Isotopic and chemical intra-shell variations in low-Mg calcite of rudist bivalves (Mollusca-Hippuritacea): disequilibrium fractionations and late Cretaceous seasonality

 Isotopic (δ¹³C, δ¹⁸O) and elemental (Mg, Sr, Mn, Fe) compositions were analysed in sclerochronological profiles of several shells of late Cretaceous rudist bivalves from Greece, Turkey, Somalia and the Arabian Peninsula. The preservation of original compositions of low-Mg calcite of outer shell layers is indicated by constant and high Sr, generally low Fe and Mn, and the preservation of fibrous-prismatic ultrastructures. Cyclic variations in δ¹⁸O and Mg are interpreted to reflect seasonal temperature/salinity cycles and, thus, annual growth increments. In shells of Torreites, amplitudes of correlated δ¹³C and δ¹⁸O cycles cannot be related to reasonable palaeotemperatures or salinity. This isotopic pattern reflects vital fractionations of an extent which is unknown from modern bivalves. In contrast, almost identical ranges and amplitudes of δ¹⁸O cycles are observed in 13 shells of five species from Santonian-Campanian localities in central Greece and northern Turkey, suggesting that seasonal variations in environmental conditions were recorded without significant vital fractionations. The effect of seasonal salinity changes on δ¹⁸O of the shells is evaluated, and mean palaeotemperatures are constrained within the range of 30–32.5  °C. The annual range of temperature was estimated to be 7  °C, assuming a constant salinity. This agrees with other isotopic proxies of Late Cretaceous palaeotemperatures, and with global circulation models which predict higher low-latitude sea-surface temperatures than the present ones. Received: 12 February 1998 / Accepted: 24 May 1999     

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

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

Inhibition of dissolution within shallow water carbonate sediments: impacts of terrigenous sediment input on syn-depositional carbonate diagenesis

The early diagenetic chemical dissolution of skeletal carbonates has previously been documented as taking place within bioturbated, shallow water, tropical carbonate sediments. The diagenetic reactions operating within carbonate sediments that fall under the influence of iron‐rich (terrigenous) sediment input are less clearly understood. Such inputs should modify carbonate diagenetic reactions both by minimizing bacterial sulphate reduction in favour of bacterial iron reduction, and by the reaction of any pore‐water sulphide with iron oxides, thereby minimizing sulphide oxidation and associated acidity. To test this hypothesis sediment cores were taken from sites within Discovery Bay (north Jamaica), which exhibit varying levels of Fe‐rich bauxite sediment contamination. At non‐impacted sites sediments are dominated by CaCO₃ (up to 99% by weight). Pore waters from the upper few centimetres of cores show evidence for active sulphate reduction (reduced SO₄/Cl^? ratios) and minor CaCO₃ dissolution (increased Ca²⁺/Cl^? ratios). Petrographic observations of carbonate grains (specifically Halimeda and Amphiroa) show clear morphological evidence for dissolution throughout the sediment column. In contrast, at bauxite‐impacted sites, the sediment is composed of up to 15% non‐carbonate and contains up to 6000 μg g^?1 Fe. Pore waters show no evidence for sulphate reduction, but marked levels of Fe(II), suggesting that bacterial Fe(III) reduction is active. Carbonate grains show little evidence for dissolution, often exhibiting pristine surface morphologies. Samples from the deeper sections of these cores, which pre‐date bauxite influence, commonly exhibit morphological evidence for dissolution implying that this was a significant process prior to bauxite input. Previous studies have suggested that dissolution, driven by sulphate reduction and sulphide oxidation, can account for the loss of as much as 50% of primary carbonate production in localized platform environments. The finding that chemical dissolution is minor in a terrigenous‐impacted carbonate environment, therefore, has significant implications for carbonate budgets and cycling, and the preservation of carbonate grains in such sediment systems.     

The geochemistry of carbonate diagenesis: The past,present and future

Stable carbon and oxygen isotopes (δ¹⁸O and δ¹³C values) and trace elements have been applied to the study of diagenesis of carbonate rocks for over 50 years. As valuable as these insights have been, many problems regarding the interpretation of geochemical signals within mature rocks remain. For example, while the δ¹⁸O values of carbonate rocks are dependent both upon the temperature and the δ¹⁸O value of the fluid, and additional information including trace element composition aids in interpreting such signals, direct evidence of either the temperature or the composition of the fluids is required. Such information can be obtained by analysing the δ¹⁸O value of any fluid inclusions or by measuring the temperature using a method such as the ‘clumped’ isotope technique. Such data speak directly to a large number of problems in interpreting the oxygen isotope record including the well‐known tendency for δ¹⁸O values of carbonate rocks to decrease with increasing age. Unlike the δ¹⁸O, δ¹³C values of carbonates are considered to be less influenced by diagenesis and more a reflection of primary changes in the global carbon cycle through time. However, many studies have not sufficiently emphasized the effects of diagenesis and other post‐depositional influences on the eventual carbon isotopic composition of the rock with the classic paradigm that the present is the key to the past being frequently ignored. Finally, many additional proxies are poised to contribute to the interpretation of carbonate diagenesis. Although the study of carbonate diagenesis is at an exciting point with an explosion of new proxies and methods, care should be taken to understand both old and new proxies before applying them to the ancient record.     

Uptake of dissolved Cd by biogenic and abiogenic aragonite: a comparison with sorption onto calcite

The uptake of Cd²⁺ by aragonite and calcite is investigated by combining macroscopic measurements with some qualitative sorption experiments performed in a hydrogel medium. Both biogenic and abiogenic aragonites were studied in order to evaluate the process on materials with different textures. Assuming that sorption occurs by surface precipitation of metal-bearing solids, the gel produces a drastic decrease in the nucleation density, which allows for the precipitation of crystallites that are large enough to be analysed by scanning electron microscopy and characterized by glancing-incidence X-ray techniques. The macroscopic study reveals that aragonite is a powerful sorbent for cadmium in aqueous environments. Microscopic observations indicate that cadmium is sorbed onto aragonite by surface precipitation of (Cd, Ca)CO₃ solid solutions with a calcite-type structure. The precipitating individuals grow randomly oriented on the surface to reach sizes in the micrometre range. As a consequence, the concentration of cadmium in the aqueous solution decreases dramatically to values controlled by the low solubility of the cadmium-rich end member. This mechanism involves simultaneous dissolution-crystallization and is the same for both abiogenic and biogenic aragonites, the only difference being a result of the higher specific surface area of the biogenic starting material. Long-term uptake of cadmium by calcite occurs through a similar dissolution-crystallization mechanism, the final outcome being virtually the same, that is, surface precipitation of (Cd,Ca)CO₃ solid solutions. In this case, however, substrate and precipitate are isostructural and the process occurs by oriented overgrowth of thin lamellar crystallites, which spread to quickly cover the surface by a layer a few nanometers thick. This epitaxial layer armors the substrate from further dissolution, so that the process stops when only a small amount of cadmium has been removed from the fluid. As a result, the “sorption capacity” of calcite is considerably lower than that of aragonite. The study illustrates reaction pathways and “partial” equilibrium endpoints in surface-precipitation processes involving solid solutions.     

Syntectonic hydrothermal calcite in a faulted carbonate platform margin (Albian of Jorrios, northern Spain)

ABSTRACT A calcite mass more than 1·5 km long and 20 m wide crops outs along the faulted margin of the Albian carbonate platform of Jorrios in northern Spain. The mass contains abundant dissolution cavities up to 7 m long and 1 m high, filled with cross‐stratified quartz sandstone and alternating sandstone–calcite laminae. Similar cavities are also present in a 50‐m‐wide zone of platform limestones adjacent to the calcite mass that are filled with limestone breccias and sandstone. The calcite mass has mean δ¹⁸O values of 19·6‰ (SMOW), whereas platform limestones have mean δ¹⁸O values of 24·4‰ (SMOW). Synsedimentary faulting of the carbonate margin and circulation of heated fault‐related waters resulted in replacement of a band of limestone by calcite. Soon after this replacement, dissolution by undersaturated fluids affected both the calcite mass and the adjacent limestones. Percolating marine quartz sand filled all dissolution cavities, sometimes alternating with precipitating calcite. The resulting cavities and fills, which recall products of meteoric diagenesis, are attributed to a hydrothermal origin based on their geometry, occurrence along the profile and synsedimentary tectonic relationships. The early faulting and diagenesis are related to local extensional tectonism in a large‐scale strike‐slip setting. Movements occurred during the early dispar/appenninica zone of the Late Albian.     

Formation of the composition and quality of carbonate mineral water of the Elburgan water bearing complex (Essentuki Town)

The problems of underground water formation in the Elburgan water bearing stratum in conditions close to a marine sedimentation basin are considered in this article. As well, we consider variations in water composition under the influence of mixing with ground waters during water pumping for commercial purposes, and the deterioration of water quality caused by a decrease in the mineralization of mixture, considered with respect to the degree of mineralization accepted for waters used for medical purposes.     

Geochemical distinctions between igneous carbonate, calcite cements, and limestone xenoliths (Polino carbonatite, Italy): spatially resolved LAICPMS analyses

Petrography-controlled laser ablation inductively coupled plasma mass spectrometry (LAICPMS) analyses of carbonate in fresh shallow level sub-volcanic Polino monticellite calcio-carbonatite tuffisite have been performed to assess the geochemical differences between fresh igneous, epigenetic carbonates and sedimentary accidental fragments. Igneous calcite has consistently high LREE/HREE ratios (La/Yb _N , 15–130) due to high LREE (ΣLREE, 425–1,269 ppm). Secondary calcite cements are characterized by progressively lower and more variable trace element contents, with lower LREE/HREE ratios. A distinguishing geochemical feature is progressively increasing negative Ce anomalies observed through coarse secondary calcite that can be related to the surface environment processes. The limestone accidental fragments in the tuffisite have trace element contents almost two orders of magnitude lower than igneous carbonate and low LREE (ΣLREE < 9.5 ppm) with low LREE/HREE fractionation (La/Yb _N ratios < 18). The stable isotope composition of different carbonate types is consistent with their formation in different environments. The tuffisitization processes during diatreme formation under high CO₂-OH fugacity conditions may account for the differences noted in the igneous carbonates.     

Anaerobic diagenesis within Recent, Pleistocene, and Eocene marine carbonate frameworks

Porewaters from a variety of Recent, Pleistocene, and Eocene lithified marine carbonate frameworks displayed similar chemical characteristics: highly depleted concentrations of dissolved oxygen (>20 μM), elevated levels of dissolved methane (25-5000 nM), and near-seawater sulphate levels. These porewaters also had low pH values (7·5-7·9), and contained elevated concentrations of sulphide (4–10 μM), dissolved inorganic carbon (2·05–2·46 mM), and inorganic nutrients. Hydrocarbon composition data indicate that the methane is biogenic, whereas the methane δ¹³C values (–47·4 ± 2·7%0) suggest that it has been subject to oxidation. The porewater dissolved inorganic carbon δ¹³C values varied from –0·6 to –39%0, suggesting input of carbon dioxide from organic matter oxidation. We conclude that anaerobic diagenesis involving bacterial degradation of organic matter is a common process in lithified marine carbonates and hypothesize that it may be an important factor controlling their carbonate geochemistry.     

Early carbonate diagenesis in slope sequences and at their boundaries, Cenozoic, offshore New Jersey (ODP Leg 150)

This paper reports the genetic links among the depth distribution, mineralogy, and stable isotopic composition of diagenetic carbonates with sedimentation rates and types and preservation of organic matter in the terrigenous and biogenic sediments of Oligocene and Miocene age on the New Jersey slope. Calcites formed close to the sediment surface at sequence boundaries and maximum flooding surfaces, when the profile of early-diagenetic reactions was stabilized in the sediment column for extended periods. Dolomites precipitated in the sulfate reduction zone when diagenetic profiles stabilized during truncation, sequence boundary formation, and the deposition of lowstand sediments that overlie the sequence boundaries. Most dolomites occur in distal slope sediments that were deposited before the shelf had prograded into the study area. Siderites formed during a later stage of burial in the methanogenic zone; they are not directly genetically related to the sequence stratigraphy of the New Jersey slope. The diagene-tic dolomites and siderites occur in widely separated depth intervals below the present sea floor. The distribution of the diagenetic carbonates and their preferential occurrence in separated depth intervals resulted from different combinations of sedimentation rates and organic matter types and preservation.     

Temperature effects on the calcite skeletal composition of deep-water gorgonians (Isididae)

We test for and calibrate a proxy for ocean temperature based on the skeletal composition of the widely distributed, deep-sea gorgonians in the family Isididae (bamboo corals), through use of three complementary methods: a short-term comparison of element/Ca ratios to a four-year temperature record, a long-term comparison with oceanographic records spanning forty years, and a geographic comparison of Isidids collected at sites ranging from the tropics to Antarctica. The assays consistently support a temperature-dependency for Mg/Ca ratios and suggest S/Ca is indirectly affected by temperature, but indicate little or no effect of temperature on P/Ca and Sr/Ca. The consensus relationship between Mg/Ca and temperature for Isidid calcite from the comparisons with the temperature time-series is T = −0.505 + 0.048 Mg/Ca, where T is in °C, Mg/Ca is in mmol/mol, and the applicable range is 3-6 °C. The results of the geographic assay, though imprecise, suggest the applicable range extends to temperatures below freezing. The scatter of data points around the regression of temperature and Mg/Ca is wide in all assays. This could reflect the effect of factors other than temperature on Mg/Ca ratios, but is also likely to reflect limitations of the field data, the effects of assumed constant growth rates in the corals and instrumental analytical error. The combined effects of micro-scale variability in growth rates and wide confidence intervals for each data point suggests that environmental reconstruction from Isidid internode calcite from sparse data or at time scales less than decades be done with caution. Comparisons within and among colonies do not indicate strong vital effects on ontogenetic variability in the corals, other than possibly close to the central pore of the coral. However, similar Mg/Ca ratios for Isidids from Antarctic and more temperate regions suggest adaptation to local conditions and hence a role for physiology at higher taxonomic levels, at least. Taxonomically higher level vital effects are also suggested by large differences between gorgonian families in their regressions between Mg/Ca and temperature, by Mg/Ca ratios that overlap over a wide temperature and habitat range, and for a non-linear relationship between temperature and the slope of the Mg/Ca-temperature relationship across the order.     

碳酸盐成岩作用的研究前沿和值得思考的问题

碳酸盐成岩作用在碳酸盐沉积学,尤其是在碳酸盐储层沉积学中具有十分重要的意义,近年在以下领域取得重要进展：（1）白云岩烃类储层的几何学和岩石成因学,尤其涉及到对已有白云化模式的评论和重新认识等。（2）碳酸盐储层热液改造的构造控制机理,涉及热液白云岩的成因及其对烃类储层的影响,尤其是深部热流体对碳酸盐成岩作用的影响。（3）对一些经典成岩理论的更新和对传统成岩理论的挑战,尤其是对混合水成岩作用带和对海水环境下的埋藏成岩作用的重新认识等。（4）锶同位素组成在海相碳酸盐研究中的广泛应用,涉及对地质事件的跟踪研究、海相地层的等时对比、定年和成岩过程中水一岩相互作用的研究等。然而,碳酸盐成岩作用研究中也存在一些问题值得我们思考：（1）深埋条件下碳酸盐最为重要的溶解介质可能是作为硫酸盐还原作用产物的H2S和CO2,但并非是温度越高,碳酸盐越溶解,相对较低的温度条件反而有利于溶解,这就是所谓的倒退溶解模式。（2）碳酸盐溶解需要有温度的降低（即必须要有足够的负△T）,这可通过两种途径实现：其一是沿断层向上运移的流体,显示断层等构造作用在碳酸盐成岩研究中的重要性;二是构造抬升,显示与构造有关的埋藏历史在碳酸盐成岩研究中的重要性。（3）控制白云石锶含量最为重要的因素是其晶体化学习性,锶在白云石中的较低的分配系数导致了白云岩普遍较低的锶含量,因此,我们不能仅利用白云岩的锶含量来判断白云化流体的性质,白云岩较低的锶含量也不能说明相应的白云化流体与海水无关。（4）与硫酸盐还原作用有关的SO4^2-的带出会诱发白云化作用或白云石的沉淀,而与硫酸盐溶解有关的SO4^2-的引入则会加速白云石的溶解。     

The genesis of calcite in carbonate rocks of the sedimentary basins: Evidence from the stable carbon and oxygen isotopes composition

The distributions of stable carbon and oxygen isotopes in modern and ancient limestones of various types were studied. Carbonate samples from modern sediments were collected in the Black and Barents Seas. Ancient carbonates were represented by Upper Jurassic (Kimmeridgian-Tithonian) limestones from the central part of the West Siberian basin. Carbonate samples include remains of modern and Upper Jurassic fauna, carbonate crust from sediments of the Black Sea, carbonate tube from sediments of the Barents Sea, and Upper Jurassic limestone from the carbonate layer found at top of Abalak, bottom of Bazhenov deposits in the central part of the West Siberian basin. According to the results of the isotope analysis and comparison with modern carbonates, Upper Jurassic limestones of the West Siberian basin belong to the group of methane-derived carbonates and precipitated as a result of anaerobic oxidation of methane (AOM). Fractures in limestones are filled with secondary calcite.     

Hauptdolomit (Norian) — stratigraphy,paleogeography and diagenesis

Geochemical and carbonate petrographical methods were coordinated in facies investigations and environmental reevaluations, related to the Hauptdolomit (Hd.) = main doimite formation (±Norian) of the Northern Calcareous Alps.It is practical to distinguish eight, environmentally controlled, facies units (1–8) and three geochemical groups (I–III). Superimposed upon the environment pattern (tidal complex, lagoonal complex, barrier bar and shoal complex) is a predictable (geochemical) dolomitization and non-carbonate distribution.The vertical and lateral facies associations, their waxing and waning in the geologic columns, allow paleogeographic reconstructions. Especially important are clayey, ±bituminous facies, commonly known as “Seefeld facies”, which are interpreted to be of mainly intertidal to very shallow near-shore, rather than of deep-water, origin. Threefold stratigraphy can be substantiated and is found to be practicable for the Hd. formation in a large part of the Northern Calcareous Alps.In an attempt to explain some of the phenomena associated with dolomitization in the Hd. formation, a model of anaerobic dolomitization has been considered, outlining steps of early diagenetic dolomitization.     

A conceptual model for near-surface kinetic controls on the trace-element and stable isotope composition of abiogenic calcite crystals

The surface of a crystal in equilibrium with solute-bearing fluid generally has a composition that differs from that of the bulk crystal. If the crystal is growing, the surface composition may be “captured” by the newly formed lattice to a degree that depends upon the growth rate and the mobility of atoms in the near-surface region: rapid growth promotes this growth “entrapment,” high near-surface mobility works against it. Natural calcites may be particularly susceptible to this kind of kinetic disequilibrium, because their precipitation rates from aqueous solution can be relatively high even at near-ambient temperatures, where ion mobility in the critical near-surface region may be limited.Existing laboratory data on trace-element uptake as a function of calcite growth rate are examined here in the context of recent discoveries concerning the structure, chemistry and kinetics of the near-surface region of calcite crystals. Recent demonstrations that ions can be mobile in the outermost few nanometers of the calcite lattice even at room temperature have the greatest potential to affect growth entrapment. The model of Watson and Liang (1995)—which quantifies entrapment efficiency in terms of growth rate, diffusivity and surface-layer thickness—is modified to include a depth-dependent diffusivity and possible depletion (as well as enrichment) of some elements in the near-surface region. With these changes, the model is shown to be qualitatively consistent with the body of experimental data on trace element uptake during calcite precipitation.This apparent success of the model invites application to stable isotopes. Constraining data are few, but available information on oxygen isotope fractionation can be used to show that growth entrapment at ambient temperatures may (depending on model assumptions) produce deviations from calcite/H₂O equilibrium of up to several ‰. The preferred choice of ¹⁸O/¹⁶O for the surface layer is lighter than the lattice equilibrium value, and leads to a reduction in ¹⁸O/¹⁶O of crystals grown at higher growth rates, mimicking “vital effects.”     

Mineralogical and chemical composition of some carbonate minerals from the Zillerthal Alps,Tyrol (Austria)

Summary 32 carbonate samples from a series of metamorphic rocks of greenschist to almandine-amphibolite facies in the Zillerthal Alps were investigated by optical and chemical methods, X-ray diffractometry, and the scanning electron microscope.The carbonates consist mainly of calcite which contains up to 11 mole % (MgCO₃+FeCO₃). Some of the calcites are characterized by skeleton-like dolomitic exsolutions of rhombohedral shape that are orientated on rhombohedron planes of the calcite matrix.The relations between metamorphic grade and calcite composition will be discussed. The (FeCO₃+MgCO₃)-content of calcite depends on the temperature of formation, CO₂ pressure, and the Fe and Mg concentrations of the carbonate-forming solutions.

---

Mineralogische und chemische Zusammensetzung von Karbonaten aus den Zillertaler Alpen, Tirol (Österreich)

Zusammenfassung 32 Karbonatproben aus den Zillertaler Alpen (Tirol, Österreich) wurden mit optischen und röntgendiffraktometrischen Methoden sowie mit dem Elektronenrastermikroskop untersucht.Die Karbonate sind Calcite, die bis zu 11 Mol% (MgCO₃+FeCO₃) enthalten. Die Calcitkristalle zeichnen sich durch skelettartige Dolomitentmischungen aus, die parallel zu Rhomboederflächen des Calcites orientiert sind.Die Karbonate stammen aus einer Serie metamorpher Gesteine der Grünschiefer- bis Almandin-Amphibolitfazies. Es werden die Beziehungen zwischen der Calcitzusammensetzung und dem Metamorphosegrad diskutiert. Der (FeCO₃+MgCO₃)-Gehalt der Calcite hängt von der Bildungstemperatur, vom CO₂-Druck und vom Fe- und Mg-Gehalt der Lösungen ab, aus denen sich die Karbonate gebildet haben.

---

---

With 10 Figures