Isotope signatures associated with early meteoric diagenesis

The environments in which carbonate diagenesis proceeds have been documented in previous studies of Holocene and late Pleistocene sediments and limestones on Barbados, West Indies. Variations in the carbon and oxygen isotopic composition of limestones, produced during early freshwater diagenesis, have been observed in this study to occur in specific patterns. Six potentially useful patterns emerge when one views stable isotope data within a stratigraphic framework: (1) the subaerial exposure surface is characterized by strongly ¹²C-enriched limestones. δ¹³C compositions of underlying limestones grow progressively heavier with increasing depth; (2) the subaerial exposure surface may also be marked by slight ¹⁸O-enrichment; (3) an abrupt shift in δ¹⁸O values may differentiate sediments above the exposure surface from those below; (4) sediments altered in the marine-meteoric mixing zone may be characterized by positive covariance between their δ¹⁸O and δ¹³C compositions; (5) the vadose-phreatic boundary may be marked by a sharp increase in δ¹³C values in the seaward portions of a fresh groundwater system; and (6) samples contemporaneously altered in a single fresh groundwater system within an areally restricted region should display a narrow range of δ¹⁸O and a wide range of δ¹³C compositions. Analysis of samples from five Palaeozoic and Mesozoic formations, which contained petrographic evidence of early freshwater diagenesis, showed that isotope patterns similar to those observed in Barbados limestones have been preserved in rocks as old as Mississippian. These isotope patterns could prove to be useful for identifying diagenetically induced porosity trends in carbonate rocks. They might be used to identify limestones diagenetically altered in meteoric environments, to identify mixing zone cements and dolomites, and to trace the regional and vertical distributions of early meteoric groundwater systems in ancient carbonate formations.     

An alternative model for positive shifts in shallow-marine carbonate δ13C and δ18O

Abstract Positive shifts in global seawater δ¹³C_DIC are related to changes in the ratio of organic relative to inorganic carbon burial in oceanic basins, whereas factors such as climatic cooling and the accumulation of polar ice are known to cause positive shifts in δ¹⁸O. Here, an alternative model is proposed for the formation of local positive isotope shifts in shallow-marine settings. The model involves geochemically altered platform-top water masses and the effects of early meteoric diagenesis on carbonate isotopic composition. Both mechanisms are active on modern (sub)tropical carbonate platforms and result in low carbonate δ¹³C and δ¹⁸O relative to typical oceanic values. During high-amplitude transgressive events, the impact of isotopically light meteoric fluids on the carbonate geochemistry is much reduced, and ¹³C-depleted platform-top water mixes with open oceanic water masses having higher isotope values. Both factors are recorded as a transient increase in carbonate ¹³C and ¹⁸O relative to low background values. These processes must be taken into consideration when interpreting the geochemical record of ancient epeiric seas.     

A first look at oxygen isotope records from modern and Holocene-aged gastropod (Stenomelania) shells from Lake Kutubu,Papua New Guinea

The oxygen isotopic composition of Stenomelania gastropod shells was investigated to reconstruct Holocene palaeoclimate change at Lake Kutubu in the southern highlands of Papua New Guinea. Oxygen isotope (δ¹⁸O) values recorded in aquatic gastropod shells change according to ambient water δ¹⁸O values and temperature. The gastropod shells appear to form in oxygen isotopic equilibrium with the surrounding water and record a shift in average shell oxygen isotopic composition through time, probably as a result of warmer/wetter conditions at ca. 600–900 and 5900–6200 cal a bp. Shorter term fluctuations in oxygen isotope values were also identified and may relate to changes in the intensity or source of rainfall. Further δ¹⁸O analyses of gastropod shells or other carbonate proxies found in the Lake Kutubu sediments are warranted. © 2020 John Wiley & Sons, Ltd.     

Primary and diagenetic isotopic signals in fossils and hemipelagic carbonates: the Lower Jurassic of northern Spain

Stable isotope and trace element analyses of 230 Jurassic (Pliensbachian–Toarcian) samples from northern Spain have been performed to test the use of geochemical variations in fossils (belemnites and brachiopods) and whole‐rock hemipelagic carbonates as palaeoceanographic indicators. Although the succession analysed (Reinosa area, westernmost Basque–Cantabrian Basin) has been subject to severe thermal alteration during burial diagenesis, the samples appear to be well preserved. The degree of diagenetic alteration of the samples has been assessed through the application of integrated petrographic, chemical and cathodoluminescence analyses. It is demonstrated that brachiopods and whole‐rock carbonates, although widely used for palaeoceanic studies, do not retain their primary marine geochemical composition after burial diagenesis. In contrast, there is strong evidence that belemnite rostra preserve original isotopic values despite pervasive diagenesis of the host rock. Well‐preserved belemnite shells (non‐luminescent to slightly luminescent) typically show stable isotope values of +4·3‰ to –0·7‰δ¹³C, +0·7‰ to –3·2‰δ¹⁸O, and trace element contents of <32 μg g^–1 Mn, <250 μg g^–1 Fe, >950 μg g^–1 Sr and Sr/Mn ratios >80. This study suggests that the degree to which diagenesis has affected the preservation of an original isotopic composition may differ for different low‐Mg calcite fossil shells and hemipelagic bulk carbonates, behaviour that should be considered when marine isotopic signatures from other ancient carbonate rocks are investigated. Multiple non‐luminescent contemporaneous belemnite samples passed the petrographic and geochemical tests to be considered as palaeoceanic recorders, yet their δ¹³C and δ¹⁸O values exhibited moderate scatter. Such variability is likely to be related to the palaeoecological behaviour of belemnites and/or high‐frequency secular variations in sea‐water chemistry superimposed on the long‐term isotopic trend. A pronounced positive carbon‐isotope excursion (up to +4·3‰) is documented in the early Toarcian serpentinus biozone, which correlates with the Toarcian δ¹³C maximum reported in other European and Tethyan regions.     

Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls

Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ¹⁸O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ¹⁸O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO₂ and aqueous HCO^?₃. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ¹⁸O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.     

Controls on the stable isotope composition of seasonal growth bands in aragonitic fresh-water bivalves (unionidae)

Water temperature, oxygen isotope composition and the δ¹³C of dissolved inorganic carbon were measured in 2 southern Michigan rivers, the Huron River and Fleming Creek, between late September 1990 and June 1992. The final full year of shell growth in 3 unionids collected in 1992 from these rivers was sampled for stable isotope analysis with a resolution of 30 μm. The δ¹⁸O of both shell nacre and the prismatic layer is accurately predicted by a fractionation relationship developed for biogenic aragonite. High resolution sampling of 3 species and bulk sampling of 3 other species suggest that all unionids adhere to this oxygen isotope fractionation relationship. This relationship is used to show that shell growth ceases below approximately 12°C. In these 2 settings the average δ¹⁸O value of shell (PDB scale) is within 0.5‰ of the average δ¹⁸O of river water (SMOW scale). Unionids can therefore be used in oxygen-isotope-based paleoclimatic and paleohydrologic reconstructions. In contrast, the carbon isotope ratio of shell is not accurately predicted by published fractionation factors between D.I.C. and carbonate. Shell δ¹³C is more negative than predicted values and the offset is highly variable suggesting a significant and variable incorporation of metabolic carbon into the shell carbonate.     

Carbonate diagenesis of the upper Jurassic successions in the west of Binalud — Eastern Alborz (NE Iran)

The upper Jurassic carbonate settings in Iran are widely exposed in north and northeastern parts. Five stratigraphic columns were selected in the north eastern Iran. Their thickness ranges from 330 to 500 m. The various diagenetic processes identified include, micritization, cementation, compaction (physical and chemical), dissolution, neomorphism, pyritization, hematitization, silicification and dolomitization, which affected these carbonates. Elemental and stable isotopes analysis indicated that these deposits have undergone both meteoric and burial diagenesis in a relatively open system with moderate water-rock interaction. The positive trend between trace elements and oxygen isotope depletion also support these burial conditions. Lighter δ^l8O values of the dolomite samples may be related to an increase in temperature during the burial, which correspond to coarser euhedral crystals. Relatively higher δ¹⁸O values in finer dolomite crystals indicate their formation at lower burial depths relative to coarser crystals. Petrographic evidences such as coarse euhedral crystals with bright and dull zonation prove this interpretation. Chert nodules also have lighter ¹⁸O values relative to carbonate host rock, thus indicating the influence of burial diagenetic processes in their formation. The average environmental palaeotemperature was estimated to be 26°C on the basis of oxygen isotope values of less altered lime-mudstones.     

Diagenesis and the reconstruction of paleoenvironments: A method to restore original δO values of carbonate and phosphate from fossil tooth enamel

Intra-tooth δ¹⁸O variations within the carbonate (δ¹⁸Oc) and phosphate (δ¹⁸Op) components of tooth apatite were measured for Miocene and Pliocene hypsodont mammals from Afghanistan, Greece and Chad in order to evaluate the resistance of enamel to diagenetic alteration. Application of water-apatite interaction models suggest that the different kinetic behaviours of the phosphate-water and carbonate-water systems can be used to detect subtle oxygen isotope disequilibria in fossil enamel when intra-individual variations are considered. Selective alteration of the oxygen isotope composition from the carbonate component of Afghan and Greek enamels suggests inorganic isotopic exchange processes. Microbially-induced isotopic exchange for phosphate is demonstrated for the first time in enamel samples from Chad, in association with extensive recrystallization. In Chad, δ¹⁸Op values were derived from partial isotopic exchange with fossil groundwater during early diagenesis. Mass balance calculations using average carbonate content in enamel as a proxy for recrystallization, and the lowest δ¹⁸Op value of dentine as a proxy for the isotopic composition of the diagenetic fluid, indicate that diagenesis can alter δ¹⁸Op by as much as 3‰ in some enamel samples. This diagenetic alteration is also responsible for a decrease in intra-individual variations of up to 1‰ in affected specimens. The effects of diagenesis on δ¹⁸Op values of fossil enamel are not systematic, however, and can only be estimated if sequential δ¹⁸Op and δ¹⁸Oc analyses are performed on fossil enamel and dentine. Reconstruction of large temporal- or spatial-scale paleoclimates based on δ¹⁸Op analyses from mammalian teeth cannot be considered valid if enamel has been affected by bacterial activity or if the data cannot be corrected for diagenetic effects.     

Geochemical peculiarities of the formation of the Novoshirokinskii gold-polymetallic deposit,Eastern Transbaikalia,Russia

The fluid inclusions in minerals and isotope composition of sulfur in sulfides and carbon and oxygen in carbonates are studied for the Novoshirokinskii gold-polymetallic deposit. The ore-forming fluids are characterized by the following physico-chemical and isotope-geochemical parameters: temperature of 290–100°C, salinity of 13–2.5 wt % NaCl-equiv., δ¹⁸O from +8 to 0‰, δ¹³C of 2.5 ± 0.5‰, and δ³⁴S of 10.5 ± 1.0‰. It is concluded that the Late Proterozoic-Early Cambrian carbonaceous-terrigenous and carbonate rocks were involved in the Late Jurassic ore-magmatic system.     

Carbon,oxygen and strontium isotope geochemistry of Proterozoic carbonate rocks of the Vindhyan Basin,central India

Carbon, oxygen and strontium isotope compositions of carbonate rocks of the Proterozoic Vindhyan Supergroup, central India suggest that they can be correlated with the isotope evolution curves of marine carbonates during the latter Proterozoic. The carbonate rocks of the Lower Vindhyan Supergroup from eastern Son Valley and central Vindhyan sections show δ¹³C values of ∼0‰ (V-PDB) and those from Rajasthan section are enriched up to +2.8‰. In contrast, the carbonate rocks of the Upper Vindhyan succession record both positive and negative shifts in δ¹³C compositions. In the central Vindhyan section, the carbonates exhibit positive δ¹³C values up to +5.7‰ and those from Rajasthan show negative values down to –5.2‰. The δ¹⁸O values of most of the carbonate rocks from the Vindhyan Supergroup show a narrow range between –10 and –5‰ (V-PDB) and are similar to the ‘best preserved’ ¹⁸O compositions of the Proterozoic carbonate rocks. In the central Vindhyan and eastern Son Valley sections, carbonates from the Lower Vindhyan exhibit best-preserved ⁸⁷Sr/⁸⁶Sr compositions of 0.7059±6, which are lower compared to those from Rajasthan (0.7068±4). The carbonates with positive δ¹³C values from Upper Vindhyan are characterized by lower ⁸⁷Sr/⁸⁶Sr values (0.7068±2) than those with negative δ¹³C values (0.7082±6). A comparison of C and Sr isotope data of carbonate rocks of the Vindhyan Supergroup with isotope evolution curves of the latter Proterozoic along with available geochronological data suggest that the Lower Vindhyan sediments were deposited during the Mesoproterozoic Eon and those from the Upper Vindhyan represent a Neoproterozoic interval of deposition.     

Carbon and oxygen stable isotopes in the middle-upper miocene and lower pliocene carbonates of the Eastern Paratethys (Kerch-Taman Region): Palaeoenvironments and post-sedimentation changes

C and O isotope composition of Middle-Upper Miocene and Lower Pliocene carbonates from Kerch-Taman Region (Eastern Paratethys) have been studied in order to reconstruct palaeoenvironmental variability and post-sedimentation changes. The δ¹³C and δ¹⁸О values of the Upper Sarmatian to Lower Pliocene organogenic carbonates reflect the desalinization of paleobasins, global Late Miocene Cooling, and increase in seasonal temperature fluctuations. Isotopic composition of the Middle Sarmatian organogenic carbonates was strongly influenced by evaporation processes, high bioproductivity, and local submarine methane emissions. Warm climate and low bioproductivity together with unstable hydrological regime during the Late Chokrakian and the Karaganian times influenced the isotope composition of primary carbonates. Calcite shell of Spiratella sp. (δ¹³C =–0.4‰ and δ¹⁸О =–0.4‰) from Tarkhanian sediments was formed in warm marine environment. Dolomitization prevails over other secondary mineralization in the studied carbonate rocks. Two groups of secondary dolomites that are characterized by negative and positive δ¹³C values have been recognized. Lowe δ¹³C values (up to–31.4‰) in dolomites indicate the influence of both dissolved inorganic carbon (DIC) from oxidized organic matter (С_org) and methane. Dolomites with positive δ¹³C values (7.0 and 7.8‰) associat with migration of CO₂- and CH₄-containing saline groundwater.     

Experimentally-controlled carbon and oxygen isotope exchange between bioapatites and water under inorganic and microbially-mediated conditions

Modern bone and enamel powders have reacted at 301 K with ¹³C- and ¹⁸O-labelled waters under inorganic and microbial conditions. The aim of the study is to investigate the resistance of stable isotope compositions of bioapatite carbonate (δ¹³C, δ¹⁸Oc) and phosphate (δ¹⁸Op) to isotopic alteration during early diagenesis. Rapid and significant carbon and oxygen isotope changes were observed in the carbonate and phosphate fractions of bone apatite before any detectable change occurred in the crystallinity or organic matter content. These observations indicate that chemical alterations of bone apatite are likely to start within days of death. Enamel crystallites are much more resistant than bone crystallites, but are not exempt of alteration. Non removable carbon and oxygen isotope enrichments were measured in the carbonate phase of bone (50-90%) and enamel (40%) after the acetic acid treatment. This result indicates that a significant part of ¹³C and ¹⁸O-labelled coming from the aqueous fluid has been durably incorporated into the apatite structure, probably through isotopic exchange or secondary carbonate apatite precipitation. As a result, acetic acid pre-treatments that are currently used to remove exogenous material by selective dissolution, are not adequate to restore pristine δ¹³C and δ¹⁸Oc values of fossil apatites. Under inorganic conditions, kinetics of oxygen isotope exchange are 10 times faster in carbonate than in phosphate. On the opposite, during biologically-mediated reactions, the kinetics of oxygen isotope exchange between phosphate and water is, at least, from 2 to 15 times faster than between carbonate and water. Enamel is a more suitable material than bone for paleoenvironmental or paleoclimatical reconstructions, but interpretations of δ¹⁸Op or δ¹³C values must be restricted to specimens for which no or very limited trace of microbial activity can be detected.     

Environmental setting, (micro)morphologies and stable C–O isotope composition of cold climate carbonate precipitates—a review and evaluation of their potential as paleoclimatic proxies

Given the growing interest in carbonate deposits from polar regions as paleoclimatic proxies, this review paper first provides a classification of the various types of cold-climate carbonate precipitates followed by a summary of the ¹³C and ¹⁸O composition of the carbonate deposits and parent water from which the carbonates precipitated. The cold-climate carbonate precipitates were classified into three broad categories: powders, crusts and speleothem. The carbonate powders include those that precipitated in relation to aufeis aggradation (cryogenic aufeis calcite) and in relation to the growth of various annual/perennial ice formations in freezing caves (cryptocrystalline calcite and calcite pearls). The carbonate crusts can be further subdivided based on their lithic environment; those that precipitated on the upper surface of bedrock/clasts (i.e. subglacially precipitated calcite and evaporative calcite crusts); those that are located on the underside of clasts (i.e. pedogenic carbonates); and those that precipitated in rock outcrop fissures (i.e. endostromatolites). The cold-climate carbonate precipitates have a highly variable isotopic composition with δ¹⁸O values ranging between −6.5‰ and 28‰ VSMOW and δ¹³C values in the −10–20‰ VPDB range. However, each type of carbonate precipitates has a specific δ¹³C and δ¹⁸O range, suggesting that their environmental setting and the mechanism by which they formed controls their ¹³C and ¹⁸O signature. It was found that carbonate deposits that precipitated under equilibrium physico-chemical conditions had a δ¹³C value that is in equilibrium with that of the parent water, while its δ¹⁸O composition was more variable, as it is in part controlled by the temperature of reaction and by the δ¹⁸O and calcite saturation state of the parent water. By contrast, the δ¹⁸O composition of biologically precipitated carbonate deposits (endostromatolites) reflect that of the parent water, while its δ¹³C composition was enriched over that of the parent water due to bacterial methanogenesis. In the case of kinetically precipitated carbonate deposits, the δ¹⁸O and δ¹³C values are out-of-equilibrium relative to that of the parent water due to the faster rate of reaction.     

Variability of Stable Isotope Fingerprints of the Serpulid Ficopomatus enigmaticus Within a Permanently Stratified Estuary: Implications for (Palaeo)environmental Interpretations

This paper examines how the mixing of freshwater and seawater, and related mixing of freshwater and marine particulate organic matter (POM) in the permanently stratified estuary of the River Krka, Croatia, are reflected in the stable isotope fingerprints of soft tissues and tubes of the serpulid Ficopomatus enigmaticus. The carbon stable isotope composition (δ¹³C values) of the river-borne POM is retained over long distances, causing a depletion in ¹³C of POM in brackish waters. A trophic depletion in ¹³C was recorded in serpulid soft tissues. The serpulid carbonate tubes were depleted in ¹³C even at locations with salinity close to that of the sea and were subject to large isotope fractionation between dissolved inorganic C (DIC) and carbonate caused by vital effects, making carbonate depleted in ¹³C by several per mil compared with DIC. These effects, though large in the freshwater zone, fade towards the sea. The carbonate δ¹⁸O values of tubes reflect the δ¹⁸O values of the water. The temperature-related differences in δ¹⁸O values of tubes from different sites are masked by source-related differences in the δ¹⁸O values of water arising from mixing of freshwater and seawater in the estuary. Therefore, in serpulide tubes, the terrestrial component can easily be overestimated because of vital effects during biomineralisation and trophic depletion in ¹³C in freshwater and brackish environments.     

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.     

Factors influencing methane-derived authigenic carbonate formation at cold seep from southwestern Dongsha area in the northern South China Sea

This paper carried out mineral and geochemical studies on a profile through a diagenetic methane-derived authigenic carbonate sample that was collected from southwestern Dongsha area of the northern South China Sea. Five samples locating in the cross-sectional middle mainly consist of dolomite and quartz, and two samples close to the surface have a small amount of Mg-calcite. The δ¹³C values of the samples vary between ?30.59 and ?0.30 % VPDB, with δ¹⁸O values ranging from 3.07 to 3.59 % VPDB, δ^44/40Ca values ranging from 1.35 to 1.47 % SRM915a, indicating a contribution of methane to the carbon pool where the precipitation of authigenic carbonates occurred. Based on the isotope values alone, it can not be distinguished if the carbon source is thermogenic gas or a mixture of biogenic methane and marine dissolved inorganic carbon. The δ¹⁸O values are in general consistent with dolomite precipitation from a fluid similar to present seawater. The observed small variation might be related to the oxygen isotope composition of seep fluid. The relative small range in calcium isotope values suggests that relatively constant growth conditions and precipitation from seawater. The central part of the carbonate nodule formed under the strong influence of methane seepage, and the external part is less influenced by methane, either due to reduced methane flux to the surface or caused by erosional exhumation of the carbonate nodule from greater depth to the sediment surface.     

Carbon and oxygen isotope compositions of Lower-Middle Ordovician carbonate rocks in the northwestern Russian platform

Carbon and oxygen isotope compositions of Lower-Middle Ordovician carbonate rocks in the northwestern Russian Platform (eastern Ladoga Klint, Lynna River, and Babino quarry sections) are considered. In the studied section interval, average δ¹³C and δ¹⁸O values are 0 ± 0.5 and ?5 ± 0.5‰ (V-PDB), respectively. Two closely-spaced negative carbon isotope excursions with the amplitude of 2‰ are established near the Lower-Middle Ordovician boundary (between the Floian and Dapingian stages). The lower part of the Darriwilian Stage is marked by the gradual decrease in δ¹³C values to 1‰. Excursions of δ¹³C do not correlate with δ¹⁸O variations and can be considered as primary. The carbon isotope event defined at the Lower-Middle Ordovician boundary is traceable at the interregional level and represents a promising stratigraphic reference level. It may likely be explained by decrease in the relative rate of organic matter burial due to sea level fall and expansion of well-aerated shallow-water basins with a low primary production of phytoplankton.     

Behavior of carbonate-associated sulfate during meteoric diagenesis and implications for the sulfur isotope paleoproxy

Although carbonate-associated sulfate (CAS) is used widely as a proxy for the sulfur isotope composition of ancient seawater, little is known about the effects of diagenesis on retention of primary δ³⁴S signals. Our case study of the Key Largo Limestone, Pleistocene, Florida, is the first systematic assessment of the impact of meteoric diagenesis on CAS properties. Geochemical and petrographic data show that meteoric diagenesis has affected the exposed coralline facies to varying degrees, yielding differences now expressed as sharp reaction fronts between primary and secondary carbonate minerals within individual coral heads. Specifically, analyses across high-resolution transects in the Key Largo Limestone show that concentrations of strontium and sodium decrease across the recrystallization front from original aragonite to meteoric low-magnesium calcite by factors of roughly 5 and 10, respectively. Predictably, δ¹⁸O values decrease across these same fronts. The δ¹³C relationships are more complex, with the most depleted values observed in the latest-formed calcite. Such trends likely reflect carbon isotope buffering capacity that decreased as reaction progressed, as well as protracted development of soil profiles and the associated terrestrial biomass and thus depleted δ¹³C during sea-level lowstand. Conversely, δ³⁴S values of CAS vary within a narrow ‘buffered’ range from 20.6 to 22.6‰ (compared to 20.8-22.0‰ of coeval Pleistocene seawater) across the same mineralogical transition, despite sulfate concentrations that drop in the diagenetic calcite by an average factor of 12. Collectively, these data point to robust preservation of primary δ³⁴S for carbonates that have experienced intense meteoric diagenesis, which is encouraging news for those using the isotopic composition of CAS as a paleoceanographic proxy. At the same time, the vulnerability of CAS concentrations to diagenetic resetting is clear.     

Geochemistry of Triassic Carbonates: Exploration Guide to Pb–Zn Mineralization in North Tunisia

The Triassic carbonate rocks in Northern Tunisia (Nappes, Domes, Jurassic Mountains zones), consist of massive carbonates, clays and gypsum with authigenic minerals. These are associated with several Pb–Zn deposits and occurrences. At Jebel Ichkeul, Bechateur and Oum Edeboua, these Triassic carbonates exhibit enrichment in Pb (0.32 to 228 ppm), Zn (17 to 261 ppm), Cd (5 to 6 ppm) and Co (0.3 to 89.5 ppm), with respect to their average contents in crustal carbonates. The enrichment is more pronounced at Oum Edeboua (near the ore zone). Permeability is one of the most effective factors of dispersion of metallic trace elements, causing the development of geochemical halos. The genetic relationship of the Triassic carbonate rocks with the ore deposits was controlled by diapirism and tectonic movements, which favored mineralization along the Triassic‐cover contact as well as the remobilization of metals from the mineralized rocks. Analysis of metallic trace elements in Triassic rocks provides clues to the presence of possible mineral deposits. These could be effectively used for both geochemical interpretation and mineral exploration. Carbon and O‐isotope data (– 9.3‰ < δ¹³C < +3‰; +21.9 < δ¹⁸O < +31‰) suggest that the Triassic carbonates of all study areas have marine carbonates as their origin; some of them show significantly lower δ¹⁸O values indicating some exchange with hydrothermal fluids. Calcites associated with mineralization at Oum Edeboua have δ¹³C of –6.2‰ to –8.22‰ and δ¹⁸O of +24.88‰ to +25‰. The C‐isotope compositions of these calcites are ¹³C depleted, indicating an organic origin.     

Small-scaled environmental changes: indications from stable isotopes of gastropods (Early Miocene, Korneuburg Basin, Austria)

The Korneuburg Basin, with mainly upper Lower Miocene (Karpatian) sediment filling, is divided by the Mollmannsdorf–Obergänserndorf Swell into two sub-basins characterised by different environmental settings. Paleoecological data indicate a marine northern part and a mainly estuarine southern part. Nevertheless, short-termed marine ingressions from the north allowed marine faunas (ostracods, molluscs, and echinoids) to temporarily settle the southern part of the basin. The carbon and oxygen isotopic composition of gastropod shells from these different environmental settings were investigated. Highest δ¹⁸O and δ¹³C values are found in Turritella shells from the northern part of the basin, and in Turritella shells from layers interpreted as a marine ingression in the south. Generally, components of the mudflat fauna (Tympanotonos cinctus, Granulolabium bicinctum, Terebralia bidendata, and Ocenebra crassilabiata) have slightly lower isotope values. Considerable freshwater influx in the southern part is documented by abundant freshwater genera such as Melanopsis, which show low carbon and oxygen isotope values. Data of identical taxa, especially Turritella and Granulolabium, reflect a trend from higher isotope values at the marine northern part to slightly lower values in the mainly estuarine southern part of the basin. Differences in δ¹⁸O between the marine and the estuarine assemblages are interpreted to be caused by changes in salinity and isotopic composition of ambient water rather than by temperature. Paleotemperature estimates derived from oxygen isotope data are in good agreement with existing paleoclimatic proxies for the Korneuburg Basin. Hence, an annual range of the sea-surface temperature from 13 to 26°C can be predicted within that protected basin.