Deep‐burial alteration of early‐diagenetic carbonate concretions formed in Palaeozoic deep‐marine greywackes and mudstones (Bardo Unit,Sudetes Mountains,Poland)

Carbonate concretions formed in bathyal and deeper settings have been studied less frequently than those formed in shallow‐marine deposits. Similarly, concretions affected by catagenetic conditions have rarely been reported. Calcite concretions in deep‐marine mudstones and greywackes of the Bardo Unit (Sudetes Mountains, Poland) formed during early diagenesis and were buried to significant depths. Petrographic and geochemical (elemental and stable C and O isotopic) analyses document their formation close to the sediment–water interface, prior to mechanical compaction within the sulphate reduction zone and their later burial below the oil window. Although the concretions were fully formed during early diagenesis, the effects of increased temperature and interaction with late‐diagenetic interstitial fluids can be discerned. During maximum burial, the concretions underwent thorough recrystallization that caused alteration of fabric and elemental and O isotope composition. The initial finely crystalline cement was replaced by more coarsely crystalline, sheaf‐like, poikilotopic calcite in the concretions. These large calcite crystals engulf and partially replace unstable detrital constituents. The extremely low δ¹⁸O values (down to ?21·2‰ Vienna Pee Dee Belemnite) in the concretions are the result of the increased temperature in combination with alteration of volcanic glass, both causing a significant ¹⁸O‐depletion of bicarbonate dissolved in the interstitial fluids. Recrystallization led to uniform O isotope ratios in the concretions, but did not affect the C isotope signature. The δ¹³C values of the late‐diagenetic cements precipitated in the greywacke and in cracks cutting through concretions imply crystallization in the catagenetic zone and decarboxylation as a source of the bicarbonate. These late‐diagenetic processes took place in a supposedly overpressured setting, as suggested by clastic dykes and hydrofractures that cut through both concretions and host rock. All of these features show how the effects of early and late diagenesis can be distinguished in such rocks.     

Rinded iron‐oxide concretions: hallmarks of altered siderite masses of both early and late diagenetic origin

Iron‐bearing concretions are valuable records of oxidation states of subsurface waters, but the first concretions to form can be altered drastically during later diagenetic events. Distinctive concretions composed of heavy rinds of iron oxide that surround iron‐poor, mud‐rich cores are common along bases of fluvial cross‐bed sets of the Cretaceous Dakota Formation, Nebraska, USA. Concretion rinds thicken inward and cores contain 46 to 89% void space. Millimetre‐scale spherosiderites are abundant in palaeosols that developed in floodplain facies. Evolution of rinded concretions began when intraformational clasts were eroded from sideritic soils, transported, abraded and deposited in river channels. Alteration of siderite and formation of rinds occurred much later, perhaps in the Quaternary when sandstone pore waters became oxic. Dakota concretions are analogous to ‘rattlestones’ in Pleistocene fluvial channels of The Netherlands, and their rinded structure is analogous to that of iron‐rich concretions in the aeolian Navajo Sandstone of Utah. In all three deposits, rinded concretions formed when pre‐existing, siderite‐cemented concretions were oxidized within a sand matrix. Unlike fluvial examples, siderite in the Navajo Sandstone was autochthonous and of late diagenetic origin, having precipitated from carbon dioxide and methane‐enriched waters moving through folded and jointed strata. Iron‐rich rinds formed in all these strata because concretion interiors remained anaerobic, even as oxygen accumulated in the pore waters of their surrounding, permeable matrix. Iron oxide first precipitated at redox boundaries at concretion perimeters and formed an inward‐thickening rind. Acid generated by the oxidation reaction drove siderite dissolution to completion, creating the iron‐poor core. Iron‐oxide rinds are indicators of the former presence of siderite, a mineral that forms only under reducing conditions, during either early or late diagenesis. Siderite is vulnerable to complete oxidation upon exposure, so the distinctive rinded concretions are valuable clues that aid in deciphering diagenetic histories and for recognizing methanic floodplain palaeoenvironments and wet palaeoclimate.     

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

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

Significance of the chemistry and morphology of diagenetic siderite in clastic rocks of the Mesozoic Scotian Basin

Siderite (FeCO₃) is a widespread minor diagenetic mineral in clastic sedimentary basins. Although eodiagenetic authigenesis of siderite is well-known, siderite formed during burial diagenesis shows habits and chemical compositions that are poorly understood. This study tests the hypothesis that diagenetic siderite cements in sandstones in the Scotian Basin, offshore eastern Canada, show systematic variability in chemistry and habit that is a response to recrystallization and changing composition of basinal fluids. Mineral textures were determined from backscattered electron images, and chemistry mostly from electron microprobe analyses. Five chemical types of siderite are identified using k-means cluster analysis, based on the amount of substitution of Ca, Mg and Mn for Fe. Eodiagenetic microcrystalline coated grains, concretions and intraclasts in sandstones are principally Fe-rich siderite and locally have recrystallised to blocky equant crystals. Mesodiagenetic Mg-rich siderite partly replaced these equant crystals and also framework mica and K-feldspar grains, showing textural evidence for coupled dissolution–reprecipitation. Slender Mg-rich siderite rhombs (lozenges, bladed or wheat-seed siderite) have precipitated before and after the formation of quartz overgrowths in geochemical microenvironments. Magnesium substitution reflects Mg-rich formation waters resulting from smectite to illite conversion. Equivalent Ca-rich siderite occurs where sandstones overlie a Jurassic carbonate bank. Late Mn-rich siderite has complex textures resembling those of Mississippi-Valley type ores, with spheroidal rims, a honeycomb-like mesh and concentric infill around secondary pores. It also occurs in veins or replacing intraclasts, post-dating late ferroan-calcite cements in sandstones that show strong dissolution by hot basinal brines. The Ca, Mg and Mn content of diagenetic siderite, coupled with textural evidence for recrystallization, can thus be used to track changes in ambient formation fluids. Siderite habits and chemistry described from the Scotian Basin are found in many clastic basins, suggesting that the observed recrystallization textures and variation in chemical type are of broad application.     

Depth and controls of Ca-rhodochrosite precipitation in bioturbated sediments of the Eastern Equatorial Pacific, ODP Leg 201, Site 1226 and DSDP Leg 68, Site 503

The occurrence of early diagenetic Ca‐rhodochrosite [(Mn,Ca)CO₃] is reported in association with ‘griotte’‐type nodular limestones from basinal settings in the geological record; however, without the comparison of analogous modern examples, the controls on precipitation remain speculative. Here the findings of four layers of primary Ca‐rich rhodochrosite recovered from a modern deep‐sea setting in the Eastern Equatorial Pacific, from bioturbated sediments 300 m below sea floor, are reported (Ocean Drilling Program, Leg 201, Site 1226). The mineralogy is similar to cements in burrows recovered during Deep Sea Drilling Project Leg 68 at Eastern Equatorial Pacific Site 503 and from Ca‐rhodochrosite laminae in sediments of the central Baltic Sea. Petrographic relationships and constant oxygen isotopic compositions in the Ca‐rhodochrosite around 5‰ at all depths indicate a shallow burial depth of formation. The onset of 1‰ heavier oxygen isotope composition of Ca‐rhodochrosite at Site 503, about 30 m below the Pliocene/Pleistocene boundary, further suggests that precipitation occurs in the range of 30 m below sea floor. The approximate depth of formation allowed an approximate empirical fractionation factor for marine Ca‐rhodochrosite to be constrained that strongly differs from previously published theoretical values. Based on the approximate precipitation depth, authigenic Ca‐rhodochrosite forms within the SO₄^2?‐reduction zone. Moderately negative δ¹³C values (around ?3‰) and total organic carbon lower than 2 wt% indicate a relatively low contribution of CO₃^2? from organic C mineralization within the expanded redox zonation in the Eastern Equatorial Pacific. It is suggested that the alkalinity is increased by a rise in pH at focused sites of Mn‐reduction coupled with S^2? oxidation. High concentrations of Mn‐oxide can accumulate in layers or burrows because of Mn‐cycling in suboxic sediments as suggested for the Baltic Sea Ca‐rhodochrosites. This study demonstrates how early diagenetic precipitates document biogeochemical processes from past diagenetic systems.     

Spherical and columnar, septarian, 18O-depleted, calcite concretions from Middle–Upper Permian lacustrine siltstones in northern Mozambique: evidence for very early diagenesis and multiple fluids

Calcite septarian concretions from the Permian Beaufort Group in the Maniamba Graben (NW Mozambique) allow controls on the composition and nature of diagenetic fluids to be investigated. The concretions formed in lacustrine siltstones, where they occur in spherical (1 to 70 cm in diameter) and columnar (up to 50 cm long) forms within three closely spaced, discrete beds totalling 2·5 m in thickness. Cementation began at an early stage of diagenesis and entrapped non‐compacted burrows and calcified plant roots. The cylindrical concretions overgrew calcified vertical plant roots, which experienced shrinkage cracking after entrapment. Two generations of concretionary body cement and two generations of septarian crack infill are distinguished. The early generation in both cases is a low‐Mn, Mg‐rich calcite, whereas the later generation is a low‐Mg, Mn‐rich calcite. The change in chemistry is broadly consistent with a time (burial)‐related transition from oxic to sub‐oxic/anoxic conditions close to the sediment–water interface. Geochemical features of all types of cement were controlled by the sulphate‐poor environment and by the absence of bacterial sulphate reduction. All types of cement present have δ¹³C ranging between 0‰ and −15‰(Vienna Peedee Belemnite, V‐PDB), and highly variable and highly depleted δ¹⁸O (down to 14‰ Vienna Standard Mean Ocean Water, V‐SMOW). The late generation of cement is most depleted in both ¹³C and ¹⁸O. The geochemical and isotopic patterns are best explained by interaction between surface oxic waters, pore waters and underground, ¹⁸O‐depleted, reducing, ice‐meltwaters accumulated in the underlying coal‐bearing sediments during the Permian deglaciation. The invariant δ¹³C distribution across core‐to‐rim transects for each individual concretion is consistent with rapid lithification and involvement of a limited range of carbon sources derived via oxidation of buried plant material and from dissolved clastic carbonates. Syneresis of the cement during an advanced stage of lithification at early diagenesis is considered to be the cause of development of the septarian cracks. After cracking, the concretions retained a small volume of porosity, allowing infiltration of anoxic, Ba‐bearing fluids, resulting in the formation of barite. The results obtained contribute to a better understanding of diagenetic processes at the shallow burial depths occurring in rift‐bound, lacustrine depositional systems.     

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.     

台湾国姓地区中新世海相菱铁矿的成因

菱铁矿很好地记录了过去地质流体的信息,能够用于示踪生物地球化学反应相关的成岩作用带。台湾国姓地区中新世海相泥页岩中发育自生的菱铁矿结核,其成因尚未厘清。野外观察发现菱铁矿以不连续透镜体平行散布于泥页岩中,主要由自生碳酸盐菱铁矿（78.63%）等矿物组成。菱铁矿的稀土元素配分模式为轻稀土亏损、中稀土富集,无Ce异常,指示菱铁矿形成于弱氧化的沉积环境,弱氧化的环境促进了菱铁矿在次氧化带的沉淀。菱铁矿的δ13C_VPDB和δ18O_VPDB值分别为-3.69‰~+0.08‰和-1.09‰~+0.25‰,指示菱铁矿形成于次氧化带,碳源很可能是海水和有机质降解混合产生。研究表明自生菱铁矿能够被用于识别沉积物中的生物地球化学过程和指示成岩作用带。     

Origin of manganese carbonates in Jurassic red shale, central Japan

Manganese carbonate deposits in Japanese Jurassic sedimentary rocks were studied petrogeochemically. The deposits are characteristically composed of spheroidal micronodules, up to 1 mm in diameter, and always contain well-preserved radiolarian shells. Chemical elemental composition and mineralogical characteristics indicate that the micronodules contain rhodochrosite in a mixed carbonate phase composition (Mn_86.7?92.2Ca_2.2?2.9Mg_2.6?6.7Fe_2.6?5.6)CO₃ Carbon and oxygen isotope values, which range from ?7.99 to ?4.78‰ and ?4.05 to 0.28‰ relative to PDB, respectively, suggest that the manganese carbonate was precipitated in a suboxic zone. The micronodules closely resemble agglutinated benthic foraminifera in shape. We suggest that agglutinated foraminiferal tests composed of radiolarian shells accumulated selectively on the sediment surface during redeposition of bottom sediments and were replaced by manganese carbonate in suboxic diagenetic conditions of manganese reduction.     

Origin and diagenetic evolution of Ca–Mg–Fe carbonates in some coalfields of Japan

Carbonate concretions, lenses and bands in the Pleistocene, Palaeogene and Upper Triassic coalfields of Japan consist of various carbonate minerals with varied chemical compositions. Authigenic carbonates in freshwater sediments are siderite > calcite > ankerite > dolomite >> ferroan magnesite; in brackish water to marine sediments in the coal measures, calcite > dolomite > ankerite > siderite >> ferroan magnesite; and in the overlying marine deposits, calcite > dolomite >> siderite. Most carbonates were formed progressively during burial within a range of depths between the sediment-water interface and approximately 3 km. The mineral species and the chemical composition of the carbonates are controlled primarily by the initial sedimentary facies of the host sediments and secondarily by the diagenetic evolution of pore water during burial. Based on the regular sequence and burial depth of precipitation of authigenic carbonates in a specific sedimentary facies, three diagenetic stages of carbonates are proposed. Carbonates formed during Stage I (< 500 m) strongly reflect the initial sedimentary facies, e.g. low Ca-Mg siderite in freshwater sediments which are initially rich in iron derived from lateritic soil on the nearby landmass, and Mg calcite and dolomite in brackish-marine sediments whose pore waters abound in Ca²⁺ and Mg²⁺ originating in seawater and calcareous shells. Carbonates formed during Stage II (500–2000 m) include high Ca-Mg siderite, ankerite, Fe dolomite and Fe–Mg calcite in freshwater sediments. The assemblage of Stage II carbonates in brackish-marine sediments in the coal measures is similar to that in freshwater sediments. This suggests similar diagenetic environments owing to an effective migration and mixing of pore water due to the compaction of host sediments. Carbonates formed during Stage III (> 2000 m) are Fe calcite and extremely high Ca-Mg siderite; the latter is exclusively in marine mudstones. The supply of Ca is partly from the alteration of silicates in the sediments at elevated burial temperatures. After uplift, calcite with low Mg content precipitates from percolating groundwater and fills extensional cracks.     

Basin‐scale thermal and fluid flow histories revealed by carbonate clumped isotopes (Δ47) – Middle Jurassic carbonates of the Paris Basin depocentre

The reconstruction of past diagenetic conditions in sedimentary basins is often under‐constrained. This results from both the analytical challenge of performing the required analyses on the minute sample amounts available from diagenetic mineral phases and the lack of tracers for some of the diagenetic parameters. The carbonate clumped isotope thermometry (Δ₄₇) opens new perspectives for unravelling the temperatures of diagenetic phases together with the source of their parent fluids, two parameters that are otherwise impossible to constrain in the absence of exploitable fluid inclusions. Here is reported the study of a large number of sedimentary and diagenetic carbonate phases (from Middle Jurassic reservoirs of the Paris Basin depocentre) by combining detailed petrographic observations with a large number of Δ₄₇ data (n  > 45) on a well‐documented paragenetic sequence, including calcite and dolomite burial cements. The data reveal carbonate crystallization at temperatures between 29°C and 98°C from fluids with δ ¹⁸O_water values between −7‰ and +2‰, in response to the progressive burial and uplift of the Paris Basin, throughout 165 Myr of basin evolution. Coupled with the time–temperature evolution previously estimated from thermal maturity modelling, these temperatures allow determining the timing of four successive cementation episodes. The overall data set indicates a history of complex water mixing with a significant contribution of hypersaline waters from the Triassic aquifers migrated upward along faults during the Cretaceous subsidence of the basin. Subsequent large‐scale infiltrations of meteoric waters induced a dilution of these pre‐existing brines in response to the Paris Basin uplift in the Tertiary. Overall, the data presented here allow proposing an integrated approach to characterize the cementation events affecting the studied carbonate reservoir units, based on temperature, oxygen isotope composition and salinity of the parent fluids as well as on petrographic grounds.     

Early diagenesis and its relationship to depositional environment and relative sea-level fluctuations (Upper Cretaceous Marshybank Formation, Alberta and British Columbia)

Early diagenesis of the Upper Cretaceous (late Coniacian to early Santonian) Marshybank Formation was controlled by depositional environment (composition of depositional water, Fe and organic content of the sediment, sedimentation rate, proximity to the shoreline) and influx of meteoric water related to relative sea-level fall. Five depositional environments, each characterized by a distinct early diagenetic mineral assemblage, have been recognized. Offshore shelf sediments that were deposited in a dysaerobic environment are characterized by abundant framboidal pyrite and rare septarian concretions, composed of ‘early’ calcite and siderite. Intense sulphate reduction, promoted by the dysaerobic depositional water, was the primary influence on early diagenesis. Offshore shelf sediments deposited under aerobic conditions are characterized by abundant concretions, composed of two generations of siderite (S1 and S2). In this environment, methanogenesis, rather than sulphate reduction, was more important. Early diagenesis of the inner shelf sands was generally limited. However, in sands deposited proximal to the shoreline, mixing of marine and meteoric waters promoted crystallization of Fe-rich chlorite and siderite. The shoreface was characterized by dissolution of detrital minerals in the upper portion, and precipitation of kaolinite or illite/smectite in the lower portion. In the coastal plain environment, brackish water and early reducing conditions resulted in formation of abundant euhedral pyrite. Ankerite, rather than siderite, is the typical early diagenetic carbonate. The δ¹⁸O values of the earliest cements (i.e. ‘early’ calcite, siderite S1, inner shelf siderite) indicate crystallization from a low-¹⁸O, marine-derived porewater. Assuming crystallization at 25°C, a δ¹⁸O value of about ?7‰ (SMOW) can be estimated for the seaway during Marshybank Formation time. Similar calculations for the overlying Dowling Member (Puskwaskau Formation) suggest that the δ¹⁸O value of the seaway increased to about ?4% (SMOW), consistent with its transgressive nature. Very low δ¹⁸O values are exhibited by siderite S2. These results indicate crystallization during intermediate diagenesis (≥60°C) from meteoric water (≥? 15‰ SMOW) that entered the Marshybank Formation during sea-level lowstand.     

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.     

Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.     

Stable oxygen and carbon isotopes of carbonate concretions of the Miocene Yeonil Group in the Pohang Basin,Korea: Types of concretions and formation condition

Carbonate concretions in the Miocene sedimentary rocks of the Yeonil Group in the Pohang Basin (Korea) were investigated in terms of stable oxygen and carbon isotope composition to delineate the origin and associated diagenetic environment for their formation. Carbonate concretions are widely distributed in all the sedimentary rocks in the Pohang Basin, showing that the calcitic concretions are preserved within the mass-flow deposits and the dolomitic ones mostly in the hemipelagic siliceous rocks (diatomites). Concretions can be classified into four different types, on the basis of the stable isotopic signatures, each of which represents its own geochemical range.Type I concretions are calcitic and are composed of micrite to microspar. They occur in the conglomerates and sandstones which were deposited by mass flows (debris flow to turbidity current). It shows relatively lower δ¹⁸O (− 14.0 to − 9.3‰) and δ¹³C (− 19.6 to − 8.4‰) values. These concretions grew in a sulfate reducing zone under the influence of residual ambient seawater which had been significantly modified by volcanogenic sediments. Type II concretions are also calcitic, composed mostly of micrite with minor microspar and found in the sandstones. These concretions are characterized by relatively high δ¹⁸O (+ 1.8 to + 2.4‰) and variable δ¹³C (− 17.3 to − 0.4‰) values. These isotopic signatures reflect that Type II concretions formed from just beneath the sediment/water interface down to the sulfate reducing zone through the early stage of methanogenesis. Type III concretions are also calcitic, and composed largely of micrite with a minor contribution of microspar. They are observed in hemipelagic mudrocks which were deposited under the influence of mass flows. They are characterized by intermediate to high δ¹⁸O (− 4.6 to + 1.6‰) and high δ¹³C (− 1.3 to + 8.8‰) values. These concretions grew in a methanogenic zone by residual ambient seawater and/or seawater slightly modified by reaction with volcanogenic sediments. Type IV concretions are dolomite with calcite inclusion, and occur in hemipelagic siliceous rocks. These concretions are mostly composed of micrite and characterized by variable δ¹⁸O (− 9.1 to + 0.7‰) and high δ¹³C (+ 3.1 to + 17.9‰) values, suggesting formation in the methanogenic zone, although the residual ambient seawater is slightly modified by volcanogenic sediments.The same type of the concretions is widely distributed throughout the basin and always shows its own distinctive stable isotopic signature. This means that the formation of the given type depends upon the lithology and composition of host sediments that are closely related to the depositional process of the fan-delta systems regardless of their localities. Further, the different types of concretions are also found at the different, but closely spaced stratigraphic levels in the same locality, displaying the distinctive diagenetic conditions for each type. Such preservation of the unique diagenetic signatures in individual type of concretion suggests that the concretions formed in a completely closed diagenetic system. Therefore, caution should be made to simplify and generalize the diagenetic condition for the formation of any concretions in a large sedimentary basin.     

柴北缘西段鄂博梁构造带储层碳酸盐胶结物成因及其油气地质意义——来自碳、氧同位素的约束

碳酸盐胶结物是古流体活动的产物,蕴含着成岩环境、成岩流体演化等方面的有益地质信息。综合运用岩石学、矿物学和地球化学方法,对柴北缘西段鄂博梁构造带侏罗系、古近系、新近系储层中普遍存在的碳酸盐胶结物的成因机制进行了研究。结果表明,研究区碳酸盐胶结物以方解石和含铁方解石为主。鄂博梁I号构造主要见方解石,其碳、氧同位素分布范围较大:-13.47‰ <δ13C_PDB <2.54‰,-15.93‰ <δ18O_PDB <-4.74‰,成因多种多样,与有机质脱羧、同生-准同生、甲烷生成等作用有关;鄂博梁III号-鸭湖构造则主要见含铁方解石,其碳、氧同位素分布集中:-4.24‰ <δ13C_PDB <-1.99‰,-11.17‰ <δ18O_PDB <-9.41‰,为沉积压实水沉淀而成。碳酸盐胶结物的成因揭示了鄂博梁构造带无机-有机流体的活动信息,从而为该地区油气成藏研究提供了重要依据。     

Calcite precipitation and Recrystallization fabrics—their significance in Jurassic Limestones of Europe

Many fabrics in Corallian (Upper Jurassic) carbonates in England, France and Switzerland are bigenetic, forming by solution/precipitation and recrystallization processes. Early precipitated cements are non‐ferroan, whereas those formed later are decidedly ferroan. Mossbauer spectroscopy has shown that the iron in the carbonates is largely divalent, substituting for calcium in the calcite lattice. The cements may be subdivided into those forming in an oxidizing environment, and those forming in a reducing environment. Fabric evidence indicates that a solution period separates the two cement phases. The diagenetic history is linked with the sedimentation pattern. Thus, under progressive build up of sediments into shallow‐water or supratidal conditions, the first‐phase cement probably precipitated from non‐marine, partially oxygenated vadose water. Subsequent subsidence and sedimentation resulted in the depression of partially cemented sediments into zones within the sedimentary pile conducive first to pyrite precipitation, and then to ferroan calcite precipitation. Fabrics can therefore be used to interpret the diagenetic environment of regressive sedimentary associations.     

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.     

Evinosponges in the Triassic Esino Limestone (Southern Alps): documentation of early lithification and late diagenetic overprint

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