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1.
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 + 28.80/00 (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.  相似文献   

2.
Three categories of fibrous calcite from early to middle Caradoc platform-marginal buildups in east Tennessee can be delineated using cathodoluminescent microscopy, minor element chemistry and stable C-O isotopic composition. Bright luminescent fibrous cement has elevated Mn (>1000 p.p.m.), negative δ13C and intermediate δ18O values relative to other types of fibrous calcite. This cement reflects fibrous calcite that interacted with reducing Mn-rich fluids. Dully luminescent fibrous cement has elevated Fe (>400 p.p.m.), positive δ13C and negative δ18O values relative to other fibrous cements. This cement was stabilized by burial fluids. Nonluminescent fibrous cement has low Mn and Fe (generally below 400 p.p.m.) and positive δ13C and δ18O values relative to other types of fibrous calcite. The latter cement is interpreted to be the best material for determining the isotopic composition of calcite precipitated in equilibrium with early to middle Caradoc seawater, which is δ13C=1% PDB and δ18O=?4 to ?5‰ PDB. Results from this study and Ashgillian brachiopods indicate that the average δ18O composition of the Ordovician ocean, during nonglacial periods, was probably never more negative than ?3‰ SMOW. Assuming an Ordovician seawater δ18O value of ?1‰ SMOW, Holston Formation fibrous cements would have precipitated at temperatures between 27 and 36 °C, which is near the upper temperature limit for metazoans. A seawater δ18O value of ?2‰ SMOW yields temperatures ranging from 23 to 31 °C, while a ?3‰ SMOW value yields temperatures of 18–26 °C.  相似文献   

3.
Chert distribution in the Lake Valley rocks is selective to mud-supported facies; it is not related to proximity to unconformities. The facies selectivity of the chertification is believed to be a function of the depositional distribution of indigenous silica as sponge spicules, an interpretation that is supported by high positive qualitative correlation of chert with spiculitic rocks. Petrography indicates that the spicules were all originally siliceous, and that they all went through a moldic stage during which many molds were compactively destroyed and distorted. Remaining molds were subsequently cemented by calcite or chalcedony. Chert distribution and spicule petrography argue for an intraformational source for much of the silica. Chert micro-fabrics are dominated by microquartz, a replacement of grains and lime mud; length-fast chalcedony, a pore-filling cement; and megaquartz, a post-chalcedony pore-filling cement. Petrography of compaction features within chert masses indicates that chertification occurred after some burial. Based on stratigraphic reconstruction this burial depth was a maximum of about 215 m. and was most likely a few metres to a few tens of metres. Petrography of chert-calcite cement relationships indicates that chertification occurred before and during first generation, pre-Pennsylvanian non-ferroan calcite cementation, and was completed before late-stage, post-Mississippian ferroan calcite precipitation. Petrography of chert clasts in basal Rancheria (Meramecian) and basal Pennsylvanian conglomerates proves these clasts derived from the Lake Valley Formation and were chertified before redeposition. Thus, some cherts in the Lake Valley are pre-Meramecian in age, but all are pre-Pennsylvanian in age. Furthermore, association of the cherts with the non-ferroan cements indicates the cherts were probably precipitated in meteoric phreatic lens established beneath the pre-Meramecian and pre-Pennsylvanian subaerial unconformities.  相似文献   

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

5.
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.  相似文献   

6.
The carbonate platforms of the Wetterstein Formation of the Eastern Alps (Drau Range and Northern Calcareous Alps) show a distinct facies zonation of reefs and lagoons. While some lagoonal areas were episodically emerged and formed lagoonal islands, others remained permanently flooded. The scale of near surface, meteoric or marine diagenesis was related to this lagoonal topography. At shallow burial depth, cementation was dominated by altered marine solutions, which additionally caused recrystallization of metastable constituents of the sediment and earlier marine cements (high magnesian calcite, aragonite) connected with a carbon and oxygen isotopic change to more negative values. Deeper burial cementation shows a succession with two types of saddle dolomite and three types of blocky calcite. Carbon and oxygen isotopic values of these cements show a trend towards more negative values from the first to the last generation, in the following succession: clear saddle dolomite—zoned blocky calcite—cloudy saddle dolomite—post-corrosion blocky calcite—replacive blocky calcite. Fluid inclusion studies of the carbonate cements are interpreted to indicate a deeper burial temperature development that first increases from 175 to 317°C, followed by a temperature decrease to 163–260°C, and subsequent increase up to 316°C, whereby the samples of the Drau Range always show the lowest values. Calculations of the isotopic composition of the water, from which the carbonate cements were precipitated, yielded positive δ18O values from 6.66 to 17.81%o (SMOW), which are characteristic for formation and/or metamorphic waters. Also, the isotopic compositions of the palaeofluids probably changed during deeper burial diagenesis, following the temperature development.  相似文献   

7.
In this study, the stable isotope and trace element geochemistries of meteoric cements in Pleistocene limestones from Enewetak Atoll (western Pacific Ocean), Cat Island (Bahamas), and Yucatan were characterized to help interpret similar cements in ancient rocks. Meteoric calcite cements have a narrow range of δ18O values and a broad range of δ13C values in each geographical province. These Pleistocene cements were precipitated from water with stable oxygen isotopic compositions similar to modern rainwater in each location. Enewetak calcite cements have a mean δ18O composition of ?6.5%0 (PDB) and δ13C values ranging from ?9.6 to +0.4%0 (PDB). Sparry calcite cements from Cat Island have a mean δ18O composition of ?4.1%0 and δ13C values ranging from ?6.3 to + 1.1%0. Sparry cements from Yucatan have a mean δ18O composition of ?5.7%0 and δ13C values of ?8.0 to ?2.7%0. The mean δ18O values of these Pleistocene meteoric calcite cements vary by 2.4%0 due to climatic variations not related directly to latitude. The δ13C compositions of meteoric cements are distinctly lower than those of the depositional sediments. Variations in δ13C are not simply a function of distance below an exposure surface. Meteoric phreatic cements often have δ13C compositions of less than —4.0%0, which suggests that soil-derived CO2 and organic material were washed into the water table penecontemporaneous with precipitation of phreatic cements. Concentrations of strontium and magnesium are quite variable within and between the three geographical provinces. Mean strontium concentrations for sparry calcite cements are, for Enewetak Atoll, 620 ppm (σ= 510 ppm); for Cat Island, 1200 ppm (σ= 980 ppm); and for Yucatan, 700 ppm (σ= 390 ppm). Equant cements, intraskeletal cements, and Bahamian cements have higher mean strontium concentrations than other cements. Equant and intraskeletal cements probably precipitated in more closed or stagnant aqueous environments. Bahamian depositional sediments had higher strontium concentrations which probably caused high strontium concentrations in their cements. Magnesium concentrations in Pleistocene meteoric cements are similar in samples from Enewetak Atoll (mean =1.00 mol% MgCO3; σ= 0.60 mol% MgCO3) and Cat Island (mean = 0.84 mol% MgCO3; σ= 0.52mol% MgCO3) but Yucatan samples have higher magnesium concentrations (mean = 2.20 mol% MgCO3: σ= 0.84mol% MgCO3). Higher magnesium concentrations in some Yucatan cements probably reflect precipitation in environments where sea water mixed with fresh water.  相似文献   

8.
W. J. MEYERS 《Sedimentology》1978,25(3):371-400
Calcite cements in Mississippian skeletal packstones and grainstones of southwestern New Mexico are dominated by echinoderm-syntaxial, inclusion-free calcites that can be divided into four major compositional zones (from oldest to youngest: zone 1, 2, 3, 5) based mainly on varying Fe11 and MnII contents. These compositional zones are interpreted as‘time stratigraphic’ units as indicated by petrographic evidence for age gaps between zones, and by consistency of their ages on a regional scale. As such, these cement zones can be correlated over most or all of the approximately 30,000 km2 of study area, based on similarity of age, number and sequence of major zones. The inclusion-free calcite cements comprise approximately 95% of the total cements, of which the pre-Pennsylvanian zones (zones 1, 2, 3) make up about 60%, and the post-Mississippian zone 5 makes up about 40% of the total cements. These cements are interpreted as meteoric phreatic on the basis of MnII and FeII content, crystal clarity, cement morphology, substrate selectivity, low Mg content, and absence of marine and vadose characteristics. In the southern part of the study area zone 2 contains significant amounts of meteoric-marine mixing-zone phreatic cements. These mixing-zone cements are identified by their similarity in morphology, luminescence and substrate selectivity to the inclusion-free meteoric phreatic cements, but contain microdolomite inclusions indicative of former high-Mg calcites. Their restriction to the south is interpreted to have resulted from relatively long residence time of the mixing zone in the south during zone 2 precipitation. Strictly marine subtidal and beachrock cements make up less than 1% of the total cements, and meteoric vadose cements are virtually absent. Regional distribution of the pre-Pennsylvanian cement zones suggests a model of cementation during a world-wide late Mississippian eustatic regression identified by Vail & Mitchum (1976). Specifically, pre-zone 1 and zone 1 meteoric phreatic cements formed during regression within a shallow oxygenated (?) groundwater system; zone 2 formed during the later part of the regression and during stillstand in a deep-seated, more extensive flow system; zone 3 formed during subsequent transgression in a shallow groundwater system. The post-Chester, pre-Pennsylvanian unconformity resulted mainly in microkarsting and weathering. The main difference, other. than scale, between this model and those derived from diagenetic studies of Quaternary limestones is that it implies that major cementation occurred during sea-level changes in cpeiric settings, rather than only during stillstands.  相似文献   

9.
Isotopic and mineralogic data from an 8500-m thick section of the Great Valley sequence, northern California, indicate that changes in the δ18O values of authigenic minerals resulted from the conversion of smectite to a 10 Å clay-mineral as temperature increased with burial in the Jurassic- Cretaceous outer-arc basin. The clay-mineral assemblage in mudstone is characterized by a proportional increase of the 10 Å clay-mineral with increasing stratigraphic depth, and by a depletion in the δ18O value of the mixed-layer smectite/10 Å clay-mineral with descending stratigraphic position from +21.9 to + 15.5%. SMOW. Modeling of the oxygen isotopic data from authigenic phases, based on equilibrium fractionation during clay-mineral diagenesis, indicates that δ18O values of calcite in mudstones and of calcite cements in sandstone precipitated along a temperature gradient of about 25°C/km during maximum burial to about 6–7 km. δD values of the mixed-layer smectite/10 Å clay-mineral range between ?69 to ?44%. SMOW. Using temperatures calculated from the oxygen isotopic data, the deuterium and oxygen isotopic data indicate that the smectite underwent late-stage dehydration and probably buffered the composition of formation waters from sea water values to isotopic compositions of δ18O ≈ +8%. SMOW and δD ≈ ?25%. SMOW. The δ13C values of calcite from mudstone and sandstone imply that crystallization of authigenic calcite was linked to organic diagenesis during which dissolved HCOt-3 was continuously enriched in 13C as temperature increased with burial. At the base of the sequence and immediately overlying the ophiolitic basement rocks, several hundred meters of strata were altered by more oxygen-depleted (δ18O ? +4 to +5%.) hydrothermal fluids emanating from the ophiolitic rocks, probably at maximum burial depth.  相似文献   

10.
A carbonate buildup of Middle Triassic age, the Esino Limestone, outcrops in the Southern Calcareous Alps of Lombardy (N Italy). Along its margin and within the open subtidal facies, the Esino Limestone contains calcite cement-filled cavities of cm to m size. These features, known as evinosponges, may form pervasive networks within the host rock. The filling consists of concentric, isopachous layers of fibrous low-Mg calcite crystals characterized by strong undulose extinction and bent cleavages. The cement crusts are non-luminescent under cathodoluminescence, but both cements and host rock are cross-cut by micro-fractures filled with bright-luminescent calcite, related to late void-filling sparite. Mixing of different carbonates is reflected in stable isotope data. On the hand specimen scale, the oxygen and carbon isotope compositions of cements and host rock show little variation. When compared on a regional scale, the values cover a broad range from δ18O(PDB)=?5‰ to ?12‰ and from δ13O =0‰ to +3‰. The linear covariant trends defined by the oxygen and carbon isotope data for different sampling regions reflect the admixture of late, isotopically depleted calcite with an isotopically enriched non-luminescent calcite of early diagenetic origin. The Esino Limestone fibrous cements, which were probably precipitated in the marine or marine-meteoric phreatic environment, were affected by late diagenetic processes that caused mineral deformation and isotopic depletion through recrystallization and the admixture of a later calcite. These later calcites precipitated from penetrative fluids possibly related to Late Triassic volcanic activity and/or to the Late Cretaceous/Early Palaeogene alpine orogeny.  相似文献   

11.
Carbonate cements in late Dinantian (Asbian and Brigantian) limestones of the Derbyshire carbonate platform record a diagenetic history starting with early vadose meteoric cementation and finishing with burial and localized mineral and oil emplacement. The sequence is documented using cement petrography, cathodoluminescence, trace element geochemistry and C and O isotopes. The earliest cements (Pre-Zone 1) are locally developed non-luminescent brown sparry calcite below intrastratal palaeokarsts and calcretes. They contain negligible Fe, Mn and Sr but up to 1000 ppm Mg. Their isotopic compositions centre around δ18O =?8.5‰, δ13C=?5.0‰. Calcretes contain less 13C. Subsequent cements are widespread as inclusion-free, low-Mg, low-Fe crinoid overgrowths and are described as having a‘dead-bright-dull’cathodoluminescence. The‘dead’cements (Zone 1) are mostly non-luminescent but contain dissolution hiatuses overlain by finely detailed bright subzones that correlate over several kilometres. Across‘dead'/bright subzones there is a clear trend in Mg (500–900 ppm), Mn (100–450 ppm) and Fe (80-230 ppm). Zone 1 cements have isotopic compositions centred around δ18O =?8.0‰ and δ13C=?2.5‰. Zone 2 cement is bright, thin and complexly subzoned. It is geochemically similar to bright subzones of Zone 1 cements. Dull Zone 3 cement pre-dates pressure dissolution and fills 70% or more of the pore space. It generally contains little Mn, Fe and Sr but can have more than 1000 ppm Mg, increasing stratigraphically upwards. The δ18O compositions range from ?5.5 to ?15‰ and the δ13C range is ?1 to + 3.20/00. Zone 4 fills veins and stylolite seams in addition to pores. It is synchronous with Pb, Ba, F ore mineralization and oil migration. Zone 4 is ferroan with around 500 ppm Fe, up to 2500 ppm Mg and up to 1500 ppm Mn. Isotopic compositions range widely; δ15O =?2.7 to ?9‰ and δ13C=?3.8 to+2.50‰. Unaltered marine brachiopods suggest a Dinantian seawater composition around δ15O = 0‰ (SMOW), but vital isotopic effects probably mask the original δ13C (PDB) value. Pre-Zone 1 calcites are meteoric vadose cements with light soil-derived δ13C and light meteoric δ18O. An unusually fractionated‘pluvial’δ15O(SMOW) value of around — 6‰ is indicated for local Dinantian meteoric water. Calcrete δ18O values are heavier through evaporation. Zone 1 textures and geochemistry indicate a meteoric phreatic environment. Fe and Mn trends in the bright subzones indicate stagnation, and precipitation occurred in increments from widespread cyclically developed shallow meteoric water bodies. Meteoric alteration of the rock body was pervasive by the end of Zone 1 with a general resetting of isotopic values. Zone 3 is volumetrically important and external sources of water and carbonate are required. Emplacement was during the Namurian-early Westphalian by meteoric water sourced at a karst landscape on the uplifted eastern edge of the Derbyshire-East Midland shelf. The light δ18O values mainly reflect burial temperatures and an unusually high local heat flow, but an input of highly fractionated hinterland-derived meteoric water at the unconformity is also likely. Relatively heavy δ13C values reflect the less-altered state of the source carbonate and aquifer. Zone 4 is partly vein fed and spans burial down to 2000 m and the onset of tectonism. Light organic-matter-derived δ13C and heavy δ18O values suggest basin-derived formation water. Combined with textural evidence of geopressures, this relates to local high-temperature ore mineralization and oil migration. Low water-to-rock ratios with host-rock buffering probably affected the final isotopic compositions of Zone 4, masking extremes both of temperature and organic-matter-derived CO2.  相似文献   

12.
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 (Tmice) are between -5 and -33°C. The broad range in the Tmice 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.  相似文献   

13.
The Wilde Kirche reef complex (Early-Late Rhaetian) grew as an isolated carbonate structure within the shallow Kössen Basin. At the Triassic/Jurassic boundary a single brief (c. 10–50 ka) period of subaerial exposure occurred. The preserved karst profile (70 m thick) displays a vadose zone, enhanced dissolution at a possible palaeo-watertable (5–15 m below the exposure surface), and a freshwater phreatic zone. Karst porosity was predominantly biomouldic. Primary cavities and biomoulds were enlarged and interconnected in the freshwater phreatic zone; cavity networks developed preferentially in patch reef facies. Resubmergence of the reef complex allowed minor modification of the palaeokarst surface by sea floor dissolution and Fe-Mn crust deposition on a sediment-starved passive margin. Fibrous calcite (FC). radiaxial fibrous calcite (RFC) and fascicular optic calcite (FOC) cements preserved as low Mg calcite (LMC) are abundant in primary and karst dissolution cavities. FC cement is restricted to primary porosity, particularly as a synsedimentary cement at the windward reef margin. FC, RFC and FOC contain microdolomite inclusions and show patchy non-/bright cathodoluminescence. δ18O values of non-luminescent portions (interpreted as near original) are − 1.16 to − 1.82%0 (close to the inferred δ18O of calcite precipitated from Late Triassic sea water). δ13C values are constant (+3 to + 2.2%0). These observations suggest FC, RFC and FOC were originally marine high Mg calcite (HMC) precipitates, and that the bulk of porosity occlusion occurred not in the karst environment but in the marine environment during and after marine transgression. The HMC to LMC transition may have occurred in contact with meteoric water only in the case of FC cement. The most altered (brightly luminescent) portions of RFC/FOC cements yield δ18O=−2.44 to − 5.8%0, suggesting HMC to LMC alteration at up to 34°C. in the shallow burial environment at depths of 180–250 m. Abundant equant cements with δ18O =−4·1 to −7.1%0 show crisp, uniform or zoned dull luminescence. They are interpreted as unaltered cements precipitated at 33–36°C at 200–290 m burial depth, from marine-derived fluids under a slightly enhanced geothermal gradient. Fluids carrying the equant cements may have induced the HMC to LMC transition in the fibrous cements.  相似文献   

14.
15.
Meteoric sphaerosiderite lines (MSLs), defined by invariant δ18O and variable δ13C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre‐scale FeCO3 nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well‐preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO3) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca2+, Mg2+ and Mn2+ for Fe2+. Examples of diagenetically altered Cretaceous sphaerosiderite‐bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic δ18O and δ13C values are preserved. All three units contain poikilotopic calcite cements with significantly different δ18O and δ13C values from the co‐occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant δ18O vs. δ13C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric δ18O and δ13C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end‐member compositions. Modelled hyperbolic fluid mixing curves for the Success S2 Formation suggest precipitation from fluids that were < 25% sea water.  相似文献   

16.
Stromatactis is a spar network whose elements in cross section have flat to undulose lower surfaces and digitate upper surfaces. The network is composed principally of isopachous crusts of centripetal cement and commonly occurs embedded in finely crystalline limestone. It is the cement filling of interconnected cavities. Stromatactis of Upper Silurian red stromatactis limestone from Gaspé Peninsula, Québec Appalachians, exhibits two types of cements: (1) an isopachous cement that lined the walls of the conduits and is interpreted as early marine; and (2) a later blocky cement that occupies the centres of cavities. The first cement is composed exclusively of non-ferroan calcite, whereas the second cement is mixed non-ferroan and ferroan calcite. The early isopachous cement is white on polished slabs and has a turbid aspect under transmitted light. In a few samples, the relative homogeneity of this early cement is broken by the presence of distinctive grey clear calcite. Under cathodoluminscence, the grey clear calcite is non-luminescent and exhibits well defined bladed crystal shapes, whereas the white turbid cement has a dull orange luminescence and indistinct crystal shapes. The relationships between the two cements indicate that the dull luminescent cement is a secondary form of the non-luminescent cement, and it is concluded that the dull cement is the product of alteration of the non-luminescent cement by burial or meteoric fluids. The later blocky cement has the same dull luminescence as the white turbid cement and is thought to have been precipitated from the same fluids as those responsible for the alteration of the early marine cements. Oxygen isotopic values of the dull cement of the early isopachous crusts (mean δ18O= -6.8%o are intermediate between those of the non-luminescent early marine cement (mean δ18O= -5.3%o) and the dull luminescent blocky cement (mean δ18O= -11.8%o), while carbon isotopic values do not differ significantly (δ13C=+2.9, +2.4 and +2.6%o, respectively). The alteration also has affected the distribution of some trace elements, particularly Mg. Both unaltered and altered cements contain less than 1% microdolomite inclusions, but the Mg content of the background calcite of unaltered cement is three times that of altered cement (14171 vs. 5502 ppm). Precursor early marine cement is thought to have been low-Mg calcite. The mean δ18O value (− 5.3%o) of unaltered early marine cement is higher than values for the oxygen isotopic signature of Silurian oceans provided by brachiopod shells.  相似文献   

17.
Deposition of the Gully Oolite was locally interrupted by emergence and a regionally extensive palaeosol is present at the top of the unit. Early diagenetic phases include isopachous, fibrous submarine cements, nonluminescent vadose cements, and mixing zone dolomite. Subsequent nonferroan phreatic cements are non- to dully luminescent and in restricted vertical intervals predate significant compaction. More usually, however, phreatic cements postdate extensive overpacking of allochems. Ooid isotopic composition (δ18O=-7·80° to -3·10° and δ13C = -2·38° to +3·28°) is similar to that of associated phreatic cements and the data suggest that the bulk of ooid stabilization and cementation occurred within meteoric groundwaters. The extensive allochem overpacking appears to have occurred during the first few tens of metres of burial and intergranular macroporosity was eliminated prior to deep burial. Fracturing of the Gully Oolite during the Hercynian Orogeny and subsequent post-orogenic uplift led to localized dolomitization, several generations of calcite veins, and the restricted occurrence of 18O depleted cements in inter- and intragranular microporosity. Some of the veins clearly relate to Triassic exhumation of the Carboniferous Limestone, but others may be related to post-Mesozoic uplift and erosion of South Wales. Fracture-associated dolomitization may have occurred within a large-scale post-orogenic groundwater system, with Mg2+ being supplied through the release of deeply buried diagenetic brines.  相似文献   

18.
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‰.  相似文献   

19.
The Pennsylvanian phylloid algal mounds exposed in the Cervatina Limestone of the Cantabrian Zone (NW Spain) developed during the highstands of high-frequency shallowing-upward cycles and lack evidence of subaerial exposure at their tops. Mound core facies are composed of massive bafflestones with variable amounts of calcite cements and anchicodiacean phylloid algae with cyathiform thalli preserved in growth position. Through standard petrographic, isotopic (δ18O and δ13C), major and trace element (Ca, Mg, Fe, Mn, Sr) and cathodoluminescence analyses, five calcite cement phases (cement 1 (C1)–cement 5 (C5)) have been identified filling primary and secondary pores. Early marine diagenesis is represented by micritization and non-luminescent to mottled-dull luminescent high-Mg calcite fibrous marine cement (C1). A dissolution phase then occurred and created vuggy and moldic pores. Based on the absence of field or petrographical or geochemical evidence of exposure, it is inferred that dissolution occurred in near-surface undersaturated marine waters with respect to aragonite related to progressive organic matter oxidation. Secondary porosity was subsequently filled by dull-bright-dull bladed high-Mg calcite (C2), which precipitated in the early shallow burial from marine-derived pore waters. Remaining porosity was occluded by shallow-burial precipitates consisting of non-luminescent scalenohedral low-Mg calcite (C3) followed by non-ferroan dull luminescent calcite spar (C4). Latter phases of calcite spar exhibiting non- and dull luminescence (C5) are associated with burial calcite veins. Low δ18O values (around ?8‰), moderately depleted δ13C values (around 0.5‰) and the homogeneity of trace element contents of carbonate matrix, cements and vein-filling calcites suggest burial isotopic re-equilibration and recrystallization, probably in Early Permian times during post-thrusting orocline formation.  相似文献   

20.
The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ34S (−38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (−38‰ to −22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ34S values (−14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ34S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The 87Sr/86Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ18O consistent with a marine environment. Its δ13C is however lower than those of marine carbonates, suggesting a contribution of 13C-depleted carbon from degradation of organic matter. δ18O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ18O values (∼+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.  相似文献   

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