Sedimentology and isotope geochemistry of lacustrine carbonates of the Oligocene Campins Basin, north-east Spain

The non-marine Campins Basin developed in the Oligocene, during a period of early rifting of the Catalan Coastal Ranges. Lacustrine deposits, interbedded between two alluvial units, comprise shallow and deep lacustrine facies. The lower, shallow lacustrine facies are made up of microbialite buildups and thin limestone beds. In the studied area, these facies are overlain by deep lacustrine facies which consist of alternations of several, metre-thick carbonate- and mudstone-dominated intervals. In addition to calcite, which is characteristic of the shallow lacustrine facies, aragonite and abundant dolomite are present in the deep lacustrine facies. This mineralogical change in the sequence reflects an overall increase in the Mg/Ca ratio of the lake waters. The deep lacustrine sequences are interpreted as having formed in a hydrologically closed basin that was subject to changes in the Mg/Ca ratio of the water, probably related to variations in the evaporation/precipitation rate. The sedimentological, mineralogical and isotopic characteristics of the Campins Basin dolomites suggest that, in general, they are primary in origin. The stable isotope data show an approximate covariance between δ¹³C and δ¹⁸O in the lower shallow lacustrine carbonates (calcite) which suggests that they formed during the onset of closure of the lake. The δ¹³C and δ¹⁸O values of the deep lacustrine carbonates display three different clusters that are roughly related to the carbonate mineralogy. Normalisation with respect to calcite of the isotopic compositions of dolomite and aragonite from the deep lacustrine carbonates allows the integration of all these isotope values into one covariant trend. The sequential appearance of different carbonate minerals and the isotopic covariant trend may indicate an overall evaporative concentration of the lake waters. The change in slope of the covariant trend for the isotope values between the shallow and the deep lacustrine carbonates might reflect the change in the waterbody morphology recorded in the basin fill sequence.     

Palaeoenvironmental reconstruction of a middle Miocene alluvial fan to cyclic shallow lacustrine depositional system in the Calatayud Basin (NE Spain)

ABSTRACT The middle Miocene sedimentary fill of the Calatayud Basin in north‐eastern Spain consists of proximal to distal alluvial fan‐floodplain and shallow lacustrine deposits. Four main facies groups characteristic of different sedimentary environments are recognized: (1) proximal and medial alluvial fan facies that comprise clast‐supported gravel and subordinate sandstone and mudstone, the latter exhibiting incipient pedogenic features; (2) distal alluvial fan facies, formed mainly of massive mudstone, carbonate‐rich palaeosols and local carbonate pond deposits; (3) lake margin facies, which show two distinct lithofacies associations depending on their distribution relative to the alluvial fan system, i.e. front (lithofacies A), comprising massive siliciclastic mudstone and tabular carbonates, or lateral (lithofacies B) showing laminated and/or massive siliciclastic mudstone alternating with tabular and/or laminated carbonate beds; and (4) mudflat–shallow lake facies showing a remarkable cyclical alternation of green‐grey and/or red siliciclastic mudstone units and white dolomitic carbonate beds. The cyclic mudflat–shallow lake succession, as exposed in the Orera composite section (OCS), is dominantly composed of small‐scale mudstone–carbonate/dolomite cycles. The mudstone intervals of the sedimentary cycles are interpreted as a result of sedimentation from suspension by distal sheet floods, the deposits evolving either under subaerial exposure or water‐saturated conditions, depending on their location on the lacustrine mudflat and on climate. The dolomite intervals accumulated during lake‐level highstands with Mg‐rich waters becoming increasingly concentrated. Lowstand to highstand lake‐level changes indicated by the mudstone/dolomite units of the small‐scale cycles reflect a climate control (from dry to wet conditions) on the sedimentation in the area. The spatial distribution of the different lithofacies implies that deposition of the small‐scale cycles took place in a low‐gradient, shallow lake basin located in an interfan zone. The development of the basin was constrained by gradual alluvial fan aggradation. Additional support for the palaeoenvironmental interpretation is derived from the isotopic compositions of carbonates from the various lithofacies that show a wide range of δ¹⁸O and δ¹³C values varying from ?7·9 to 3·0‰ PDB and from ?9·2 to ?1·7‰ PDB respectively. More negative δ¹⁸O and δ¹³C values are from carbonate‐rich palaeosols and lake‐margin carbonates, which extended in front of the alluvial fan systems, whereas more positive values correspond to dolomite beds deposited in the shallow lacustrine environment. The results show a clear trend of δ¹⁸O enrichment in the carbonates from lake margin to the centre of the shallow lake basin, thereby also demonstrating that the lake evolved under hydrologically closed conditions.     

Reconstruction of the Holocene climate based on a carbonate sedimentary record from shallow saline Lake Verkhnee Beloe (western Transbaikalia)

We present results of mineralogical and crystallochemical studies of the Holocene carbonate sediments of a small saline lake localized in the Borgoi dry-steppe region, western Transbaikalia. Mg-calcites with a varying Mg content are predominant in the assemblage of endogenic carbonate minerals from bottom sediments. Mathematical modeling of the XRD spectra of carbonates permitted us to identify excess-Ca dolomites, which are an indicator of a shallow (playa) lake. The studies showed that the lacustrine Mg-calcites do not form a continuous series from low- to high-Mg varieties. We discuss the cause of this phenomenon and also consider the existing viewpoints of the structure of low-temperature Mg-calcites and excess-Ca dolomites and their formation conditions in lacustrine sediments. Juxtaposing the carbonate record with the data of lithological analysis, determined stable isotopes (δ¹⁸O and δ¹³C), and distribution of some geochemical indicators of climatic changes, we reconstructed the intricate evolution of Lake Verkhnee Beloe, which was controlled by the regional climate since the postglacial period till the present day.     

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.     

Primary dolomite in the Late Triassic Travenanzes Formation,Dolomites, Northern Italy: Facies control and possible bacterial influence

In the late Carnian (Late Triassic), a carbonate‐clastic depositional system including a distal alluvial plain, flood basin and sabkha, tidal flat and shallow carbonate lagoon was established in the Dolomites (Northern Italy). The flood basin was a muddy supratidal environment where marine carbonates and continental siliciclastics interfingered. A dolomite phase made of sub‐micrometre euhedral crystals with a mosaic microstructure of nanometre‐scale domains was identified in stromatolitic laminae of the flood basin embedded in clay. This dolomite is interpreted here as primary and has a nearly stoichiometric composition, as opposed to younger early diagenetic (not primary) dolomite phases, which are commonly calcian. This primary dolomite was shielded from later diagenetic transformation by the clay. The stable isotopic composition of dolomite was analyzed along a depositional transect. The δ¹³C values range between ca ?6‰ and +4‰, with the most ¹³C‐depleted values in dolomites of the distal alluvial plain and flood basin, and the most ¹³C‐enriched in dolomites of the tidal flat and lagoon. Uniform δ¹⁸O values ranging between 0‰ and +3‰ were found in all sedimentary facies. It is hypothesized that the primary dolomite with mosaic microstructure nucleated on extracellular polymeric substances secreted by sulphate reducing bacteria. A multi‐step process involving sabkha and reflux dolomitization led to partial replacement and overgrowth of the primary dolomite, but replacement and overgrowth were facies‐dependent. Dolomites of the landward, clay‐rich portion of the sedimentary system were only moderately overgrown during late dolomitization steps, and partly retain an isotopic signature consistent with bacterial sulphate reduction with δ¹³C as low as ?6‰. In contrast, dolomites of the marine, clay‐free part of the system were probably transformed through sabkha and reflux diagenetic processes into calcian varieties, and exhibit δ¹³C values of ca +3‰. Major shifts of δ¹³C values strictly follow the lateral migration of facies and thus mark transgressions and regressions.     

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.     

Alluvial-fan-carbonate facies with evaporites, Eocene Guarga Formation, Southern Pyrenees, Spain

Continental carbonates of the basal part of the Guarga Formation, Upper Eocene, have been studied in the field and in the laboratory. Both geographic pattern and vertical sequences served as a basis for sedimentary models. The pattern reveals that carbonate deposition was greater in the western part of the Tremp-Graus Basin than in the eastern part. Studies of slabs and thin sections suggest high energy deposition in the eastern part of the basin and low energy deposition in the western part. Gross lithology, petrography, and faunal/floral associations indicate sedimentary environments which include calcimorphic palaeosoils, caliche nodule zones, solid caliche nodule zones, caliche crusts, fluvial carbonates, paludal carbonates, and pond/lake carbonates. Distribution pattern of the carbonate bodies and lithologies seem to be controlled by alluvial-fan processes. They are typical fining-upward sequences in the sense of Collinson (1978) which furthermore can be assigned to a channel-bound group and a succession independent of fluvial channels. Referring to fan-physiography the sequences can be subdivided into fluvial proximal interchannel, fluvial distal interchannel, lacustrine distal interchannel, nearshore lacustrine-paludine, and lacustrine offshore carbonate facies. The two last categories are distal alluvial plain and/or fan-edge associations. The presence of especially charophyte oogonia adjacent to pseudomorphs of lenticular gypsum in the lacustrine carbonates of the western Tremp-Graus Basin indicates that their depositional environment was that of shallow lakes with alternating salinities. Diagenetic alterations consist of three major phenomena: (a) general cementation of the carbonates by low-Mg calcite, (b) pseudomorphs of lenticular gypsum, and (c) silification. The relationship of gypsum and silica diagenesis to the regional distribution of lacustrine carbonates suggests early diagenetic processes for their formation. Gypsum pseudomorphs are small and are found to be replaced by Fe-calcite throughout the whole area, or are large and replaced preferentially by silica in the west only. There is experimental evidence (Cody, 1979) that distribution of gypsum morphology and crystal sizes can be related to increased salinities and increased organic production in the west. Chert-gypsum fabrics from that area resemble the ‘silex nectique’ of Cayeux (1929). The occurrence of this noteworthy type of chert together with length-slow chalcedony is an indication of relatively early silification of the gypsum. It is suggested that the sediments containing the silicified lenticular gypsum hosted brines of partly marine origin which alternately became brackish or fresh. An attempt was made to check the influence of evaporation during carbonate deposition by determining the stable isotope composition of the carbonates and of the chert. The data show no distinct variations with respect to the presumed palaeoenvironments. The ranges in the carbonates (δ¹³C ? 5,0 to ?7,9; δ¹⁸ O ?4,5 to ?7,7) fit among the data given in the literature. The values derived from chert (δ¹⁸O 26,9 to 31 SMOW) support a concept of alternating salinities. Distribution of carbonate lithofacies indicate a systematic change in sedimentation from fluvial/ephemeral to permanent lacustrine from east to west. Diagenetic alterations suggest an increase of salinities of pore waters in the same direction. In addition the lacustrine limestones in the west were due to frequent changes in pore-water salinity. Similar sequences lacking subtidal and/or lagoonal fossil associations but including pseudomorphs of carbonate and chert after lenticular gypsum were described from the Lower Purbeckian of Dorset (West, 1964, 1975, 1979), and from the Tertiary of the Paris Basin (Fontes, 1968). Guarga limestone environments of especially the western Tremp-Graus Basin probably resembled the modern semi-arid ephemeral saline lakes in Australia (Burne, Bauld & De Dekker, 1980). Gypsum precipitation in these environments can be compared to the one in modern sabkhas from the Mediterranean coast of Egypt (West, Ali & Hilmy, 1979; Ali West & Hilmy, 1980).     

Petrological and isotopic implications of some contrasting Late Precambrian carbonates, NE Spitsbergen

The dominantly shallow-marine Vendian succession of NE Spitsbergen contains distinctive types of carbonate rock. Limestones deposited before Vendian glaciation resemble those described from other Upper Proterozoic successions, being high in Sr and inferred to have been originally aragonitic, including the distinctive 5–10 Jim equant polygonal calcite of cemented shrinkage cracks. In contrast, manganoan stromatolitic limestones within marginal-marine glacial-outwash deposits, and consisting of micrite, microspar and fascicular-optic calcite are interpreted as originally calcitic. The restriction of primary marine calcite to cold seawater is comparable with Recent and Permian carbonates, although the Precambrian example formed in a sea diluted with meltwater. There is good textural preservation of relatively ¹⁸O-rich oolitic dolostones which were cemented in a supratidal environment by artesian fluids. Nevertheless, early diagenetic replacement is inferred, immediately prior to a glacial episode. Post-glacial dolostones are either replacive marine, or evaporative lacustrine, but share rather more negative δ¹⁸O values, closer to the mean of Late Precambrian dolostones. The heaviest oxygen isotope values constrain seawater δ¹⁸O to no more negative than — 2 to — 4_SMOW. The main reason for the pronounced oxygen isotopic depletion of most Late Precambrian carbonates is their initial metastable mineralogy. The possibility of determining palaeolatitudes of the enigmatic widespread Late Proterozoic glaciations by isotopic analysis of freshwater periglacial calcareous precipitates is raised. Significant carbon isotope variations reflect changes in depositional water chemistry: some of these could be global in extent.     

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.     

Lacustrine carbonates and pedogenesis: sedimentology and origin of palustrine deposits from the Early Cretaceous Rupelo Formation, W Cameros Basin, N Spain

The Berriasian Rupelo Formation of the W Cameros Basin consists of a 2–200 m thickness of marginal and open lacustrine carbonate and associated deposits. Open lacustrine facies contain a non-marine biota with abundant charophytes (both stems and gyrogonites), ostracods, gastropods and rare vertebrates. Carbonate production was mainly biogenic. The associated marginal lacustrine (‘palustrine’) facies show strong indications of subaerial exposure and exhibit a wide variety of pedogenic fabrics. Silicified evaporites found near to the top of the sequence reflect a short hypersaline phase in the lake history. The succession was laid down in a low gradient, shallow lake complex characterized by wide fluctuations of the shoreline. Carbon and oxygen stable isotope analyses from the carbonates show non-marine values with ranges of δ¹³ from ? 7 to ? 11‰and δ¹⁸ from ? 3 to ? 7.5‰. Differences in the isotopic composition of open lacustrine carbonates are consistent with sedimentary evidence of variation in organic productivity within the lake. Analyses from the entire sample suite plot on a linear trend; isotopic compositions become lighter with increasing evidence of pedogenic modification. This suggests progressive vadose zone diagenesis and influence of meteoric waters rich in soil-derived CO². The stable isotope data thus support evidence from petrography and facies relations that ‘palustrine’limestones form through pedogenic modification of lake carbonates.     

Carbon and oxygen isotopic composition and foraminifers of condensed basal Zechstein (Upper Permian) strata in western Poland: environmental and stratigraphic implications

The basinal facies of the Lopingian Zechstein Limestone in SW Poland consists of thin (often less than 1 m thick) limestones and/or dolomites, often containing the Kupferschiefer (few tens of centimetres thick) at their base, and local thick (up to 90 m) reefal carbonates. The δ¹³C curve of these basal Zechstein deposits strongly suggests that even when the Kupferschiefer is lacking, the thin (condensed) sequences record the entire interval of the Zechstein prior to the onset of evaporite deposition, in contrast to the thick reef sequences which lack the characteristic δ¹³C curve for the lowermost part of the Zechstein. The calcite samples show considerable ranges of δ¹⁸O values. If the maximum δ¹⁸O values are considered to be the closest to the pristine original ones and if δ¹⁸O_water value = 0 is assumed, then the calculated range of palaeotemperatures for the Kupferschiefer and Zechstein Limestone calcite ranges from 19 to 34 °C. The faunal restriction, common dwarf foraminifers and the predominance of lagenids in the foraminiferal assemblage indicate continual dysaerobic conditions and possibly elevated salinity of seawater during deposition of thin basinal Zechstein Limestone deposits. The mixing of shallow and deeper waters in the stratified Zechstein Basin caused by upwelling could result in prolific carbonate precipitation in reefs located at the slope of the marginal carbonate platform of the Zechstein Limestone and in isolated reefs related to palaeohighs within the basin; however, there is no isotopic record of eventual upwelling. Copyright © 2014 John Wiley & Sons, Ltd.     

Oxygen and carbon isotope composition of Gordon Group carbonates (Ordovician), Florentine Valley,Tasmania, Australia

The Gordon Group carbonates consist of biota of the Chlorozoan assemblage, diverse non‐skeletal grains and abundant micrite and dolomite, similar to those of modern warm water carbonates. Cathodoluminescence studies indicate marine, meteoric and some burial cements. Dolomites replacing burrows, mudcracks and micrite formed during early diagenesis.

δ¹⁸O values (‐5 to ‐7%ō PDB) of the non‐luminescent fauna and marine cement are lighter than those of modern counterparts but are similar to those existing within low latitudes during the Ordovician because of the light δ¹⁸O values of Ordovician seawater (‐3 to ‐5%o SMOW). The δ¹⁸O difference (2%o) between marine and meteoric calcite indicates that Ordovician meteoric water was similar to that in modern subtropics. Values of δ¹³C relative to δ¹⁸O indicate that during the Early Ordovician there were higher atmospheric CO₂ levels than at present but during the Middle and Late Ordovician they became comparable with the present because of a change from ‘Greenhouse’ to glacial conditions. δ¹⁸O values of Late Ordovician seawater were heavier than in the Middle Ordovician mainly because of glaciation.

Dolomitization took place in marine to mixed‐marine waters while the original calcium carbonate was undergoing marine to meteoric diagenesis.     

The nature and origin of sideritic ironstone bands in the Tertiary Lowmead and Duaringa Basins,Queensland

Sideritic ironstones in Tertiary lacustrine oil shale from the Lowmead and Duaringa Basins in Queensland, contain two distinctive types of siderite in the ironstone bands: sphaerosiderite in the mudstone and coal, and finely crystalline siderite in the lamosite. The petrological evidence indicates that the siderite in the ironstone bands formed eogenetically by growing displacively within the soft sediment. Chemically the siderite is very pure though the sphaerosiderite sometimes shows compositional zoning. Stable oxygen and carbon isotope analyses of the siderite show a wide range of values from ‐12.8‰ to ‐2.4 %₀ δ¹⁸O (PDB) and ‐5.5‰ to +12.9‰ δ¹³C (PDB) for the Lowmead Basin; and ‐9.6‰ to ‐1.2‰ δ¹⁸O (PDB) and ‐18.6‰ to +16.4‰ δ¹³C (PDB) for the Duaringa Basin. The oxygen isotope data indicate that the siderite formed in freshwater environments but not in isotopic equilibrium with the formation waters. Kinetic factors offer the most plausible explanation for the anomalously light δ¹⁸O values of many of the siderites. The carbon isotope data show that the carbonate for the formation of the siderite originated predominantly from methanogenic fermentation processes but there was also the varying influence of bacterial oxidation processes. The different petrological and isotopic characteristics of the ironstones broadly reflect variations in their depositional environments and the variable eogenetic conditions in which the siderite formed. There is no suitable single model to explain the genesis of all the different types of ironstones other than that a synsedimentary iron‐enrichment process is involved.     

Palaeoenvironmental and diagenetic reconstruction of a closed‐lacustrine carbonate system – the challenging marginal setting of the Miocene Ries Crater Lake (Germany)

Chemostratigraphic studies on lacustrine sedimentary sequences provide essential insights on past cyclic climatic events, on their repetition and prediction through time. Diagenetic overprint of primary features often hinders the use of such studies for palaeoenvironmental reconstruction. Here the potential of integrated geochemical and petrographic methods is evaluated to record freshwater to saline oscillations within the ancient marginal lacustrine carbonates of the Miocene Ries Crater Lake (Germany). This area is critical because it represents the transition from shoreline to proximal domains of a hydrologically closed system, affected by recurrent emergent events, representing the boundaries of successive sedimentary cycles. Chemostratigraphy targets shifts related to subaerial exposure and/or climatic fluctuations. Methods combine facies changes with δ ¹³C–δ ¹⁸O chemostratigraphy from matrix carbonates across five closely spaced, temporally equivalent stratigraphic sections. Isotope composition of ostracod shells, gastropods and cements is provided for comparison. Cathodoluminescence and back‐scatter electron microscopy were performed to discriminate primary (syn‐)depositional, from secondary diagenetic features. Meteoric diagenesis is expressed by substantial early dissolution and dark blue luminescent sparry cements carrying negative δ ¹³C and δ ¹⁸O. Sedimentary cycles are not correlated by isotope chemostratigraphy. Both matrix δ ¹³C and δ ¹⁸O range from ca −7·5 to +4·0‰ and show clear positive covariance (R  = 0·97) whose nature differs from that of previous basin‐oriented studies on the lake: negative values are here unconnected to original freshwater lacustrine conditions but reflect extensive meteoric diagenesis, while positive values probably represent primary saline lake water chemistry. Noisy geochemical curves relate to heterogeneities in (primary) porosity, resulting in selective carbonate diagenesis. This study exemplifies that ancient lacustrine carbonates, despite extensive meteoric weathering, are able to retain key information for both palaeoenvironmental reconstruction and the understanding of diagenetic processes in relation to those primary conditions. Also, it emphasizes the limitation of chemostratigraphy in fossil carbonates, and specifically in settings that are sensitive for the preservation of primary environmental signals, such as lake margins prone to meteoric diagenesis.     

Petrographic and geochemical evidence for the formation of primary, bacterially induced lacustrine dolomite: La Roda 'white earth' (Pliocene, central Spain)

Upper Pliocene dolomites (‘white earth’) from La Roda, Spain, offer a good opportunity to evaluate the process of dolomite formation in lakes. The relatively young nature of the deposits could allow a link between dolomites precipitated in modern lake systems and those present in older lacustrine formations. The La Roda Mg‐carbonates (dolomite unit) occur as a 3·5‐ to 4‐m‐thick package of poorly indurated, white, massive dolomite beds with interbedded thin deposits of porous carbonate displaying root and desiccation traces as well as local lenticular gypsum moulds. The massive dolomite beds consist mainly of loosely packed 1‐ to 2‐μm‐sized aggregates of dolomite crystals exhibiting poorly developed faces, which usually results in a subrounded morphology of the crystals. Minute rhombs of dolomite are sparse within the aggregates. Both knobbly textures and clumps of spherical bodies covering the crystal surfaces indicate that bacteria were involved in the formation of the dolomites. In addition, aggregates of euhedral dolomite crystals are usually present in some more clayey (sepiolite) interbeds. The thin porous carbonate (mostly dolomite) beds exhibit both euhedral and subrounded, bacterially induced dolomite crystals. The carbonate is mainly Ca‐dolomite (51–54 mol% CaCO₃), showing a low degree of ordering (degree of ordering ranges from 0·27 to 0·48). Calcite is present as a subordinate mineral in some samples. Sr, Mn and Fe contents show very low correlation coefficients with Mg/Ca ratios, whereas SiO₂ and K contents are highly correlated. δ¹⁸O‐ and δ¹³C‐values in dolomites range from ?3·07‰ to 5·40‰ PDB (mean=0·06, σ=1·75) and from ?6·34‰ to ?0·39‰ PDB (mean=?3·55, σ=1·33) respectively. Samples containing significant amounts of both dolomite and calcite do not in general show significant enrichment or depletion in ¹⁸O and ¹³C between the two minerals. The correlation coefficient between δ¹⁸O and δ¹³C for dolomite is extremely low and negative (r=?0·05), whereas it is higher and positive (r=0·47) for calcite. The lacustrine dolomite deposit from La Roda is interpreted mainly as a result of primary precipitation of dolomite in a shallow, hydrologically closed perennial lake. The lake was supplied by highly saturated HCO₃^?/CO₃^2? groundwater that leached dolomitic Mesozoic formations. Precipitation of dolomite from alkaline lake waters took place under a semi‐arid to arid climate. However, according to our isotopic data, strong evaporative conditions were not required for the formation of the La Roda dolomite. A significant contribution by bacteria to the formation of the dolomites is assumed in view of both petrographic and geochemical evidence.     

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.     

Early Callovian ingression in southwestern Gondwana. Palaeoenvironmental evolution of the carbonate ramp (Calabozo Formation) in southwestern Mendoza,Neuquen basin,Argentina

The carbonatic sequence of the Calabozo Formation (Lower Callovian) developed in southwestern Gondwana, within the northern area of the Neuquén basin, and is widespread in thin isolated outcrops in southwestern Mendoza province, Argentina. This paper describes the facies, microfacies and geochemical-isotopic analysis carried out in five studied localities, which allowed to define the paleoenvironmental conditions of a homoclinal shallow ramp model, highly influenced by sea level fluctuations, where outer, mid and inner ramp subenvironments were identified. The outer ramp subenvironment was only recognized in the south of the depocenter and is characterized by proximal outer ramp facies with shale levels and interbedded mudstone and packstone layers. The mid ramp subenvironment is formed by low energy facies (wackestone) affected by storms (packstones, grainstones and floatstones). The inner ramp subenvironment is the most predominant and is characterized by tidal flat facies (wackestones, packstones and grainstones) over which a complex of shoals (grainstones and packstones) dissected by tidal channels (packstone, grainstones and floatstones) developed. In the north area, protected environment facies were recorded (bioturbated wackestones and packstones). The vertical distribution of facies indicates that the paleoenvironmental evolution of the Calabozo Formation results from a highstand stage in the depocenter, culminating in a supratidal environment, with stromatolitic levels interbedded with anhydrite originated under restricted water circulation conditions due to a progressive isolation of the basin. δ¹³C and δ¹⁸O values of the carbonates of the Calabozo Formation suggest an isotopic signature influenced by local palaeoenvironmental parameters and diagenetic overprints. The δ¹³C and δ¹⁸O oscillations between the carbonates of the different studied sections are related with lateral facies variations within the carbonate ramp accompanied with dissimilar reactivities in relation to diagenetic fluids. The δ¹⁸O values of all sections exhibit a rather broad scatter which may be attributed to diagenesis and recrystallisation while the carbon isotopic composition has been less affected by those processes. Carbon isotope system has best retained the primary isotopic signal and δ¹³C values (0–3.9‰) are within the Callovian isotope range. The ⁸⁷Sr/⁸⁶Sr ratios of the bulk carbonates of El Plomo creek, La Vaina creek and Potimalal River sections are in agreement with the Callovian seawater Sr-isotope curve.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

美国怀俄明州拉那依段岩相及碳氧同位素地球化学特征

1980年6月,本文作者之一的K. Kelts曾去美国参加由经济古生物学者和矿物学者协会组织的地质旅行。该行主要是观察和研究怀俄明州西南始新统绿河组的沉积环境。对此次旅行中带回瑞士苏黎世联邦理工学院地质研究所的样品,曾作了切片、X-射线衍射和碳氧同位素分析。     

Climatic and tectonic controls on carbonate deposition in syn‐rift siliciclastic fluvial systems: A case of microbialites and associated facies in the Late Jurassic

This work provides new insights to assess the factors controlling carbonate deposition in the siliciclastic fluvial systems of rift basins. Sedimentological and stable‐isotope data of microbialites and associated carbonate facies, along with regional geological information, are shown to reveal the influence of climate and tectonics on the occurrence and attributes of carbonate deposits in these settings. The Vega Formation – a 150 m thick Lower Kimmeridgian siliciclastic fluvial sequence in Asturias Province (northern Spain) – constitutes a candidate for this approach. This unit includes varied facies (stromatolites; rudstones, packstones and wackestones containing oncoids, intraclasts, charophytes and shell bioclasts; marlstones and polygenic calcareous conglomerates) that formed in a low‐gradient fluvial–lacustrine system consisting of shallow, low‐sinuosity oncoid‐bearing channels and pools within marshy areas, with sporadic coarse alluvial deposition. The sedimentological attributes indicate common erosion by channel overflow and rapid lateral changes of subenvironments caused by water‐discharge variations. The carbonate fluvial–lacustrine system developed near uplifted marine Jurassic rocks. The occurrence of the system was conditioned by normal faults (active during the deposition of the unit) that favoured: (i) springs of HCO₃–Ca‐rich water from a Rhaetian–Sinemurian carbonate rock aquifer; and (ii) carbonate deposition in areas partially isolated from the adjacent siliciclastic fluvial system. The microbialite δ¹³C and δ¹⁸O values support deposition in a hydrologically open system, fed by ambient‐temperature meteoric water, with riparian vegetation. Three types of lamination in the stromatolites and oncoids reflect distinct morphological types of cyanobacterial communities. The textural pattern of lamination parallels δ¹³C and δ¹⁸O changes, suggesting short‐term cycles of precipitation and temperature. A moderately to strongly contrasted seasonal and/or pluriannual precipitation regime is inferred from the cyclic δ¹³C pattern of the lamination and from the discontinuous and asymmetrical growth of oncoids. Thus, the isotopic and sedimentological attributes of the carbonate deposits were linked to short‐term climate changes associated with semi‐arid conditions, consistent with the studied climatic zone.