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1.
Petrography demonstrates the presence of three types of fibrous calcite cement in buildup deposits of the Kullsberg Limestone (middle Caradoc), central Sweden. Translucent fibrous calcite has intrinsic blue luminescence (CL) indicative of pure calcite. This cement has 2–5 mol% MgCO3, low Mn and Fe (≤ 100 p.p.m.), and is considered to be slightly altered to unaltered, primary low- to intermediate-Mg calcite. Grey turbid fibrous calcite has variable but generally low MgCO3 content (most analyses <2 mol%) and variable CL response, with Mn and Fe concentrations up to 1200 and 500 p.p.m., respectively. The heterogeneous characteristics of this variety of fibrous calcite are caused by diagenetic alteration of a translucent fibrous calcite precursor. Light-brown turbid fibrous calcite has low MgCO3 (near 1 mol%) and variable Mn (up to 800 p.p.m.) and Fe (up to 500 p.p.m.) concentrations, with an abundance of bright luminescent patches, which formed during alteration caused by reducing diagenetic fluids. The δ13C and δ18O values of all fibrous calcite form a tight field (δ13C=1·7 to 3·1‰ PDB, δ18O= ? 2·6 to ? 4·1‰ PDB) compared with fibrous calcite isotope values from other units. Fibrous calcite δ18O values are larger than adjacent meteoric or burial cements, which have δ18O δ ? 8‰ PDB. Consequently, most diagenetic alteration of Kullsberg fibrous calcite is interpreted to have occurred in the marine diagenetic realm. First-generation equant and bladed calcite cements, which pre-date fibrous calcite, are interpreted as unaltered, low-Mg calcite marine cements based on δ13C and δ18O data (δ13C = 2·3 to 2·7‰ PDB, δ18O= ? 2·8 to ? 3·5‰ PDB). Unlike fibrous cement, which reflects global sea water chemistry, first-generation equant and bladed calcite are indicators of localized modification of seawater chemistry in restricted settings. Kullsberg abiotic marine cements have larger δ18O values than most Caradoc marine precipitates from equatorial Laurentia. Positive Kullsberg δ18O values are attributed to lower seawater temperatures and/or slightly elevated salinity on the Baltic platform relative to seawater from which other marine precipitates formed.  相似文献   

2.
A bored and encrusted late Pleistocene ooid grainstone was recovered from the seafloor at a depth of approximately 40 m on the outer continental shelf of eastern Florida. Ooid cortices are dominantly bimineralic, generally consisting of inner layers of radial magnesian calcite and outer layers of tangential aragonite. Ooid nuclei are dominantly rounded cryptocrystalline grains, although quartz grains and a variety of skeletal grains also occur as nuclei. Ooids are partially cemented by blocky calcite, and interparticle porosity is partially filled by micrite. Radial cortex layers are composed of brightly cathodoluminescent magnesian calcite having a composition of approximately 12 mol% MgCO3 and 1000 ppm strontium. The iron and manganese concentrations in radial cortex layers are generally in the range of 500–1000 ppm and 100–250 ppm, respectively. Tangential cortex layers are composed of noncathodoluminescent aragonite containing approximately 11 500 ppm strontium and less than 0.5 mol% MgCO3. Iron concentrations in tangential cortex layers are generally in the range of 150–400 ppm, and manganese concentrations are generally below the detection limit of 100 ppm. Echinoderm skeletal fragments, which are present as accessory grains, are composed of brightly cathodoluminescent magnesian calcite. Some ooid nuclei and the thin outer edges of some blocky calcite cement are cathodoluminescent; micrite matrix and the bulk of blocky calcite cement are noncathodoluminescent. Ooids do not exhibit textural evidence of recrystallization. The ooid grainstone underwent an episode of meteoric diagenesis. but ooid cortices were not affected by the event. We propose a previously unrecognized process by which the magnesian calcite cortex layers underwent diagenetic alteration in oxygen-depleted seawater. During this diagenesis, magnesium was lost and manganese was incorporated without apparent textural alteration and without mineralogical stabilization. Thus, we Suggest that cathodoluminescence may result from diagenetic alteration on the sea-floor.  相似文献   

3.
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   

4.
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   

5.
The sandbodies of the Bearreraig Sandstone Formation (Inner Hebrides, UK) are cemented by two generations of calcite. The first generation, an inhomogeneous ferroan calcite (0.05?3.28 mol% FeCo3) formed during sulphate reduction (δ13C =?24 to ?32%o PDB) in marine porewaters (δ18O of cement from ?1 to ?4%o PDB) at very shallow burial depths (a few centimetres). These cements are rare but form millimetre-scale clusters of crystals which acted as nuclei to the later, concretionary cements. The second generation of cements are more homogeneous ferroan calcites (mean 1?58% mol% FeCo3) which evolve to progressively higher Fe/Mg ratios. They are sourced by shell dissolution (δ13C of cement from +1 to ?3%o PDB) into meteoric (δ18O of cement from ?6 to ?10%o PDB) or mixed marine meteoric waters (δ18O of cement from ?4 to ?6%o SMOW). These were introduced into the formation either during Bathonian times as a freshwater lens, or, subsequent to partial inversion, by confined aquifer flow. Corroded feldspars within the concretions suggest that an interval of at least 8 Ma separated the deposition of the sediments from the onset of concretion growth. Abundant concretions are preferentially developed at certain horizons within the sandbodies, where the early generation of ferroan calcite cements provided nuclei. The latter formed close to the sediment-water interface, the concentration of cement within the sediment being related to sedimentation rate. The relatively high concentrations of the first generation of cement, upon which the concretionary horizons are nucleated, formed during periods of minimal sedimentation.  相似文献   

6.
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   

7.
This paper describes the occurrence of dolomite and the mechanism of dolomitization of the Upper Triassic-Lower Jurassic K?z?loren Formation in the autochthonous Bolkardag? unit of the middle Taurus Mountains in south western Turkey. Dolomites were analyzed for geochemical, isotopic and crystallographic variation. Dolomites occur as a replacement of precursor carbonate and cement. The dolomite crystals range from <10 to ~1000 μm existing as both replacements and cements. Sr concentrations range between 84 and 156 ppm, and the molar Sr/Ca ratios of dolomitizing fluids are estimated to range between 0.0066 to 0.013 ratios. Dolomites are Ca-rich (with average CaCO3 and MgCO3 equal to 56.43 and 43.57 mol%, respectively) and they are non-stoichiometric, with an average Sr=116 ppm, Na=286 ppm, Mn=81 ppm, Fe=1329 ppm, and δ18O and δ13C ranges from –0.6‰ to –6.1‰ Pee Dee Belemnite [PDB], and +1.2 to +3.9‰ PDB. The North American Shale Composition [NASC]-normalized rare earth element (REE) values of the both limestone and dolomite sample groups show very similar REE patterns characterized by small positive Eu (mean=1.32 and mean=1.42, respectively) and slightly or considerably negative Ce (mean=0.61 and mean=0.72, respectively) anomalies and a clear depletion in all REE species. The K?z?loren Formation dolomites have been formed as early diagenetic from mixing zone fluids at the tidal-subtidal environment and at the late diagenetic from basinal brines at the shallow-deep burial depths.  相似文献   

8.
Although carbonate-associated sulfate (CAS) is used widely as a proxy for the sulfur isotope composition of ancient seawater, little is known about the effects of diagenesis on retention of primary δ34S signals. Our case study of the Key Largo Limestone, Pleistocene, Florida, is the first systematic assessment of the impact of meteoric diagenesis on CAS properties. Geochemical and petrographic data show that meteoric diagenesis has affected the exposed coralline facies to varying degrees, yielding differences now expressed as sharp reaction fronts between primary and secondary carbonate minerals within individual coral heads. Specifically, analyses across high-resolution transects in the Key Largo Limestone show that concentrations of strontium and sodium decrease across the recrystallization front from original aragonite to meteoric low-magnesium calcite by factors of roughly 5 and 10, respectively. Predictably, δ18O values decrease across these same fronts. The δ13C relationships are more complex, with the most depleted values observed in the latest-formed calcite. Such trends likely reflect carbon isotope buffering capacity that decreased as reaction progressed, as well as protracted development of soil profiles and the associated terrestrial biomass and thus depleted δ13C during sea-level lowstand. Conversely, δ34S values of CAS vary within a narrow ‘buffered’ range from 20.6 to 22.6‰ (compared to 20.8-22.0‰ of coeval Pleistocene seawater) across the same mineralogical transition, despite sulfate concentrations that drop in the diagenetic calcite by an average factor of 12. Collectively, these data point to robust preservation of primary δ34S for carbonates that have experienced intense meteoric diagenesis, which is encouraging news for those using the isotopic composition of CAS as a paleoceanographic proxy. At the same time, the vulnerability of CAS concentrations to diagenetic resetting is clear.  相似文献   

9.
Geochemical and petrographic data suggest early submarine cementation of hardgrounds from the Lincolnshire Limestone Formation, Middle Jurassic, England. The three hardgrounds, from Cowthick, Castle Bytham and Leadenham quarries, developed in tidal-inlet, on-barrier and lagoonal sub-environments of a carbonate barrier-island complex. At Cowthick early composite (acicular-bladed) radial-fibrous cements, which pre-date aragonite dissolution, completely fill intergranular pore-space at the hardground surface; away from it isopachous fringing cements decrease in thickness. Microprobe analyses demonstrate zoning within the fringes with magnesium concentrations (> 2 wt % MgCO3) higher than those in allochems or later, ferroan cement (?0.5 wt % MgCO3, 1.7 wt % FeCO3). At Castle Bytham early granular isopachous cements, which post-date aragonite dissolution, occur within 5 cm of the surface. At Leadenham early lithification is superficial and represented by ferruginous crusts and micritic internal sediment. Late blocky cement fills residual pore-space in all three examples. Carbon and oxygen isotopic composition of whole-rock samples taken at intervals away from each hardground surface demonstrate the increasing proportion of late 18O depleted cements (δ18O – 8 to – 10). Early cements must have a marine isotopic composition; different δ18O values from each hardground reflect the intensity of early lithification and exclusion of late cements at the hardened surface. There is no isotopic evidence for subaerial cement precipitation during possible emergence at Castle Bytham. Oyster samples (with δ18O, – 2.9 and δ13C, 2.4) give estimated palaeotemperatures of 22–25°C. Early cements from Cowthick are enriched in 18O and 13C (δ18O = 0 δ13C ? 3‰) compared to the oyster values. In conjunction with trace element data this is interpreted as evidence for high-magnesium calcite precursor cements which underwent replacement in a system with a low water: rock ratio. The intensity of early lithification is related to depositional environment: maximum circulation of sea-water producing the most lithified hardground (Cowthick). This is directly analogous to the formation of Recent hardgrounds.  相似文献   

10.
Lower Cretaceous (Hauterivian) bioclastic sandstone turbidites in the Scapa Member (North Sea Basin) were extensively cemented by low-Mg calcite spars, initially as rim cements and subsequently as concretions. Five petrographically distinct cement stages form a consistent paragenetic sequence across the Scapa Field. The dominant and pervasive second cement stage accounts for the majority of concretions, and is the focus of this study. Stable-isotope characterization of the cement is hampered by the presence of calcitic bioclasts and of later cements in sponge spicule moulds throughout the concretions. Nevertheless, trends from whole-rock data, augmented by cement separates from synlithification fractures, indicate an early calcite δ18O value of+0·5 to -1·5‰ PDB. As such, the calcite probably precipitated from marine pore fluids shortly after turbidite deposition. Carbon isotopes (δ13C=0 to -2‰ PDB) and petrographic data indicate that calcite formed as a consequence of bioclastic aragonite dissolution. Textural integrity of calcitic nannoplankton in the sandstones demonstrates that pore fluids remained at or above calcite saturation, as expected for a mineral-controlled transformation. Electron probe microanalyses demonstrate that early calcite cement contains <2 mol% MgCO3, despite its marine parentage. Production of this cement is ascribed to a combination of an elevated aragonite saturation depth and a lowered marine Mg2+/Ca2+ ratio in early Cretaceous ‘calcite seas’, relative to modern oceans. Scapa cement compositions concur with published models in suggesting that Hauterivian ocean water had a Mg2+/Ca2+ ratio of ≤1. This is also supported by consideration of the spatial distribution of early calcite cement in terms of concretion growth kinetics. In contrast to the dominant early cement, late-stage ferroan, 18O-depleted calcites were sourced outwith the Scapa Member and precipitated after 1–2 km of burial. Our results emphasize that bioclast dissolution and low-Mg calcite cementation in sandstone reservoirs should not automatically be regarded as evidence for uplift and meteoric diagenesis.  相似文献   

11.
Isotopic compositions of oxygen, carbon and strontium of calcite cleats in coal seams of southern Victoria Land, Antarctica, and Tuscarawas County, Ohio, contain a record of the conditions a the time of their formation. The Antarctic calcites (δ 18O(SMOW) = +9.14 to +11.82%0) were deposited from waters enriched in 16O whose isotopic composition was consistent with that of meteoric precipitation at low temperature and high latitude. The carbon of the calcite cleats (δ 13C(PDB) = ?15.6 to ?16.9%0) was derived in part from the coal (δ 13C(PDB) = ?23.5 to ?26.7%0) as carbon dioxide and by oxidation of methane or other hydrocarbon gases. The strontium (87Sr86Sr = 0.71318–0.72392) originated primarily from altered feldspar grains in the sandstones of the Beacon Supergroup.Calcite cleats in the Kittaning No. 6 coal seam of Ohio (δ 18O(SMOW) = +26.04 to +27.79%0) were deposited from waters that had previously exchanged oxygen, possibly with marine carbonate at depth. The carbon (δ 13C(PDB) = 0.9 to +2.4%0) is enriched in 13C even though that cleats were deposited in coal that is highly enriched in 12C and apparently originated from marine carbonates. Strontium in the cleats (Sr87 0.71182–0.71260) is not of marine origin but contains varying amounts of radiogenic 87Sr presumably derived from detrital Rb-bearing minerals in the adjacent sedimentary rocks. The results of this study suggest that calcite cleats in coal of southern Victoria Land, Antarctica, were deposited after the start of glaciation in Cenozoic time and that those in Ohio precipitated from formation waters derived from the underlying marine carbonate rocks, probably in the recent geologic past.  相似文献   

12.
Carbonate nodules and slabs in late Holocene shelly terrigenous deposits of the modern Fraser River delta (~49°N) are formed close to the seafloor by precipitation from saline pore waters of mainly fibrous to bladed crystals of high-Mg (~ 10–20 mol% MgCO3) calcite cement as coalescing isopachous crusts on grains. Previous reports that the cement is low-Mg calcite are not supported by this study. Highly negative δ13C values of ? 7 to ? 59‰ for the cements indicate that the bulk of their carbonate carbon was derived from the microbiological degradation of organic matter in the deltaic deposits during shallow burial. In particular, the production of biogenic methane (CH4) by anaerobic bacterial fermentation, its upward migration, chemical or biological oxidation to CO2 and neutralization in the near-surface sediment, and diffusion to microenvironments relatively enriched in organic components, are a possible set of conditions influencing the process and sites of carbonate cementation. Methane-derived Mg-calcite appears also to be the major submarine cement in several other modern occurrences of lithified shallow-water terrigenous sands and muds at non-tropical latitudes.  相似文献   

13.
MUCHEZ  NIELSEN  SINTUBIN  & LAGROU 《Sedimentology》1998,45(5):845-854
Two calcite cements, filling karst cavities and replacing Lower Carboniferous limestones at the Variscan Front Thrust, were precipitated after mid-Jurassic Cimmerian uplift and subsequent erosion but before late Cretaceous strike-slip movement. The first calcite (stage A) is nonferroan and crystals are coated by hematite and/or goethite. These minerals also occur as inclusions along growth zones. The calcite lattice contains < 0·07 mol.% Fe, but Mn concentrations can be as high as 0·72 mol.% in bright yellow luminescent zones. Primary, originally one-phase, all-liquid, aqueous inclusions have a final melting temperature between ?0·2° and +0·2 °C, indicating a meteoric origin of the ambient water. The δ13C and δ18O values of the calcites are between ?7·3‰ and ?6·3‰, ?7·8‰ and ?5·5‰ on the Vienna PeeDee Belemnite (VPDB) scale, respectively. The second calcite (stage B) consists of ferroan (0·13–0·84 mol.% Fe) blocky crystals with Mn concentrations between 0·34 and 0·87 mol.%. Primary, single-phase aqueous fluid inclusions indicate precipitation from a meteoric fluid below 50 °C . The δ13C values of stage B calcites vary between ?7·3‰ and ?2·1‰ VPDB and the δ18O values between ?7·9‰ and ?7·2‰ VPDB. A precipitation temperature below 50 °C for the stage A calcites and the presence of iron oxide/hydroxide inclusions in the crystals indicate near-surface precipitation conditions. Within this setting, the geochemistry of the nonferroan stage A calcites reflects precipitation under oxic to suboxic conditions. The ferroan stage B calcites precipitated in a reducing environment. The evolution from the stage A to stage B calcites and the associated geochemical changes are interpreted to be related to the change from semiarid to humid conditions in western Europe during late Jurassic–Cretaceous times. A change in humidity can explain the evolution of groundwater from oxic/suboxic to reducing conditions during calcite precipitation. The typically higher δ13C values of the stage B compared to the stage A calcites can be explained by a smaller contribution of carbon derived from soil-zone processes than from carbonate dissolution in the groundwater under humid conditions. The small shift to lower δ18O between stage A and B calcites may be caused by a higher precipitation temperature or a decrease in the δ18O value of the meteoric water. This decrease could have been caused by a change in the source of the air masses or by an increase in the amount of rainfall during the early mid-Cretaceous. Although the latter interpretation is preferred, it cannot be proven.  相似文献   

14.
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.  相似文献   

15.
Holocene beachrocks of Northeast Brazil are composed predominantly of quartz (90%) with minor carbonate fragments (6% algal detritus) and feldspars (4%). The cement shows three textural varieties: (1) calciferous, surrounding siliciclastic grains; (2) micritic, with an acicular fringe; and (3) cryptocrystalline calcite in pores. Sandstone structures and composition show evidence of submerged and low-energy beaches. Cement is formed by ~20 mol% MgCO3; the δ13C in cement ranges from ?1.3‰ to +3.5‰ PDB and δ18O varies from ?2.1 to +1.2‰PDB. The cement was precipitated under high CO2 pressure, as a result of the interaction of CaCO3? saturated seawater and nonsaturated groundwater, in a beach environment.  相似文献   

16.
Pervasive dolomites occur preferentially in the stromatoporoid biostromal (or reefal) facies in the basal Devonian (Givetian) carbonate rocks in the Guilin area, South China. The amount of dolomites, however, decreases sharply in the overlying Frasnian carbonate rocks. Dolostones are dominated by replacement dolomites with minor dolomite cements. Replacement dolomites include: (1) fine to medium, planar‐e floating dolomite rhombs (Rd1); (2) medium to coarse, planar‐s patchy/mosaic dolomites (Rd2); and (3) medium to very coarse non‐planar anhedral mosaic dolomites (Rd3). They post‐date early submarine cements and overlap with stylolites. Two types of dolomite cements were identified: planar coarse euhedral dolomite cements (Cd1) and non‐planar (saddle) dolomite cements (Cd2); they post‐date replacement dolomites and predate late‐stage calcite cements that line mouldic vugs and fractures. The replacement dolomites have δ18O values from ?13·7 to ?9·7‰ VPDB, δ13C values from ?2·7 to + 1·5‰ VPDB and 87Sr/86Sr ratios from 0·7082 to 0·7114. Fluid inclusion data of Rd3 dolomites yield homogenization temperatures (Th) of 136–149 °C and salinities of 7·2–11·2 wt% NaCl equivalent. These data suggest that the replacive dolomitization could have occurred from slightly modified sea water and/or saline basinal fluids at relatively high temperatures, probably related to hydrothermal activities during the latest Givetian–middle Fammenian and Early Carboniferous times. Compared with replacement dolomites, Cd2 cements yield lower δ18O values (?14·2 to ?9·3‰ VPDB), lower δ13C values (?3·0 to ?0·7‰ VPDB), higher 87Sr/86Sr ratios (≈ 0·7100) and higher Th values (171–209 °C), which correspond to trapping temperatures (Tr) between 260 and 300 °C after pressure corrections. These data suggest that the dolomite cements precipitated from higher temperature hydrothermal fluids, derived from underlying siliciclastic deposits, and were associated with more intense hydrothermal events during Permian–Early Triassic time, when the host dolostones were deeply buried. The petrographic similarities between some replacement dolomites and Cd2 dolomite cements and the partial overlap in 87Sr/86Sr and δ18O values suggest neomorphism of early formed replacement dolomites that were exposed to later dolomitizing fluids. However, the dolomitization was finally stopped through invasion of meteoric water as a result of basin uplift induced by the Indosinian Orogeny from the early Middle Triassic, as indicated by the decrease in salinities in the dolomite cements in veins (5·1–0·4 wt% NaCl equivalent). Calcite cements generally yield the lowest δ18O values (?18·5 to ?14·3‰ VPDB), variable δ13C values (?11·3 to ?1·2‰ VPDB) and high Th values (145–170 °C) and low salinities (0–0·2 wt% NaCl equivalent), indicating an origin of high‐temperature, dilute fluids recharged by meteoric water in the course of basin uplift during the Indosinian Orogeny. Faults were probably important conduits that channelled dolomitizing fluids from the deeply buried siliciclastic sediments into the basal carbonates, leading to intense dolomitization (i.e. Rd3, Cd1 and Cd2).  相似文献   

17.
The geochemical significance of three selected ions (Mg2+, Na+, and Sr2+) supports a model of dolomitization by brackish groundwater. This groundwater zone contains sufficient quantities of Mg2+ to facilitate dolomitization (MgCaratios 1). Rising and falling of sea level and fluctuations of the phreatic zone related to climatic variations account for the thickness of the dolomite layers and the chemical distributions within these layers. Sodium concentrations in the calcite are 70–185 ppm, indicating formation in brackish water. Dolomite has sodium concentrations between 50–1400 ppm, suggesting formation in waters of similar salinity.Strontium in calcite ranges from 320–600 ppm, suggesting diagenesis in slightly saline waters in an open system. Dolomite contains 241 ppm Sr2+ on the average and calcite has 418 ppm Sr2+. The Sr2+ concentrations of the dolomite are characteristic of diagenesis in water less saline than sea water. Average strontium concentrations in the dolomite occur in two distinct groups, 260 ppm for dolomite with 39–43 mole-% MgCo3 and 195 ppm for the dolomite with 44–50 mole-% MgCO3. The difference in the Sr2+ concentrations of the two dolomite groups indicates the higher mole-% MgCO3 dolomite recrystallized in a less saline environment than the lower mole-% MgCO3 dolomite. These different environments are attributed to a relatively more saline coastal environment and a less saline inland environment.The more nearly stoichiometric dolomite (44–50 mole-% MgCO3) has less scatter when mole-% MgCO3 is plotted against Sr2+ and Na+. This suggests a greater approach to equilibrium with the dolomitizing fluid than the lower mole-% MgCO3 (39–43) dolomite. The more saline environment has higher Mg/Ca ratios and promotes more calcium-rich dolomite during diagenesis because of the inhibition from competing foreign ions and because it is thermodynamically a more favorable environment which causes more rapid crystallization. The less saline waters allow recrystallization to proceed more slowly, producing better ordering in the dolomites, textural preservation and development of subhedral to euhedral rhombic crystals.  相似文献   

18.
This paper describes the occurrence of dolostone and the mechanism of dolomitization of the Upper Devonian Gölbo?az? Formation in the allochthonous Taurus Mountains Alada? unit in Turkey. The Upper Devonian Gölbo?az? Formation carbonates, with dominant ostracod-bearing mudstone and wackestone, formed tidal and subtidal environments, and some of these rocks were dolomitized from shallow to deep burial. On the basis of the field, the petrographic and geochemical features, four different replaceable and cement dolostone phases have been recognized. The replacive dolostones contain (1) very fine to fine crystalline planar-s dolostone (df1), (2) medium to coarse crystalline planar-s to planar-e dolostone (df2), (3) coarse to very coarse crystalline non-planar-a dolostone (df3), and (4) coarse to very coarse crystalline planar dolostone cement (df4). The replacive dolostones are disordered to moderate the ordered and calcium-rich. They are non-stoichiometric and have 46–59 mol% CaCO3 and 41–54 mol% MgCO3 total contents. The df1 dolostones have MgCO3 contents of 41–54 mol%, the df2 dolostones have 41–53 mol%, the df3 dolostones have 49 mol%, and the df4 dolostones have 49–50 mol%, respectively. The Gölbo?az? dolostones have δ18O values of ?9.44 to ?2.20‰ Vienna Pee Dee Belemnite (VPDB) and δ13C values of ?1.58 to +2.52 VPDB. Sr, Na, Mn, and Fe concentrations of replacive dolostones are 74–184, 148–593, below detection level (bdl)–619, and 1049–9233 ppm, respectively. The petrographic and geochemical data demonstrate that the replacive dolostones occurred prior to the chemical compaction at shallow to intermediate burial depths from Late Devonian seawater and/or seawater lightly modified by water–rock interaction process and later recrystallized by basinal brines at increasing burial depths and temperature. The North American Shale Composite-normalized rare earth element values of both limestone and dolostone show very similar rare earth element patterns characterized by slightly or considerably negative cerium (Ce) anomalies and a clear depletion in all rare earth element species. The dedolomitization observed in the Gölbo?az? Formation is thought to occur by the oxidizing effect of the meteoric water in the shallow burial environment during the telodiagenesis.  相似文献   

19.
The Pongkor gold–silver deposit is the largest low‐sulfidation epithermal precious metal deposit in Indonesia, and is of Pliocene age. The deposit consists of nine major subparallel quartz–adularia–carbonate veins with very low sulfide content. Vein infill records five paragenetic sequences, dominated by calcite in the early stage and quartz in the later stage of the hydrothermal evolution. Fluid inclusions in hydrothermal calcite and quartz of all stages indicate a temperature ranging from 180 to 220°C and a meteoric water origin (very low salinity close to 0 wt% NaCl equivalent). Carbon isotope data on calcite display a narrow range from ?6.5 to ?3.0‰δ13C. The oxygen isotope values have a wider range of +4.6 to +10.1‰δ18O. The broadly positive correlation of the δ13C versus δ18O plot suggests that the carbon species, which equilibrated during the formation of calcite, is dominated by H2CO3 not far from equilibrium with HCO3?. The abundance of rare earth and yttrium (REY) in carbonate samples is very low (>REY mostly <2 ppm). However, there is always a positive Eu anomaly, which indicates a deeper fluid reservoir at >250°C.  相似文献   

20.
Holocene meteoric dolomitization of Pleistocene limestones, North Jamaica   总被引:3,自引:0,他引:3  
Wholesale removal of the unstable carbonate phases aragonite and Mg-calcite, and precipitation of calcite and dolomite is currently taking place where phreatic waters (the modern water table) invade 120,000-year-old Pleistocene biolithites (Falmouth Formation), North Jamaica. Pleistocene rocks presently in the vadose zone are relatively unaltered, and consist of mineralogically unstable scleractinian biolithites. At the water table, a narrow zone of solution, a ‘water table cave’ is commonly encountered. Below the water table the rocks are invariably more highly altered than those above. Mg-calcites are very rare, and considerable dissolution of aragonite has commonly occurred. Dolomite occurs as 8–25 μm, subhedral to euhedral crystals replacing micrite, or precipitated as void linings. The isotopic composition of the dolomite (δO18=-1·0 %0, δC13=-8·4 %0), and its high strontium content (3000 p.p.m.) suggest precipitation as CO2-oversaturated meteoric groundwaters invade the mineralogically unstable biolithites, dissolve Mg-calcites and Sr-rich aragonites, and de-gas. Because some dolomitized rocks are enriched in magnesium relative to unaltered biolithites, addition of magnesium to the system is necessitated, and is probably derived from sea water in the mixing zone. Phreatic meteoric diagenesis is thus demonstrated to be a rapid process, and to be capable of dolomitization.  相似文献   

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