Dolomitization by hypersaline reflux into dense groundwaters as revealed by vertical trends in strontium and oxygen isotopes: Upper Muschelkalk,Switzerland

The Trigonodus Dolomit is the dolomitized portion of the homoclinal ramp sediments of the Middle Triassic Upper Muschelkalk in the south‐east Central European Basin. Various dolomitizing mechanisms, followed by recrystallization, have been previously invoked to explain the low δ¹⁸O, high ⁸⁷Sr/⁸⁶Sr, extensive spatial distribution and early nature of the replacive matrix dolomites. This study re‐evaluates the origin, timing and characteristics of the dolomitizing fluids by examining petrographic and isotopic trends in the Trigonodus Dolomit at 11 boreholes in northern Switzerland. In each borehole the ca 30 m thick unit displays the same vertical trends with increasing depth: crystal size increase, change from anhedral to euhedral textures, ultraviolet‐fluorescence decrease, δ¹⁸O_VPDB decrease from ?1·0‰ at the top to ?6·7‰ at the base and an ⁸⁷Sr/⁸⁶Sr increase from 0·7080 at the top to 0·7117 at the base. Thus, dolomites at the top of the unit record isotopic values similar to Middle Triassic seawater (δ¹⁸O_VSMOW = 0‰; ⁸⁷Sr/⁸⁶Sr = 0·70775) while dolomites at the base record values similar to meteoric groundwaters from the nearby Vindelician High (δ¹⁸O_VSMOW = ?4·0‰; ⁸⁷Sr/⁸⁶Sr = >0·712). According to water–rock interaction modelling, a single dolomitizing or recrystallizing fluid cannot have produced the observed isotopic trends. Instead, the combined isotopic, geochemical and petrographic data can be explained by dolomitization via seepage‐reflux of hypersaline brines into dense, horizontally‐advecting groundwaters that already had negative δ¹⁸O and high ⁸⁷Sr/⁸⁶Sr values. Evidence for the early groundwaters is found in meteoric calcite cements that preceded dolomitization and in fully recrystallized dolomites with isotopic characteristics identical to the groundwaters following matrix dolomitization. This study demonstrates that early groundwaters can play a decisive role in the formation and recrystallization of massive dolomites and that the isotopic and textural signatures of pre‐existing groundwaters can be preserved during seepage‐reflux dolomitization in low‐angle carbonate ramps.     

Formation of magnesium‐smectite during lacustrine carbonates early diagenesis: Study case of the volcanic crater lake Dziani Dzaha (Mayotte – Indian Ocean)

The volcanic crater lake of Dziani Dzaha in Mayotte is studied to constrain the geochemical settings and the diagenetic processes at the origin of Mg‐phyllosilicates associated with carbonate rocks. The Dziani Dzaha is characterized by intense primary productivity, volcanic gases bubbling in three locations and a volcanic catchment of phonolitic/alkaline composition. The lake water has an alkalinity of ca 0·2 mol l^?1 and pH values of ca 9·3. Cores of the lake sediments reaching up to one metre in length were collected and studied by means of carbon–hydrogen–nitrogen elemental analyzer, X‐ray fluorescence spectrometry and X‐ray powder diffraction. In surface sediments, the content of total organic carbon reaches up to 20 weight %. The mineral content consists of aragonite and hydromagnesite with minor amounts of alkaline feldspar and clinopyroxene from the volcanic catchment. Below 30 cm depth, X‐ray diffraction analyses of the <2 μm clay fraction indicate the presence of a saponite‐like mineral, a Mg‐rich smectite. The saponite‐like mineral accumulates at depth to reach up to ca 30 weight %, concurrent with a decrease of the contents of hydromagnesite and organic matter. Thermodynamic considerations and mineral assemblages suggest that the evolution of the sediment composition resulted from early diagenetic reactions. The formation of the saponite‐like mineral instead of Al‐free Mg‐silicates resulted from high aluminum availability, which is favoured in restricted lacustrine environments hosted in alkaline volcanic terrains commonly emplaced during early stages of continental rifting. Supersaturation of the lake water relative to saponite is especially due to high pH values, themselves derived from high primary productivity. This suggests that a genetic link may exist between saponite and the development of organic‐rich carbonate rocks, which may be fuelled by the input of CO₂‐rich volcanic gases. This provides novel insights into the composition and formation of saponite‐rich deposits under a specific geodynamic context such as the Cretaceous South Atlantic carbonate reservoirs.     

Reef Fabrics, biotic crusts and syndepositional cements of the Latemar reef margin (Middle Triassic), northern Italy

The Latemar reef buildup of the central Dolomites (northern Italy) provides a rare opportunity to examine an in-place Middle Triassic (Upper Anisian to Lower Ladinian) platform margin that is not strongly deformed or dolomitized. The margin lies between the flat lying platform interior and steeply dipping foreslope clinoforms. Across this transition, the depositional profile relates directly to a consistent lateral facies pattern: (1) restricted-biota grainstone of the platform interior, (2) ‘Tubiphytes’-rich boundstone and (3) diverse-biota grainstone that grades into (4) foreslope breccia beds. The boundstone and diverse-biota grainstone facies comprise the platform margin. The boundstone facies consists of a framework of small (< 10 cm) skeletal remains (< 10% by volume) with associated biotic crusts, internal sediments and syndepositional cements. Crusts and cements constitute most of the rock volume and created the boundstone fabric. Biotic crusts exhibit gravity-defying geometries and range from a light grey, ‘structure grumeleuse’ rind to dark grey, micritic laminae. Both cements and biotic crusts occur as redeposited talus in the foreslope talus deposits, indicating a syndepositional origin. The diverse-biota grainstone facies primarily consists of skeletal-peloidal grainstone with a diverse open marine biotic assemblage, in contrast to the restricted biota grainstones of the platform interior that have a low diversity, restricted marine biota. Metre scale hexacoral boundstone and centimetre-scale sponge boundstone and microbial boundstone occur as isolated patches (tens to hundreds of metres apart) within the diverse-biota grainstone facies. The depositional profile, facies zonation and biotic constituents all indicate that the Latemar buildup had a shallow water reef margin, in contrast to previous interpretations that these were upper slope reefs. The syndepositional biotic crusts and inorganic cementation played key roles in stabilizing the boundstone fabric to form a wave-resistant reef fabric.     

Significance of shallow core transects for reef models and sea‐level curves,Heron Reef,Great Barrier Reef

A sequence of shallow reef cores from Heron Reef, Great Barrier Reef, provides new insights into Holocene reef growth models. Isochron analysis of a leeward core transect suggests that the north‐western end of Heron Reef reached current sea‐level by ca 6·5 kyr bp and then prograded leeward at a rate of ca 19·6 m/kyr between 5·1 kyr and 4·1 kyr bp (pre‐1950) to the present reef margin. A single short core on the opposing margin of the reef is consistent with greater and more recent progradation there. Further to the east, one windward core reached modern sea‐level by ca 6·3 kyr bp , suggesting near ‘keep‐up’ behaviour at that location, but the opposing leeward margin behind the lagoon reached sea‐level much more recently. Hence, Heron Reef exhibited significantly different reef growth behaviour on different parts of the same margin. Mean reef accretion rates calculated from within 20 m of one another in the leeward core transect varied between ca 2·9 m and 4·7 m/kyr depending on relative position in the prograding wedge. These cores serve as a warning regarding the use of isolated cores to inform reef growth rates because apparent aggradation at any given location on a reef varies depending on its location relative to a prograding margin. Only transects of closely spaced cores can document reef behaviour adequately so as to inform reef growth models and sea‐level curves. The cores also emphasize potential problems in U‐series dates for corals within a shallow (ca 1·5 m) zone beneath the reef flat. Apparent age inversions restricted to that active diagenetic zone may reflect remobilization and concentration of Th in irregularly distributed microbialites or biofilms that were missed during sample vetting. Importantly, the Th‐containing contaminant causes ages to appear too old, rather than too young, as would be expected from younger cement.     

Formation of lacustrine dolomite in the late Miocene marginal lakes of the East Mediterranean (Northern Israel)

The study focuses on the formation of lacustrine dolomite in late Miocene lakes, located at the East Mediterranean margins (Northern Israel). These lakes deposited the sediments of the Bira (Tortonian) and Gesher (Messinian) formations that comprise sequences of dolostone and limestone. Dolostones are bedded, consist of small‐sized (<7 μm), Ca‐rich (52 to 56 mol %) crystals with relatively low ordering degrees, and present evidence for replacement of CaCO₃ components. Limestones are comprised of a wackestone to mudstone matrix, freshwater macrofossils and intraclasts (mainly in the Bira Formation). Sodium concentrations and isotope compositions differ between limestones and dolostones: Na = ~100 to 150 ppm; ~1000 to 2000 ppm; δ¹⁸O = ?3·8 to ?1·6‰; ?2·0 to +4·3‰; δ¹³C = ?9·0 to ?3·4‰; ?7·8 to 0‰ (VPDB), respectively. These results indicate a climate‐related sedimentation during the Tortonian and early Messinian. Wet conditions and positive freshwater inflow into the carbonate lake led to calcite precipitation due to intense phytoplankton blooms (limestone formation). Dry conditions and enhanced evaporation led to precipitation of evaporitic CaCO₃ in a terminal lake, which caused an increased Mg/Ca ratio in the residual waters and penecontemporaneous dolomitization (dolostone formation). The alternating lithofacies pattern reveals eleven short‐term wet–dry climate‐cycles during the Tortonian and early Messinian. A shift in the environmental conditions under which dolomite formed is indicated by a temporal decrease in δ¹⁸O of dolostones and Na content of dolomite crystals. These variations point to decreasing evaporation degrees and/or an increased mixing with meteoric waters towards the late Messinian. A temporal decrease in δ¹³C of dolostones and limestones and appearance of microbial structures in close association with dolomite suggest that microbial activity had an important role in allowing dolomite formation during the Messinian. Microbial mediation was apparently the main process that enabled local growth of dolomite under wet conditions during the latest Messinian.     

Effect of pedogenesis on the stable isotopic composition of calcretes and n‐alkanes: Implications for palaeoenvironmental reconstruction

In a fluvial system, depending on sub‐aerial exposure, non‐pedogenic pond calcretes can be modified into pedogenic calcretes. The present study attempts to understand the effect of sub‐aerial exposure and pedogenesis on calcretes using carbon and oxygen isotopic composition. For this purpose, two profiles (profile‐A and profile‐B) from the same stratigraphic level in Rayka from the western part of India were selected. The profiles are separated by a distance of 500 m and showed differences in calcrete characteristics. In profile‐A, the calcretes showed pedogenic features (root traces and void filling spar) whereas calcretes in profile‐B showed non‐pedogenic characteristics (fine laminations). However, some of the calcretes in profile‐A exhibited remnants of fine laminations suggesting that initially the calcretes had a non‐pedogenic origin but were modified due to pedogenesis. In profile‐A, the carbon and oxygen isotope values of pedogenic calcrete (δ¹³C_PC and δ¹⁸O_PC) showed more variation compared with non‐pedogenic pond calcretes (δ¹³C_SPC and δ¹⁸O_SPC) in profile‐B. The δ¹³C_PC and δ¹³C_SPC values exhibited a spread of 3·0‰ and 1·3‰, respectively, and δ¹⁸O_PC and δ¹⁸O_SPC values showed a spread of 2·3‰ and 1·3‰, respectively. The differences in the isotopic composition between the two profiles suggest that pedogenesis controlled the isotopic inheritance in calcretes. In addition, the carbon isotopic composition of organic matter (δ¹³C_OM) and n‐alkanes (δ¹³C_n‐alk) that forms the basis of palaeovegetational reconstruction have also been measured to understand the effect of pedogenesis on organic matter in both of the profiles. The average δ¹³C_OM values in profile‐A and profile‐B are ?23·4‰ and ?21·1‰, respectively. The disparity in δ¹³C_OM values is a result of the difference in the sources and preservation of organic matter. However, the δ¹³C_n‐alk values show a similar trend in profile‐A and profile‐B, indicating that sources of n‐alkanes are the same in both of the profiles and δ¹³C_n‐alk values are unaffected by the pedogenic modifications.     

Formation,diagenesis and palaeoenvironmental significance of upper Ediacaran fibrous dolomite cements

Neoproterozoic marine dolomite cements represent reliable, albeit complex, archives of their palaeoenvironment. Petrological and high-resolution geochemical data from well-preserved fibrous dolomite and pyrite in the upper Ediacaran (ca 551·1 to 548·0 Ma) Dengying Formation in south-west China are presented and discussed here. The aim of this research is to reconstruct the redox state of late Ediacaran shallow seawater and porewater in the Sichuan Basin using early marine diagenetic fabrics. Based on crystalline texture and axis, four basic types of fibrous dolomite cements formed penecontemporaneously in a microbialite reef setting at the platform margin: (i) bladed dolomites (replacement from a high-Mg calcite precursor); (ii) fascicular fast dolomites (replacement from an aragonitic precursor); (iii) fascicular slow dolomites; and (iv) radial slow dolomites. The latter two fabrics are considered direct marine porewater precipitates due to their length-slow character, cathodoluminescent zonation, and enriched copper and cobalt concentrations. Marine cements yield rare earth element and yttrium patterns comparable to modern seawater and represent a refined set of archive data relative to previously published bulk dolostones. Redox-sensitive elements and cathodoluminescence indicate that the fascicular fast dolomites formed in suboxic seawater, while fascicular slow and radial slow dolomites formed in euxinic marine porewaters. Microbial sulphate reduction during the formation of fascicular slow and radial slow dolomites is recognized by nanometre-scale spheroidal ankerite and sulphur-containing dolomite, and intergrown pyrite grains with U-shaped δ³⁴S transects. Data shown here suggest predominantly suboxic shallow late Ediacaran seawater and euxinic marine porewaters, with microbial activity promoting the direct precipitation of dolomite.     

Composition and origin of stromatactis‐bearing mud‐mounds (Upper Devonian,Frasnian), southern Rocky Mountains,western Canada

Stromatactis‐bearing mud‐mounds remain an enigmatic reef type despite being common in Palaeozoic ramp settings. Two well preserved Upper Devonian (Frasnian) mud‐mounds in the Mount Hawk Formation crop out side by side in the southern Rocky Mountains of west‐central Alberta and provide an opportunity to develop a new case study that can be compared with the other coeval examples, such as those well‐known ones in southern Belgium, as well as evaluate competing hypotheses for mud‐mound formation. The southern mud‐mound is 46·2 m thick and 38·6 m wide at the base, whilst the northern one is 53·3 m thick and 72·2 m wide at the base, and they exhibit three or four growth stages indicated by interfingering and onlapping geometries with flanking strata. The biota is diverse, but fossils only occupy 10·7% by volume, among which sponge spicules, echinoderms, ostracods, brachiopods and calcimicrobes belonging to Girvanella and Rothpletzella are the most common. Five microfacies are discriminated in the mud‐mounds: biomicrite, clotted micrite, spiculite, stromatolite and laminite, with clotted micrite comprising the largest proportion. There is no internal vertical or lateral palaeoecological zonation, and the presence of calcimicrobes and calcareous algae throughout indicates accretion entirely within the photic zone, in a deeper ramp setting seaward of a large carbonate platform to the east. Stromatactis is abundant and the cavities were mostly due to excavation by currents rather than physical collapse of spiculate siliceous sponges. Formation of lime mud involved a combination of multiple organisms, mechanisms and processes. Cyanobacteria were integral to mud‐mound frame‐building and accretion because they stabilized the surface, often permineralized to form Girvanella and provided organic matter that was decomposed by bacteria. This induced precipitation of micrite, forming early indurated rigid masses, evidenced by the presence of intraclasts, stromatactis cavities, isopachous marine cements, absence of bioturbation and rare synsedimentary brittle deformation. The same microbial components, invertebrate biota and clotted micrite occur in underlying strata, suggesting that there was a protracted period of potential mud‐mound initiation before the exact conditions arose to trigger it. The ramp setting, antecedent sea floor topography and relative sea‐level likely contributed together to control this. This study indicates that mud‐mound formation was controlled by a combination of processes, but they are essentially a microbial buildup.     

Three‐fold nature of coastal progradation during the Holocene eustatic highstand,Po Plain,Italy – close correspondence of stratal character with distribution patterns

Although general trends in transgressive to highstand sedimentary evolution of river‐mouth coastlines are well‐known, the details of the turnaround from retrogradational (typically estuarine) to aggradational–progradational (typically coastal/deltaic) stacking patterns are not fully resolved. This paper examines the middle to late Holocene eustatic highstand succession of the Po Delta: its stratigraphic architecture records a complex pattern of delta outbuilding and coastal progradation that followed eustatic stabilization, since around 7·7 cal kyr bp . Sedimentological, palaeoecological (benthic foraminifera, ostracods and molluscs) and compositional criteria were used to characterize depositional conditions and sediment‐dispersal pathways within a radiocarbon‐dated chronological framework. A three‐stage progradation history was reconstructed. First, as soon as eustasy stabilized (7·7 to 7·0 cal kyr bp ), rapid bay‐head delta progradation (ca 5 m year^?1), fed mostly by the Po River, took place in a mixed, freshwater and brackish estuarine environment. Second, a dominantly aggradational parasequence set of beach‐barrier deposits in the lower highstand systems tract (7·0 to 2·0 cal kyr bp ) records the development of a shallow, wave‐dominated coastal system fed alongshore, with elongated, modestly crescent beaches (ca 2·5 m year^?1). Third, in the last 2000 years, the development of faster accreting and more rapidly prograding (up to ca 15 m year^?1) Po delta lobes occurred into 30 m deep waters (upper highstand systems tract). This study documents the close correspondence of sediment character with stratal distribution patterns within the highstand systems tract. Remarkable changes in sediment characteristics, palaeoenvironments and direction of sediment transport occur across a surface named the ‘A–P surface’. This surface demarcates a major shift from dominantly aggradational (lower highstand systems tract) to fully progradational (upper highstand systems tract) parasequence stacking. In the Po system, this surface also reflects evolution from a wave‐dominated to river‐dominated deltaic system. Identifying the A–P surface through detailed palaeoecological and compositional data can help guide interpretation of highstand systems tracts in the rock record, especially where facies assemblages and their characteristic geometries are difficult to discern from physical sedimentary structures alone.     

A steep-fronted Carboniferous carbonate platform: clinoformal geometry and lithofacies (Picos de Europa, NW Spain)

A steep‐margined carbonate platform is developed in the Carboniferous synorogenic foreland basin of northern Spain. Dips of 60–90° produced during Late Carboniferous thrusting enable cross‐sections of a 4‐km‐wide portion of the marginal area of this platform (Las Llacerias outcrop) to be studied in aerial photographs at a seismic scale. Three stratal domains are observed: (1) a horizontal‐bedded platform; (2) a clinoformal‐bedded margin with a relief of up to 500 m; and (3) a low‐angle toe‐of‐slope, where slope beds interfinger with basin sediments. The slope shows well‐bedded sigmoidal clinoforms with depositional dips ranging from 15° to 32°. Based on lithology and stratal patterns, four facies groups have been recognized: (1) a flat‐topped platform, in which thick algal boundstone, skeletal packstone–grainstone and peloidal micrite wackestone with a poorly rhythmic character prevail; (2) the platform margin and upper slope, characterized by microbial boundstone spanning a bathymetric range of ≈150 m measured from the break of slope; (3) a slope, predominantly composed of margin‐derived rudstones and breccias; and (4) a toe‐of‐slope to basin zone, where a cyclic alternation of spiculitic siltstones, packstone to grainstone calciturbidites and rudstone/breccia is visible. Five successive stages of platform development are deduced: (1) Bashkirian: flooding of the pre‐existing Serpukhovian platform giving rise to the nucleation of a low‐angle ramp to the south‐east of the study area with microbial mud‐mound accumulations, and breccias and calciturbidites on the margins; (2) Early Moscovian: an influx of siliciclastic sediment buried part of the platform and reduced the area of carbonate sedimentation; (3) Moscovian: aggradation and progradation of the carbonate system produced an extensive steep‐margined and flat‐topped shallow‐water platform (shelf system); (4) Latest Moscovian–earliest Kasimovian: drowning of the platform; and (5) Kasimovian: covering of the platform by marly calcareous ramp sediments.     

Sublacustrine hydrothermal seeps and silicification of microbial bioherms in the Ediacaran Oued Dar'a caldera,Anti‐Atlas,Morocco

This paper presents a case study of the sublacustrine precipitation of hydrothermal silica ± TiO₂ in the Ediacaran Mançour Group of the Saghro inlier, Anti‐Atlas, Morocco. Lacustrine carbonates containing stromatolitic mats and bioherms occur in ephemeral ponds developed within the Oued Da'ra caldera. Its syn‐eruptive infill consists of pyroclastites, ashflow tuffs, and subsidiary lava flows and sills, whereas inter‐eruptive deposition is mainly represented by slope‐related debris‐flow breccias and landslides, alluvial fans and fluvial channels. Carbonate production took place in a mosaic of differentially subsiding, fault‐bounded intra‐caldera blocks controlled by episodic collapse‐induced drowning, pyroclastic blanketing and migration of alluvial/fluvial environments. After microbial carbonate production, the carbonates recorded several early‐diagenetic processes, punctuated by polyphase fissuring (controlling secondary permeability) locally linked to hydrothermal influx. Three generations of carbonate cements are recognisable: (i) fibrous, botryoidal and blocky/drusy mosaics of calcite; (ii) idiotopic mosaics of dolomite caused by flushing of hypersaline Mg‐rich brines; and (iii) euhedral to drusy calcite via dedolomitization. The δ¹³C and δ¹⁸O values from carbonate cements broadly become successively isotopically lighter, as a result of meteoric and hydrothermal influence, and were probably overprinted by the Panafrican‐3 phase that affected the top of the Mançour Group. Two mechanisms of silicification are involved: (i) early‐diagenetic occlusion of interparticle pores at the sediment/water interface of pyroclastic substrates and reefal core and flanks; and (ii) hydrothermal precipitation of silica ± TiO₂ lining fissures and vuggy porosity encased in the host rock. Silica conduits cross‐cutting lacustrine mats and bioherms exhibit high potential of preservation in collapsed volcanic calderas. Primary fluid inclusions of hydrothermal silica contain brine relics with NaCl/CaCl₂ ratios of 2·1 to 4·4, representing minimum entrapment temperatures of about 142 to 204°C, and abiotic hydrocarbons (heavy alkanes) related to serpentinization of the volcanic and volcanosedimentary basement of the Oued Dar'a caldera.     

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.     

Growth mechanisms and geochemistry of carbonate concretions from the Cambrian Wheeler Formation (Utah,USA)

Carbonate concretions provide unique records of ancient biogeochemical processes in marine sediments. Typically, they form in organic‐rich mudstones, where a significant fraction of the bicarbonate required for carbonate precipitation is supplied from the decomposition of organic matter in the sediments. As a result, carbonates that comprise concretions are usually characterized by broad ranges in δ¹³C and include values that are significantly depleted relative to seawater. This article reports results from a physical, petrographic and geochemical analysis of 238 concretions from the Wheeler Formation (Cambrian Series 3), Utah, USA, which are unusual in several respects. Most prominently, they formed in organic‐poor mudstones (total organic carbon = 0·1 to 0·5%) and are characterized by a narrow range of δ¹³C that onlaps the range of contemporaneous seawater values. Subtle centre to edge trends in δ¹³C demonstrate that concretion precipitation was initiated by local chemical gradients set up by microbial activity in the sediments, but was sustained during growth by a large pool of inorganic bicarbonate probably derived from alkaline bottom waters. The large inorganic pool appears to have been important in facilitating rapid precipitation of the concretion matrix, which occurred via both displacive and replacive carbonate precipitation during early diagenesis. Stable isotope data from cogenetic pyrite (δ³⁴S) and silica (δ¹⁸O) phases provide insight into the evolution of biogeochemical processes during concretion growth, and suggest that concretions were formed almost entirely during sulphate reduction, with only minor modification thereafter. Concretions of the Wheeler Formation appear to represent an end‐member system of concretion formation in which rapid growth was promoted by ions supplied from sea‐water. As such, they offer insight into the spectrum of processes that may influence the growth of carbonate concretions in marine sediments.     

Jurassic septarian concretions from NW Scotland record interdependent bacterial, physical and chemical processes of marine mudrock diagenesis

Septarian concretions in the Staffin Shales Formation (Kimmeridgian, Isle of Skye) allow controls on concretion rheology and septarian cracking to be investigated. Stratabound concretions consist of anhedral ferroan calcite microspar enclosing clay and minor pyrite. Intergranular volumes range from 77% to 88%, and calcite δ¹³C and δ¹⁸O values in most concretion bodies range from ?10·0‰ to ?17·3‰ and +0·3‰ to ?0·6‰ respectively, consistent with rapid and pervasive cementation in marine pore fluids. Septarian rupture occurred during incipient cementation, with a sediment volume reduction of up to 43%. Crack‐lining brown fibrous calcite records pore fluid re‐oxygenation during a depositional hiatus, followed by increasing Fe content and δ¹³C related to bacterial methanogenesis. Brown colouration results from an included gel‐like polar organic fraction that probably represents bacterially degraded biomass. A new hypothesis for concretion growth and septarian cracking argues that quasi‐rigid ‘proto‐concretions’ formed via binding of flocculated clays by bacterial extracellular polysaccharide substances (EPS). This provided rheological and chemical conditions for tensional failure, subcritical crack growth, volume contraction, calcite nucleation, and incorporation of degraded products into crack‐lining cements. Bacterial decay of EPS and syneresis of host muds provided internal stresses to initiate rupture at shallow burial. Development of septarian (shrinkage) cracks in muds is envisaged to require pervasive in situ bacterial colonization, and to depend on rates of carbonate precipitation versus EPS degradation and syneresis. Subsequent modification of septarian concretions included envelopment by siderite and calcite microspar, hydraulic fracturing associated with Cretaceous shallow burial or Palaeogene uplift; and cementation by strongly ferroan, yellow sparry calcite that records meteoric water invasion of the host mudrocks. An abundance of fatty acids in these spars indicates aqueous transport of organic breakdown products, and δ¹³C data suggest a predominantly methanogenic bicarbonate source. However, the wide δ¹⁸O range for petrographically identical cement (?1·3‰ to ?15·6‰) is difficult to explain.     

Holocene and Pleistocene fringing reef growth and the role of accommodation space and exposure to waves and currents (Bora Bora,Society Islands,French Polynesia)

Holocene fringing reef development around Bora Bora is controlled by variations in accommodation space (as a function of sea‐level and antecedent topography) and exposure to waves and currents. Subsidence ranged from 0 to 0·11 m kyr^?1, and did not create significant accommodation space. A windward fringing reef started to grow 8·7 kyr bp , retrograded towards the coast over a Pleistocene fringing reef until ca 6·0 kyr bp , and then prograded towards the lagoon after sea‐level had reached its present level. The retrograding portion of the reef is dominated by corals, calcareous algae and microbialite frameworks; the prograding portion is largely detrital. The reef is up to 13·5 m thick and accreted vertically with an average rate of 3·12 m kyr^?1. Lateral growth amounts to 13·3 m kyr^?1. Reef corals are dominated by an inner Pocillopora assemblage and an outer Acropora assemblage. Both assemblages comprise thick crusts of coralline algae. Palaeobathymetry suggests deposition in 0 to 10 m depth. An underlying Pleistocene fringing reef formed during the sea‐level highstand of Marine Isotope Stage 5e, and is also characterized by the occurrence of corals, coralline algal crusts and microbialites. A previously investigated, leeward fringing reef started to form contemporaneously (8·78 kyr bp ), but is thicker (up to 20 m) and solely prograded throughout the Holocene. A shallow Pocillopora assemblage and a deeper water Montipora assemblage were identified, but detrital facies dominate. At the Holocene reef base, only basalt was recovered. The Holocene windward–leeward differences are a consequence of less accommodation space on the eastern island side that eventually led to a more complex reef architecture. As a result of higher rates of exposure and flushing, the reef framework on the windward island side is more abundant and experienced stronger cementation. In the Pleistocene, the environmental conditions on the leeward island side were presumably unfavourable for fringing reef growth.     

Facies and sequence stratigraphic architecture of the Mural Limestone (Albian), Arizona: Carbonate response to global and local factors and implications for reservoir characterization

This study documents the detailed facies and sequence stratigraphic architecture of a multi-cyclic patch-reef and its associated ramp interior facies that formed during Oceanic Anoxic Event 1b in the Mural Limestone, Arizona, USA. Ramp interior facies are comprised of bedded wackestone/packstone, rudist build-up and coral–algal patch-reef facies located north of Bisbee, Arizona, at the Grassy Hill locality. The larger multi-cyclic patch-reef that developed coevally ca 5 km to the south of Grassy Hill consists of a high-angle windward margin with a narrow ca 70 m long reef frame containing vertically zonated Microsolena, Actinastrea, diverse branching coral and rudist assemblages, and an 870 m long low-angle leeward margin comprised of reef debris rudstone and grainstone shoal facies. Similar reef geomorphology and orientation is documented across the Gulf of Mexico and reflects the shelf-wide north to north-east-trending prevailing wind and current energies. Controls affecting reef formation and growth patterns include changes in accommodation space associated with low-amplitude global sea-level rise and regional thermotectonic subsidence, local accommodation space and nutrient fluctuations associated with the inner shelf depositional setting within a humid and siliciclastic-rich environment. Four aggradational to retrogradational high-frequency sequences are documented in Arizona: High-frequency sequences 1 and 2 represent the first pulse of patch-reef development in an overall second-order marine transgression over the Sonora/Bisbee Shelf. These sequences correlate to δ¹³C signatures associated with Oceanic Anoxic Event 1b across the Gulf of Mexico and suggest that carbonate reefs persisted on the ramp interior during this time. High-frequency sequences 3 and 4 record a second brief transgression and backstepping of reef facies followed by the final regression of shallow shelf carbonates that correlates to more robust patch-reef development in Sonora, Mexico. The patch-reef at Paul Spur is an excellent outcrop analogue for productive patch-reefs in the Maverick Basin (Comanche Shelf) of Texas. Detailed facies mapping of this outcrop analogue shows that the greatest reservoir potential is contained within the backreef grainstone shoals where primary porosity of up to 15% is observed.     

Dolomitization,gypsum calcitization and silicification in carbonate–evaporite shallow lacustrine deposits

This paper describes and interprets the mineral and facies assemblages that occur in carbonate–evaporite shallow lacustrine deposits, considering the importance of the processes pathway (i.e. dolomitization, gypsum calcitization and silicification). The Palaeogene deposits of the Deza Formation (Almazán Basin, central‐northern Spain) are selected as a case study to determine the variety of physicochemical processes taking place in carbonate–evaporite shallow lakes and their resulting diagenetic features. Dolostones are the predominant lithology and are composed mainly of dolomite with variable amounts of secondary calcite (5 to 50%), which mainly mimic lenticular gypsum (pseudomorphs). Five morphological types of dolomite crystal were identified as follows: dolomite tubes, dolomite cylinders, rhombohedral dolomite, spheroidal and quasi‐rhombohedral dolomite, and cocoon‐shaped dolomite. The dolomite cylinders and tubes are interpreted as the dolomitized cells of a widespread microbial community. The sequence of diagenetic processes started with growth of microlenticular interstitial gypsum in a calcareous mud deposited on the playa margin mudflats, and that sometimes included microbial sediments. Immediately following growth of gypsum, dolomite replaced the original calcite (or possibly aragonite) muds, the microbial community and the gypsum. Partial or total replacement of gypsum by dolomite was related mainly to the biomineralization of endolithic microbial communities on gypsum crystals. Later calcitization took place under vadose, subaerial exposure conditions. The development of calcrete in distal alluvial settings favoured the release of silica and subsequent silicification on the playa margin mudflats. Stable isotope compositions of calcite range from ?9·02 to ?5·83‰ δ¹³C_PDB and ?7·10 to 1·22‰ δ¹⁸O_PDB; for the dolomite, these values vary from ?8·93 to ?3·96‰ δ¹³C_PDB and ?5·53 to 2·4‰ δ¹⁸O_PDB. Quartz from the cherts has δ¹⁸O_SMOW values ranging from 27·1 to 31·1‰. Wide variation and relatively high δ¹⁸O_SMOW values for dolomite indicate evaporitic and closed hydrological conditions; increased influx of meteoric waters reigned during the formation of secondary calcite spar.     

Sedimentary evolution and environmental history of Lake Van (Turkey) over the past 600 000 years

The lithostratigraphic framework of Lake Van, eastern Turkey, has been systematically analysed to document the sedimentary evolution and the environmental history of the lake during the past ca 600 000 years. The lithostratigraphy and chemostratigraphy of a 219 m long drill core from Lake Van serve to separate global climate oscillations from local factors caused by tectonic and volcanic activity. An age model was established based on the climatostratigraphic alignment of chemical and lithological signatures, validated by ⁴⁰Ar/³⁹Ar ages. The drilled sequence consists of ca 76% lacustrine carbonaceous clayey silt, ca 2% fluvial deposits, ca 17% volcaniclastic deposits and 5% gaps. Six lacustrine lithotypes were separated from the fluvial and event deposits, such as volcaniclastics (ca 300 layers) and graded beds (ca 375 layers), and their depositional environments are documented. These lithotypes are: (i) graded beds frequently intercalated with varved clayey silts reflecting rising lake levels during the terminations; (ii) varved clayey silts reflecting strong seasonality and an intralake oxic–anoxic boundary, for example, lake‐level highstands during interglacials/interstadials; (iii) CaCO₃‐rich banded sediments which are representative of a lowering of the oxic–anoxic boundary, for example, lake level decreases during glacial inceptions; (iv) CaCO₃‐poor banded and mottled clayey silts reflecting an oxic–anoxic boundary close to the sediment–water interface, for example, lake‐level lowstands during glacials/stadials; (v) diatomaceous muds were deposited during the early beginning of the lake as a fresh water system; and (vi) fluvial sands and gravels indicating the initial flooding of the lake basin. The recurrence of lithologies (i) to (iv) follows the past five glacial/interglacial cycles. A 20 m thick disturbed unit reflects an interval of major tectonic activity in Lake Van at ca 414 ka bp . Although local environmental processes such as tectonic and volcanic activity influenced sedimentation, the lithostratigraphic pattern and organic matter content clearly reflect past global climate changes, making Lake Van an outstanding terrestrial archive of unprecedented sensitivity for the reconstruction of the regional climate over the last 600 000 years.     

A lost Tethyan evaporitic basin: Evidence from a Cretaceous hemipelagic meta‐selenite – red chert association in the Eastern Mediterranean realm

Ancient evaporite deposits are geological archives of depositional environments characterized by a long‐term negative precipitation balance and bear evidence for global ocean element mass balance calculations. Here, Cretaceous selenite pseudomorphs from western Anatolia (‘Rosetta Marble’) — characterized by their exceptional morphological preservation — and their ‘marine’ geochemical signatures are described and interpreted in a process‐oriented context. These rocks recorded Late Cretaceous high‐pressure/low‐temperature, subduction‐related metamorphism with peak conditions of 1·0 to 1·2 GPa and 300 to 400°C. Metre‐scale, rock‐forming radiating rods, now present as fibrous calcite marble, clearly point to selenitic gypsum as the precursor mineral. Stratigraphic successions are recorded along a reconstructed proximal to distal transect. The cyclical alternation of selenite beds and radiolarian ribbon‐bedded cherts in the distal portions are interpreted as a two type of seawater system. During arid intervals, shallow marine brines cascaded downward into basinal settings and induced precipitation. During more humid times, upwelling‐induced radiolarian blooms caused the deposition of radiolarite facies. Interestingly, there is no comparable depositional setting known from the Cenozoic world. Meta‐selenite geochemical data (δ¹³C, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr) plot within the range of reconstructed middle Cretaceous seawater signatures. Possible sources for the ¹³C‐enriched (mean 2·2‰) values include methanogenesis, gas hydrates and cold seep fluid exhalation. Spatially resolved component‐specific analysis of a rock slab displays isotopic variances between meta‐selenite crystals (mean δ¹³C 2·2‰) and host matrix (mean δ¹³C 1·3‰). The Cretaceous evaporite‐pseudomorphs of Anatolia represent a basin wide event coeval with the Aptian evaporites of the Proto‐Atlantic and the pseudomorphs share many attributes, including lateral distribution of 600 km and stratigraphic thickness of 1·5 to 2·0 km, with the evaporites formed during the younger Messinian salinity crisis. The Rosetta Marble of Anatolia may represent the best‐preserved selenite pseudomorphs worldwide and have a clear potential to act as a template for the study of meta‐selenite in deep time.     

Origin of blocky aragonite cement in Cenozoic glaciomarine sediments,McMurdo Sound,Antarctica

Inorganic aragonite occurs in a wide spectrum of depositional environments and its precipitation is controlled by complex physio-chemical factors. This study investigates diagenetic conditions that led to aragonite cement precipitation in Cenozoic glaciomarine deposits of McMurdo Sound, Antarctica. A total of 42 sandstones that host intergranular cement were collected from the CIROS-1 core, located proximal to the terminus of Ferrar Glacier. Standard petrography, Raman spectroscopy and electron microprobe analysis reveal a prominent aragonite cement phase that occurs as a pore-filling blocky fabric throughout the core. Oxygen isotope compositions (δ¹⁸O = −30·0 to −8·6‰ Vienna Pee-Dee Belemnite) and clumped isotope temperatures (TΔ₄₇ = 13·1 to 31·5°C) determined from the aragonite cements provide precise constraints on isotopic compositions (δ¹⁸O_w) of the parent fluid, which mostly range from −10·8 to −7·2‰ Vienna Standard Mean Ocean Water. The fluid δ¹⁸O_w values are consistent with those of pore water, previously identified as cryogenic brine in the nearby AND-2A core. Petrographic and geochemical data suggest that aragonite cement in the CIROS-1 core precipitated from a similar brine. The brine likely formed and infiltrated sediments in flooded glacial valleys along the western margin of McMurdo Sound during the middle Miocene Climatic Transition, and subsequently flowed basinward in the subsurface. Consequently, the brine forms as a longstanding subsurface fluid that has saturated Cenozoic sediments below southern McMurdo Sound since at least the middle Miocene. Aragonite cementation in the CIROS-1 core is interpreted to reflect its proximal position to sites of brine formation and greater likelihood of experiencing brines with sustained high carbonate saturation states and Mg/Ca ratios. This unusual occurrence expands the range of known natural occurrences of aragonite cement. Given the potential for cryogenic brine formation in glaciomarine settings, blocky aragonite, as the end member of the spectrum of aragonite cement morphology, may be more widespread in glaciomarine sediments than currently thought.