the plane‐bedded facies is uniformly affected by diagenetic alteration. In contrast to carbonate nodules, plane‐bedded facies often show compaction features. Although both types of pelagic carbonate rocks show very similar petrographic characteristics, scanning electron microscopy studies reveal that nodular limestone consists of micrite (< 5 μm in diameter), whereas samples of the plane‐bedded facies are composed of calcite crystals ca 10 μm in size showing pitted, polished surfaces. These observations suggest that nodular and plane‐bedded facies underwent different diagenetic pathways determined by the prevailing mineralogy of the precursor sediment, i.e. probably high‐Mg calcite in the nodular facies and aragonite in the case of the plane‐bedded facies. Similar to Middle Triassic nodular facies, Upper Triassic nodular limestones of the Lagonegro Basin are also characterized by uncorrelated δ¹³C and δ¹⁸O values and exhibit small, less than 5 μm size, crystals. The alternation of calcitic and aragonitic precursors in the Middle Triassic of the Dolomites is thought to mirror rapid changes in the type of carbonate production of adjacent platforms. Bioturbation and dissolution of metastable carbonate grains played a key role during early lithification of nodular limestone beds, whereby early stabilization recorded the carbon isotopic composition of sea water. The bulk carbonate δ¹³C values of Middle and Upper Triassic hemipelagites from Italy agree with those of Tethyan low‐Mg calcite shells of articulate brachiopods, confirming that Triassic hemipelagites retained the primary carbon isotopic composition of the bottom sea water. A trend of increasing δ¹³C from the Late Anisian to the Early Carnian, partly seen in the data set presented here, is also recognized in successions from tropical palaeolatitudes elsewhere. The carbon isotopic composition of Middle and Upper Triassic nodular hemipelagic limestones can thus be used for chemostratigraphic correlation and palaeoenvironmental studies.     

Palaeoenvironmental and diagenetic reconstruction of a closed‐lacustrine carbonate system – the challenging marginal setting of the Miocene Ries Crater Lake (Germany)

Chemostratigraphic studies on lacustrine sedimentary sequences provide essential insights on past cyclic climatic events, on their repetition and prediction through time. Diagenetic overprint of primary features often hinders the use of such studies for palaeoenvironmental reconstruction. Here the potential of integrated geochemical and petrographic methods is evaluated to record freshwater to saline oscillations within the ancient marginal lacustrine carbonates of the Miocene Ries Crater Lake (Germany). This area is critical because it represents the transition from shoreline to proximal domains of a hydrologically closed system, affected by recurrent emergent events, representing the boundaries of successive sedimentary cycles. Chemostratigraphy targets shifts related to subaerial exposure and/or climatic fluctuations. Methods combine facies changes with δ ¹³C–δ ¹⁸O chemostratigraphy from matrix carbonates across five closely spaced, temporally equivalent stratigraphic sections. Isotope composition of ostracod shells, gastropods and cements is provided for comparison. Cathodoluminescence and back‐scatter electron microscopy were performed to discriminate primary (syn‐)depositional, from secondary diagenetic features. Meteoric diagenesis is expressed by substantial early dissolution and dark blue luminescent sparry cements carrying negative δ ¹³C and δ ¹⁸O. Sedimentary cycles are not correlated by isotope chemostratigraphy. Both matrix δ ¹³C and δ ¹⁸O range from ca −7·5 to +4·0‰ and show clear positive covariance (R  = 0·97) whose nature differs from that of previous basin‐oriented studies on the lake: negative values are here unconnected to original freshwater lacustrine conditions but reflect extensive meteoric diagenesis, while positive values probably represent primary saline lake water chemistry. Noisy geochemical curves relate to heterogeneities in (primary) porosity, resulting in selective carbonate diagenesis. This study exemplifies that ancient lacustrine carbonates, despite extensive meteoric weathering, are able to retain key information for both palaeoenvironmental reconstruction and the understanding of diagenetic processes in relation to those primary conditions. Also, it emphasizes the limitation of chemostratigraphy in fossil carbonates, and specifically in settings that are sensitive for the preservation of primary environmental signals, such as lake margins prone to meteoric diagenesis.     

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.     

Diagenesis of a mixed siliciclastic/evaporitic sequence of the Middle Muschelkalk (Middle Triassic), the Catalan Coastal Range, NE Spain

The Middle Muschelkalk (Middle Triassic) of the Catalan Coastal Range (north-east Spain) comprises sandstone, mudstone, anhydrite and minor carbonate layers. Interbedded sandstones and mudstones which are dominant in the north-eastern parts of the basin are terminal alluvial fan deposits. South-westward in the basin, the rocks become dominated by interbedded evaporites and mudstones deposited in sabkha/mudflat environments. The diagenetic and pore water evolution patterns of the Middle Muschelkalk suggest a strong facies control. During eodiagenesis, formation of microdolomite, anhydrite, baryte, magnesite, K-feldspar and mixed-layer chlorite/smectite was favoured within and adjacent to the sabkha/mudflat facies, whereas calcite, haematite, mixed-layer illite/smectite and quartz formed mainly in the alluvial facies. Low δ¹⁸O_SMOW values for microdolomite (+23.7 to +28.4%) and K-feldspar overgrowths (+17.3 to +17.7%) suggest either low-temperature, isotopic disequilibrium or precipitation from low-¹⁸O porewaters. Low-¹⁸O waters might have developed, at least in part, during low-temperature alteration of volcanic rock fragments. During mesodiagenesis, precipitation of quartz overgrowths and coarse dolomite occurred in the alluvial sandstones, whereas recrystallization of microdolomite was dominant in the sabkha/mudflat facies. The isotopic compositions of these mesogenetic phases reflect increasing temperature during burial. Upon uplift and erosion, telogenetic calcite and trace haematite precipitated in fractures and replaced dolomite. The isotopic composition of the calcite (δ¹⁸O_SMOW=+21.5 to +25.6%o; δ¹³C= 7.7 to - 5.6%o) and presence of haematite indicate infiltration of meteoric waters.     

Calcium-isotope fractionation in selected modern and ancient marine carbonates

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

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

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