Magnesian calcite cements and their diagenesis: dissolution and dolomitization, Mururoa Atoll

The most ubiquitous syn-sedimentary cements affecting Mururoa atoll are composed of magnesian calcite. Three main types are distinguished: fibrous, bladed and sparitic on the basis of petrography, morphology and MgCO₃ concentration of the constituting crystals, while peloid infills, a particular form of HMC chemical precipitation, also exist. Petrographic evidence and isotopic signatures are compatible with marine precipitation. Mururoa atoll was exposed several times to meteoric diagenesis resulting in varied diagenetic alterations including selective dissolution and partial dolomitization of Mg-calcite cements. These alterations are responsible for substantial modifications of the initial cement fabrics and may introduce unconformities in the diagenetic chronology. The first stage of the partial dissolution of Mg-calcite induces the development of chalky, white friable zones within the initially crystalline, hard cement layers. At ultrascale, this is due to the creation of micro-voids along the elongate cement fibres. Advanced dissolution includes total disappearance of cement portions as attested to by large voids within the cement crust and/or between superposed cement layers. Mg-calcite dissolution is related to meteoric diagenesis during periods of Quaternary exposure. The creation of voids within Mg-calcite layers is due to the mechanical removal of previously altered calcium carbonate, a process suggesting marine or non-marine water flow, probably in the vadose environment. Selective dolomitization of Mururoa cements involves alternations of calcite and dolomite which form successive cement-like rinds within primary cavities. At Mururoa, these alternations are the result of selective dolomitization of the pre-existing Mg-calcite cements rather than successive precipitation of calcite and dolomite. Selective dolomitization of Mg-calcite cements at Mururoa indicates that a given cement succession is not necessarily a simple chronological sequence. Oxygen isotope values of dolomites are enriched in δ¹⁸6 by about 3‰ PDB within calcite-dolomite pseudo-alternations. The dolomitizing fluid at Mururoa seems similar to present marine water although some mixture with meteoric water is probable to favour dissolution associated with dolomitization.     

Calcite cementation during bacterial manganese, iron and sulphate reduction in Jurassic shallow marine carbonates

Faunally restricted argillaceous wackestones from the Middle Jurassic of eastern England contain evidence of early diagenetic skeletal aragonite dissolution and stabilization of the carbonate matrix, closely followed by precipitation of zoned calcite cements, and precipitation of pyrite. Distinctive cathodoluminescence and trace element trends through the authigenic calcites, their negative δ¹³C compositions and the location of pyrite in the paragenetic sequence indicate that calcite precipitation took place during sequential bacterial Mn, Fe and sulphate reduction. Calcite δ¹⁸O values are compatible with cementation from essentially marine pore fluids, although compositions vary owing to minor contamination with ¹⁸O-depleted ‘late’cements. Mg and Sr concentrations in the calcites are lower than those in recent marine calcite cements. This may be a result of kinetic factors associated with the shallow burial cementation microenvironments. Bicarbonate for sustained precipitation of the authigenic calcites was derived largely from aragonite remobilization, augmented by that produced through anaerobic organic matter oxidation in the metal and sulphate reduction environments. Aragonite dissolution is thought to have been induced by acidity generated during aerobic bacterial oxidation of organic matter. Distinction of post-oxic metal reduction and anoxic sulphate reduction diagenetic environments in modern carbonate sediments is uncommon outside pelagic settings, and early bacterially mediated diagenesis in modern platform carbonates is associated with extensive carbonate dissolution. High detrital Fe contents of the Jurassic sediments, and their restricted depositional environment, were probably the critical factors promoting early cementation. These precipitates constitute a unique example of calcite authigenesis in shallow water limestones during bacterial Mn and Fe reduction.     

Solution-collapse breccias of the Minkinfjellet and Wordiekammen Formations, Central Spitsbergen, Svalbard: a large gypsum palaeokarst system

Large volumes of carbonate breccia occur in the late syn-rift and early post-rift deposits of the Billefjorden Trough, Central Spitsbergen. Breccias are developed throughout the Moscovian Minkinfjellet Formation and in basal parts of the Kazimovian Wordiekammen Formation. Breccias can be divided into two categories: (i) thick, cross-cutting breccia-bodies up to 200 m thick that are associated with breccia pipes and large V-structures, and (ii) horizontal stratabound breccia beds interbedded with undeformed carbonate and siliciclastic rocks. The thick breccias occur in the central part of the basin, whereas the stratabound breccia beds have a much wider areal extent towards the basin margins. The breccias were formed by gravitational collapse into cavities formed by dissolution of gypsum and anhydrite beds in the Minkinfjellet Formation. Several dissolution fronts have been discovered, demonstrating the genetic relationship between dissolution of gypsum and brecciation. Textures and structures typical of collapse breccias such as inverse grading, a sharp flat base, breccia pipes (collapse dolines) and V-structures (cave roof collapse) are also observed. The breccias are cemented by calcite cements of pre-compaction, shallow burial origin. Primary fluid inclusions in the calcite are dominantly single phase containing fresh water (final melting points are ca 0 °C), suggesting that breccia diagenesis occurred in meteoric waters. Cathodoluminescence (CL) zoning of the cements shows a consistent pattern of three cement stages, but the abundance of each stage varies stratigraphically and laterally. δ¹⁸O values of breccia cements are more negative relative to marine limestones and meteoric cements developed in unbrecciated Minkinfjellet limestones. There is a clear relationship between δ¹⁸O values and the abundance of the different cement generations detected by CL. Paragenetically, later cements have lower δ¹⁸O values recording increased temperatures during their precipitation. Carbon isotope values of the cements are primarily rock-buffered although a weak trend towards more negative values with increasing burial depth is observed. The timing of gypsum dissolution and brecciation was most likely related to major intervals of exposure of the carbonate platform during Gzhelian and/or Asselian/Sakmarian times. These intervals of exposure occurred shortly after deposition of the brecciated units and before deep burial of the sediments.     

Low-Mg calcite marine cement in Cretaceous turbidites: origin, spatial distribution and relationship to seawater chemistry

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.     

The application of cathodoluminescence to interpreting the diagenesis of an ancient calcrete profile

A laterally extensive calcrete profile has been identified in the Late Asbian (Lower Carboniferous) shallow marine shelf limestones of the Llangollen area, North Wales. The upper surface of the profile is defined by a laterally discontinuous palaeokarstic surface and by laminated calcareous crusts which developed within the underlying limestone. The profile contains a unique series of early pore-filling vadose cements which only occur down to 1 m below the palaeokarstic surface. Cathodoluminescence reveals that these cements pre-date the late pore-filling meteoric phreatic cements which occur throughout local Asbian lithologies. A spar cement stratigraphy has been established for the calcrete profile. Subaerial vadose cements comprise two generations of non-luminescent cement, followed by a brightly luminescent generation which occasionally shows an acicular habit. This needle-fibre calcite represents the final stage of vadose cementation. Precipitation of vadose cements was contemporary with subaerial alteration and micritization of the limestone. Textures, visible only with cathodoluminescence, provide evidence of recurrent periods of fabric dissolution. The most extensive phase of dissolution occurred immediately after the precipitation of the non-luminescent subaerial vadose cements. Several different textures have been recorded, each reflecting the morphology of a partially dissolved substrate. Dissolution textures are generally confined to the walls of the larger pores and to early brecciation fractures. These probably acted as fluid pathways in the calcrete during early subaerial diagenesis. Much of the non-marine micrite in the calcrete profile appears as needle-fibre calcite under cathodoluminescence. This acicular calcite was probably formed in response to localized supersaturation of meteoric pore fluids caused by periods of near-surface evaporation. Since needle-fibre luminescence is strongly variable, these ambient conditions are not believed to have directly controlled the activator ion concentrations of cementing pore waters. Needle-fibre calcite is considered to be a cement precipitate which has almost completely recrystallized to micrite, probably during the late stages of subaerial diagenesis. Two generations of subaerial micrite which define a ‘micrite stratigraphy’, have been distinguished under cathodoluminescence. Reconstructing the diagenetic history of this ancient calcrete profile has revealed that subaerial alteration was multistaged, with many diagenetic processes acting simultaneously during a single phase of emergence.     

Deposition and diagenesis of debris flows in Upper Ordovician limestones, Hadeland, Norway

The Upper Ordovician rocks of Hadeland, Norway, form a sequence of thin bedded nodular limestones (wackestones) and shales, hosting five distinctive sedimentary breccia complexes. These breccias contain blocks of varying sizes and shapes in a wackestone and grainstone matrix. Blocks differ in lithology, and in their included biotas and cement sequences. The thin bedded limestones are interpreted as turbidites, deposited against a background of hemipelagic calcareous shales. The breccias occupy channels cut into this sequence. The lithologies and biotas of blocks in the breccias record deposition in differing sedimentary environments, whereas their cements are the results of contrasting diagenetic histories. Blocks were eroded from a diverse and mature carbonate platform, close to sea level, which probably lay 5–10 km east of Hadeland. The breccias are interpreted as debris flow deposits, transported as channellized flows. Following channel cutting events, perhaps triggered by sea level change, channels were characterized by deposition rather than erosion. Wackestones and grainstones associated with the breccias also reflect resedimentation, their less diverse biota suggesting local derivation on the slope. The reworking of calcarenaceous muds locally produced clean washed calcarenites (now grainstones). A fall in sea level resulted in emergence of the upper slope and erosion of the debris flow complex to form caverns and fissures. As sea level rose again crinoidal calcarenites, now grainstones, were deposited within these cavities. Cement sequences in blocks record early marine and burial conditions on the shelf, and also precipitation of new marine cements following downslope transport. Those cements in lithologies formed in situ document later shallowing, culminating in emergence. The localized dissolution of cements in both blocks and associated grainstones reflects the infiltration of ‘aggressive’meteoric waters through permeable channel deposits. A subsequent rise in sea level is recorded in the generation of an additional marine cement with final burial reflected in the deposition of blocky calcite. The debris flow deposits therefore maintained their distinctive character from deposition through diagenesis.     

Diagenetic model of carbonate rocks of Guri Member of Mishan Formation (Lower to Middle Miocene) SE Zagros basin,Iran

In order to understand the post-depositional history of carbonate rocks of Guri Member (Lower to Middle Miocene), three stratigraphic sections were selected in north Bandar-Abbas in southeast of Iran. Sampling was carried out, analyzed for selective parameters such as oxygen and carbon isotopic compositions (δ¹⁸O and δ¹³C) and interpreted in the present study. We recognized several diagenetic processes including micritization, cementation, neomorphism, compaction, dissolution, silicification, dolomitization, fracturing and vein filling. Some of the diagenetic processes occurred at different conditions, so in order to achieve precise interpretation, samples from different carbonate components such as, micrite, fracture cement, solution pore cement, intergranular cement, and some biotic allochems were analyzed. In this study micrite samples were subdivided into two groups including micro-spary and micrite. They were recognized under Cathodoluminescence microscope. In addition, micrite samples were classified into five groups based on their depositional environments: supratidal, lagoon, coral bar, open sea, and open basin. There were minor changes in stable isotope ratios based on the sedimentary environments, stratigraphy successions, and micro-spary or micrite properties. In this study, similar calcite cements in petrography studies were differentiated by stable isotope data. Those calcite cements have formed in different diagenetic environments such as meteoric and burial cements. Paragenetic sequence of carbonate rocks were interpreted by integration of petrographic and isotopic studies. We have reconstructed diagenetic models of Guri Member into four stages including marine, meteoric, burial, and uplifting.     

Physico-chemical environment of pedogenic carbonate formation in Devonian vertic palaeosols, central Appalachians, USA

The morphology and geochemistry of pedogenic carbonate found in vertic claystone palaeosols in the Devonian Catskill Formation in central Pennsylvania preserve a record of the physical and chemical environment of carbonate precipitation. The carbonate is characterized by three distinct petrographic generations. Pedogenic rhizoliths and nodules are the earliest precipitated generation, and typically consist of dull red-brown luminescent micrite. Clear, equant calcite spar cement fills voids in the centres of rhizoliths, as well as circumgranular cracks and septarian voids in nodules. Early spar cements are non-luminescent to dull luminescent, whereas later spar cements exhibit bright yellow-orange luminescence. Late stage pedogenic fractures are always occluded with very bright yellow-orange luminescent spar cements. The incorporation of progressively higher concentrations of Mn (up to 34000 ppm) into successively younger calcite spar cements, without concomitant increases in Fe, suggests carbonate precipitation from an evolving meteoric water in which Mn²⁺ became increasingly mobile over time. The increased mobility is possibly due to decreasing Eh, resulting from oxidation of organic matter after rapid soil burial on the floodplain. The amount of Fe²⁺ available for incorporation into calcite was limited because most iron was immobile, having been earlier oxidized and bound to the palaeosol clay matrix as a poorly crystallized ferric oxide or oxyhydroxide mineral. Carbon isotope compositions of pedogenic carbonate correlate with the inferred depth of carbonate precipitation. Rhizoliths preserved below the lowest stratigraphic occurrences of pedogenic slickensides are consistently depleted in ¹³C relative to nodules, which formed stratigraphically higher, within the zone of active soil shrink and swell processes. Nodular carbonate, precipitated in proximity to deep cracks in the soil, is enriched due to increased gas exchange with isotopically heavy atmospheric CO₂. Accordingly, rhizolith compositions will most accurately estimate palaeoatmospheric levels of CO₂; the use of nodule compositions may result in overestimation of P_CO2 by as much as 30%.     

The concretions of the Bearreraig Sandstone Formation: geometry and geochemistry

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.     

Carbonate cementation of some Pleistocene temperate marine sediments

Carbonate cementation of some carbonate and quartz sands in three raised beaches of temperate origins was investigated. The carbonate of the cements was found to have been derived from the dissolution of skeletal debris. The sandstones, so produced, now possess only low-magnesium calcite, but the original sediments, like adjacent modern beach and blown sands, probably contained low-magnesium calcite, aragonite and some high-magnesium calcite, all of skeletal origin. In meteoric water the dissolution has occurred of all carbonate within minute, tubulelike, volumes of sand. Concurrent deposition in adjacent volumes of sand of low-magnesium calcite formed cements that are irregularly nodular or uneven on a small scale. Aragonite within the minute nodules has been replaced paramorphically by low-magnesium calcite. Additional local carbonate cements were formed at later dates, around and within solution pipes.     

Diagenesis of an Upper Triassic reef complex, Wilde Kirche, Northern Calcareous Alps, Austria

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.     

The diagenesis of the late Dinantian Derbyshire-East Midland carbonate shelf, central England

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 + 3.2^0/00. 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.     

Methane-derived high-Mg calcite submarine cement in Holocene nodules from the Fraser Delta, British Columbia, Canada

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.     

Controls of facies and sediment composition on the diagenetic pathway of shallow-water Heterozoan carbonates: the Oligocene of the Maltese Islands

Relatively few studies have so far addressed diagenetic processes in Heterozoan carbonates and the role that sediment composition and depositional facies exert over diagenetic pathways. This paper presents a study of Oligocene shallow-water, Heterozoan carbonates from the Maltese Islands. We investigate stratigraphic distribution, abundance and timing of diagenetic features and their relationship to sediment composition and depositional facies. The studied carbonate rocks comprise rud- to packstones of the Heterozoan association predominantly containing coralline red algae, bryozoans, echinoids and benthic foraminifers. XRD analyses show that all high-Mg calcite has been transformed to low-Mg calcite and that no aragonite is preserved. Diagenetic processes include dissolution of aragonitic biota, neomorphism of high-Mg calcitic biota to low-Mg calcite and cementation by fibrous, bladed, epitaxial and blocky cements. Stable isotopes on bulk rock integrated with petrographic data suggest that the study interval was not exposed to significant meteoric diagenesis. We interpret early cementation to have taken place in the marine and marine burial environment. The distribution and abundance of early diagenetic features, determining the diagenetic pathway, can be related to the primary sediment composition and depositional texture. Sorting and micrite content are important controls over the abundance of diagenetic features.     

Changes in carbon and oxygen isotope composition during limestone diagenesis

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

Contrasting diagenesis of two Carboniferous Oolites from South Wales: a tale of climatic influence

Two oolites in the Dinantian (Mississippian/Lower Carboniferous) of Glamorgan, SW Britain, were deposited in similar depositional environments but have contrasting diagenetic histories. The Brofiscin and Gully Oolites occur in the upper parts of shallowing-upward sequences, formed through strandplain progradation and sand shoal and barrier growth upon a southward-dipping carbonate ramp. The Brofiscin Oolite is characterized by a first-generation cement of equant calcite spar, preferentially located at grain-contacts and forming non-isopachous fringes around grains, interpreted as meteoric vadose and phreatic in origin. Isopachous fibrous calcite fringes of marine origin are rather rare and occur only at a few horizons. Burial compaction was not important and porosity was occluded by poikilotopic calcite spar. Fitted grain-grain contacts locally occur and could be the result of near-surface vadose dissolution-compaction. Syntaxial overgrowths on echinoderm debris are common. Pre-compaction overgrowths are cloudy (inclusion-rich) and probably of meteoric origin, and post-compaction overgrowths are inclusion-free. By contrast, the Gully Oolite has little first-generation cement. However, marine fibrous calcite is common in oolitic intraclasts, as isopachous fringes of acicular calcite crystals closely associated with peloidal internal sediment; and early equant, drusy calcite spar occurs in the uppermost part of the Gully, beneath a prominent palaeokarst where pedogenic cements also occur. The major feature of Gully diagenesis is burial compaction, resulting in extensive grain-grain dissolution and microstylolitic grain contacts, and post-compaction poikilotopic spar occluded remaining porosity. The Brofiscin Oolite is pervasively dolomitized up-dip but the Gully Oolite for the most part only contains scattered pre-compaction dolomite rhombs and late veins of baroque dolomite, with less pervasive dolomitization. The difference in diagenetic style of the two Dinantian oolites is attributed to prevailing climate. The paucity of early meteoric cements in the Gully is a result of an arid climate, and this is supported by the nature of the capping palaeokarst. The abundant meteoric cements in the Brofiscin reflect a more humid climate, and effective meteoric recharge also resulted in up-dip pervasive mixing-zone dolomitization. The style of early diagenesis in these two oolites exerted a major control on the later burial diagenesis: in the Brofiscin, the early cements inhibited grain-grain dissolution and pressure solution, while these processes operated extensively in the Gully Oolite. Thus, prevailing climate can influence a limestone's diagenetic history from near-surface through into deep burial.     

Selective blackening of bioclasts via mixing‐zone aragonite neomorphism in Late Triassic limestone,Zlatibor Mountains,Serbia

A peculiar facies of the Norian–Rhaetian Dachstein‐type platform carbonates, which contains large amounts of blackened bioclasts and dissolutional cavities filled by cements and internal sediments, occurs in the Zlatibor Mountains, Serbia. Microfacies investigations revealed that the blackened bioclasts are predominantly Solenoporaceae, with a finely crystalline, originally aragonite skeleton of fine cellular structure. Blackening of other bioclasts also occurs subordinately. Solenoporacean‐dominated reefs, developed behind the platform margin patch‐reef tract, were the main source of sand‐sized detritus. The blackened and other non‐blackened bioclasts are incorporated in automicrite cement. Radiaxial fibrous calcite cements in the dissolutional cavities are also black, dark grey or white. Reworked black pebbles were reported from many occurrences of peritidal deposits; in those cases, the blackening took place under pedogenic, meteoric diagenetic conditions. In contrast, in the inner platform deposits of the Ilid?a Limestone, the blackening of bioclasts occurred in a marine–meteoric mixing‐zone, as indicated by petrographic features and geochemical data of the skeleton‐replacing calcite crystals. Attributes of mixing‐zone pore waters were controlled by mixing corrosion, different solubility of carbonate minerals and microbial decomposition of organic matter. In the moderate‐energy inner platform environment, large amounts of microbial organic tissue were accumulated and subsequently decomposed, triggering selective blackening in the course of early, shallow burial diagenesis. The δ¹⁸O and δ¹³C values of the mixing‐zone precipitates and replacive calcite do not produce a linear mixing trend. Variation mainly resulted from microbial decomposition of organic matter that occurred under mixing‐zone conditions. The paragenetic sequence implies cyclic diagenetic conditions that were determined by marine, meteoric and mixing‐zone pore fluids. The diagenetic cycles were controlled by sea‐level fluctuations of moderate amplitude under a semi‐arid to semi‐humid climate.     

The complex diagenetic history of discontinuities in shallow‐marine carbonate rocks: New insights from high‐resolution ion microprobe investigation of δ18O and δ13C of early cements

Sedimentary gaps are a major obstacle in the reconstruction of a carbonate platform's history. In order to improve the understanding of the early diagenesis and the succession of events occurring during the formation of discontinuity surfaces in limestones, secondary ion mass spectrometry was used for the first time to measure the δ ¹⁸O and δ ¹³C signatures of 11 early cement and fabric stages in several discontinuity surfaces from the Jurassic carbonate platform of the Paris Basin, France. Pendant cements show a high variability in δ ¹⁸O, which was impossible to detect by the less precise microdrilling method. The morphology of a given cement can be produced in various environments, and dogtooth cements especially can precipitate in marine phreatic and meteoric phreatic to vadose environments. Marine dogtooth cements and micritic microbially induced fabrics precipitated directly as low‐magnesium calcite in marine waters, as attested to by the preservation of their initial δ ¹⁸O and δ ¹³C signals. Five discontinuity types are recognized based on high‐resolution geochemical analyses, and their palaeoenvironmental history can be reconstructed. Two exposure surfaces with non‐ferroan pendant or meniscus cements formed in the oxidizing vadose zone. A hardground displays marine fibrous cements and non‐ferroan dogtooth cements that formed in a subtidal environment in oxidizing water. Two composite surfaces have undergone both marine and subaerial lithification. Composite surface 1 displays non‐luminescent ferroan dogtooth cements that precipitated in reduced conditions in seawater, followed by brown‐luminescent dogtooth cements characteristic of a meteoric phreatic environment. Composite surface 2 exhibits microbially induced fabrics that formed in marine water with abundant organic matter. The latter discontinuity, initially formed in a subtidal environment, was subsequently exposed to meteoric conditions, as evidenced by ferroan geopetal cements. A high‐resolution ion microprobe study is essential to precisely document the successive diagenetic environments that have affected carbonate rocks and discontinuities with a polygenic and intricate history.     

东营凹陷中央隆起带沙河街组碳酸盐胶结物发育特征及其形成机制

碳酸盐胶结物是东营凹陷中央隆起带砂岩储层中重要的自生矿物,但其形成机制目前尚无深入研究.首先在岩相观察下针对东营凹陷中央隆起带沙河街组的碳酸盐胶结物进行期次划分并归纳其发育特征,再依据各期碳酸盐胶结物的共生矿物、碳氧同位素组成、流体包裹体温度、元素化学成分等信息对其形成机制进行研究.研究结果表明:研究区碳酸盐胶结物的碳不仅受到有机质成熟过程中排放的有机酸的影响,还受到沙四段沉积的湖相碳酸盐岩溶解的影响.研究区沙河街组主要发育四期碳酸盐胶结物:第一期碳酸盐胶结物以白云石为主,其形成过程与甲烷细菌对有机质的分解作用有关;第二期碳酸盐胶结物以方解石为主,与第一期碳酸盐胶结物之间夹有一层绿泥石薄膜,胶结物的形成与孔隙流体的浓缩导致的Ca、HCO₃-过饱和现象相关;第三期碳酸盐胶结物主要为方解石、白云石和铁白云石,以充填长石溶孔和原生孔隙为特征,其物质来源于长石的溶蚀及泥岩的脱水作用;第四期碳酸盐胶结物多为铁方解石和铁白云石,以充填早期碳酸盐溶蚀后形成的次生孔隙为特征,物质来源于粘土矿物的转化,多与黄铁矿颗粒共生,其形成过程受到烃类流体活动的影响.      

Diagenesis in the Middle Jurassic Khatatba Formation sandstones in the Shoushan Basin,northern Western Desert,Egypt

The Middle Jurassic Khatatba Formation acts as a hydrocarbon reservoir in the subsurface in the Western Desert, Egypt. This study, which is based on core samples from two exploration boreholes, describes the lithological and diagenetic characteristics of the Khatatba Formation sandstones. The sandstones are fine‐ to coarse‐grained, moderately to well‐sorted quartz arenites, deposited in fluvial channels and in a shallow‐marine setting. Diagenetic components include mechanical and chemical compaction, cementation (calcite, clay minerals, quartz overgrowths, and a minor amount of pyrite), and dissolution of calcite cements and feldspar grains. The widespread occurrence of an early calcite cement suggests that the Khatatba sandstones lost a significant amount of primary porosity at an early stage of its diagenetic history. In addition to calcite, several different cements including kaolinite and syntaxial quartz overgrowth occur as pore‐filling and pore‐lining cements. Kaolinite (largely vermicular) fills pore spaces and causes reduction in the permeability of the reservoir. Based on framework grain–cement relationships, precipitation of the early calcite cement was either accompanied by or followed the development of part of the pore‐lining and pore‐filling cements. Secondary porosity development occurred due to partial to complete dissolution of early calcite cements and feldspar. Late kaolinite clay cement occurs due to dissolved feldspar and has an impact on the reservoir quality of the Khatatba sandstones. Open hydraulic fractures also generated significant secondary porosity in sandstone reservoirs, where both fractures and dissolution took place in multiple phases during late diagenetic stages. The diagenesis and sedimentary facies help control the reservoir quality of the Khatatba sandstones. Fluvial channel sandstones have the highest porosities and permeabilities, in part because of calcite cementation, which inhibited authigenic clays or was later dissolved, creating intergranular secondary porosity. Fluvial crevasse‐splay and marine sandstones have the lowest reservoir quality because of an abundance of depositional kaolinite matrix and pervasive, shallow‐burial calcite and quartz overgrowth cements, respectively. Copyright © 2013 John Wiley & Sons, Ltd.