Oxygen Isotope Composition Of Carbonates Research Articles

A discussion on carbon and oxygen isotopes of secondary carbonates in loess-paleosol sequences

Although carbon and oxygen isotopic compositions of carbonates are valuable for Quaternary climate reconstruction due to their sensitivity to paleoclimate changes, a comprehensive understanding regarding the formation, factors influencing isotopic variations, and age uncertainties of secondary carbonates in loess deposits remains elusive. This study investigates the microstructure and stable isotopes of secondary carbonates, specifically calcified root cells (CRC) and needle-fiber calcite (NFC), found within the loess deposits of the last glacial period in the northwestern region of the Chinese Loess Plateau. The average δ13C values of soil total organic matter, CRC, NFC, and total inorganic carbonates in the YuanBao sections are −22.1‰, −14.9‰, −7.0‰, −4.6‰, respectively. Radiocarbon dating results reveal that both CRC and NFC were not of synsedimentary origin. The pronounced negativity of the carbon isotopic composition and the microstructures offer insights that CRC formation is closely tied to C3 plants. The synchronous depletion of δ13CCRC and δ18OCRC values during the transition period from the last glacial to the Holocene, underscores the sensitivity of isotopic composition of CRC to local environmental changes, making it a potential candidate for paleo-climate studies. Additionally, CRC formed during the glacial period provides a close approximation to the true sedimentation age. The radiocarbon dating of NFC highlights a significant fluctuation in carbon source translocation depth, resulting in a pronounced temporal and spatial decoupling between NFC formation and the surrounding deposits. Consequently, values of δ13CNFC and δ18ONFC seem to exhibit no significant trend across the limited depth range in this research. We propose that, when using NFC for paleoclimate reconstruction, careful consideration of variations in translocation depths of carbon sources is imperative to prevent misestimations. NFC could potentially be more fitting for broader temporal-scale paleoclimate reconstructions rather than high-resolution investigations.

Multi-proxy record of ocean-climate variability during the last two millennia on the Mackenzie Shelf, Beaufort Sea

A 2,000 year-long oceanographic history, in sub-centennial resolution, from a Canadian Beaufort Sea continental shelf site (60meters water depth) near the Mackenzie River outlet is reconstructed from ostracode and foraminifera faunal assemblages, shell stable isotopes (delta 18O, delta 13C) and sediment biogenic silica. The chronology of three sediment cores making up the composite section was established using 137Cs and 210Pb dating for the most recent 150 years and combined with linear interpolation of radiocarbon dates from bivalve shells and foraminifera tests.Continuous centimeter-sampling of the multicore and high-resolution sampling of a gravity and piston core yielded a time-averaged faunal record of every approximately 40 years from 0 to 1850 CE and every approximately 24 years from 1850 to 2013 CE. Proxy records were consistent with temperature oscillations and related changes in organic carbon cycling associated with the Medieval Climate Anomaly (MCA) and the Little Ice Age (LIA). Abundance changes in dominant microfossil species, such as the ostracode Paracyprideis pseudopunctillata and agglutinated foraminifers Spiroplectammina biformis and S. earlandi, are used as indicators of less saline, and possibly corrosive/turbid bottom conditions associated with the MCA (approximately 800 to 1200 CE) and the most recent approximately 60 years (1950–2013). During these periods, pronounced fluctuations in these species suggest that prolonged seasonal sea-ice melting, changes in riverine inputs and sediment dynamics affected the benthic environment. Taxa analyzed for stable oxygen isotope composition of carbonates show the lowest delta 18O values during intervals within the MCA and the highest during the late LIA, which is consistent with a 1 degree to 2 degree C cooling of bottom waters. Faunal and isotopic changes during the cooler LIA (1300 to 1850 CE) are most apparent at approximately 1500 to 1850 CE and are particularly pronounced during 1850 to approximately 1900 CE, with an approximate 0.5 per mil increase in delta 18O values of carbonates from median values in the analyzed taxa. This very cold 50-year period suggests that enhanced summer sea ice suppressed productivity,which is indicated by low sediment biogenic silica values and lower delta 13C values in analyzed species. From 1900CE to present, declines in calcareous faunal assemblages and changes in dominant species (Cassidulina reniforme and P. pseudopunctillata) are associated with less hospitable bottom waters, indicated by a peak in agglutinated foraminifera from 1950 to 1990 CE.

Ocean temperatures through the Phanerozoic reassessed

The oxygen isotope compositions of carbonate and phosphatic fossils hold the key to understanding Earth-system evolution during the last 500 million years. Unfortunately, the validity and interpretation of this record remain unsettled. Our comprehensive compilation of Phanerozoic δ18O data for carbonate and phosphate fossils and microfossils (totaling 22,332 and 4615 analyses, respectively) shows rapid shifts best explained by temperature change. In calculating paleotemperatures, we apply a constant hydrosphere δ18O, correct seawater δ18O for ice volume and paleolatitude, and correct belemnite δ18O values for 18O enrichment. Similar paleotemperature trends for carbonates and phosphates confirm retention of original isotopic signatures. Average low-latitude (30° S–30° N) paleotemperatures for shallow environments decline from 42.0 ± 3.1 °C in the Early-to-Middle Ordovician to 35.6 ± 2.4 °C for the Late Ordovician through the Devonian, then fluctuate around 25.1 ± 3.5 °C from the Mississippian to today. The Early Triassic and Middle Cretaceous stand out as hothouse intervals. Correlations between atmospheric CO2 forcing and paleotemperature support CO2’s role as a climate driver in the Paleozoic.

Application of the Data on δ13C and δ18O of Carbonates for the Study of Unconventional Reservoirs on the Example of the Bazhenov Source Rocks, Western Siberia, Russia

This paper addresses potential application of data on stable carbon and oxygen isotope composition of carbonates for study of organic rich source rocks on the example of the Late Jurassic–Early Cretaceous Bazhenov Formation (West Siberian petroleum basin, Russia). Geochemical studies were conducted for sections located in central (most productive) and peripheral (northern and southern) regions of the Bazhenov Formation distribution area, containing deposits formed under different conditions. We identified key factors impacting stable isotope composition of carbonate minerals and established relation of their isotope composition to the formation conditions. Using a thermodynamic model of carbon and oxygen isotope exchange in the carbonate–water–carbon dioxide system, it is shown that variations in the isotope composition of secondary carbonates are affected by isotopic composition of primary carbonates in sediments and by the isotope exchange reactions with water and carbon dioxide, generated during the source rocks transformation. Our results demonstrate that stable isotope data for carbonates in the Bazhenov Formation together with standard geochemical methods can be efficiently applied to determine sedimentation conditions and secondary alteration processes of oil source rocks.

Isotopic Composition (δ13C and δ18O) and Genesis of Mn-bearing Sediments in the Ushkatyn-III Deposit, Central Kazakhstan

The Ushkatyn-III deposit is located 300 km west of Karaganda (Central Kazakhstan). It is classified as a weakly metamorphosed Atasu-type hydrothermal-sedimentary ore deposit. Stratiform iron, manganese, and barite–lead orebodies occur in the Upper Devonian (D3fm2) carbonate sequence of this deposit. The Fe- and Mn-bearing rocks were studied. Iron ores are composed of hematite, calcite, and quartz. Manganese ores are divided into two (braunite and hausmannite) types. Braunite ores are composed of braunite, calcite, quartz, and albite; hausmannite ores are composed of hausmannite, rhodochrosite, Mn-calcite, tephroite (sometimes with sonolite and alleghanyite), and friedelite. The mineral composition of ores was formed during the burial of metal-bearing sediments containing oxides of Fe3+ and Mn3+/Mn4+. The nature and intensity of the postdepositional processes was controlled by the content of organic matter (OM) in initial rocks. Braunite ores formed under oxidizing conditions; hausmannite ores, under reducing conditions. The initial presence of OM is indicated by the carbon isotope composition in carbonates. High δ13Ccarb values (from –0.3 to 2.1‰) in hematite ores, braunite ores, and host limestones are close to those in the seawater bicarbonate precipitated as a part of biogenic calcite (e.g., shell fragments). At the same time, low δ13Ccarb values (average –12.3‰) in rhodochrosite and Mn-calcite from hausmannite ores indicate the influence of carbon from the OM buried in sediments. The general oxygen isotope composition in iron ores, manganese ores, and host rocks was determined by variations of the isotope ratio in the initial precipitates of 18O-rich calcite and 16O-rich Fe/Mn oxides. Conversion of the primary sedimentary Fe3+ and Mn3+/Mn4+ oxides to hematite, braunite, and hausmannite slightly changes the oxygen isotope composition of Fe–Mn minerals. Average values of δ18Otot determined in the hematite (1.7‰), braunite (14.8‰), and hausmannite (12.7‰) ores are close to those in the sedimentogenic iron (0‰) and manganese oxides (11.5‰). The oxygen isotope composition suggests that initial manganese oxides did not participate in the formation of carbonates in braunite ores. Average oxygen isotope composition of carbonates in these ores (δ18Ocarb 19.1‰) is close to that in host limestones (20.8‰). During the formation of hausmannite ores, in contrast, manganese oxides reacted with OM leading to the formation of rhodochrosite and silicates. Consequently, the light isotope oxygen in the starting oxides was fixed in carbonates (δ18Ocarb 15.9‰) and rocks in general (δ18Ototal 12.7‰). The oxygen isotope composition was not averaged during the formation of hausmannite ores even in the mineralogically similar aggregates in the adjacent rock layers.

Factors controlling the oxygen isotopic composition of lacustrine authigenic carbonates in Western China: implications for paleoclimate reconstructions

In the carbonate-water system, at equilibrium, the oxygen isotopic composition of carbonate is dependent not only on the temperature but also on the isotopic composition of host water in which the carbonate is formed. In this study, lake surface sediment and water samples were collected from 33 terminal lakes in Western China to evaluate controls on the oxygen isotopic composition of lacustrine authigenic carbonates (δ18Ocarb) and its spatial distribution. Our results show that water oxygen isotopic composition (δ18Owater) rather than lake summer water temperature (Twater), is the main determinant of δ18Ocarb, irrespective of whether oxygen isotope equilibrium is achieved. There are significant linear correlations between δ18Ocarb and elevation, as well as that between δ18Ocarb and latitude for lakes located on the Tibetan Plateau. In Western China, the spatial distribution of δ18Ocarb is consistent with that of δ18Owater, and is ultimately controlled by the isotopic composition of local precipitation (δ18Oprecipitation) that depends on the source of water vapor. Therefore, changes in δ18Ocarb can be predominantly interpreted as variations of δ18Owater, which in turn represent changes in δ18Oprecipitation for paleoclimate reconstructions in this region, and may be relevant to studies of other areas.

Isotope Characteristics of Carbonates from Rocks of Greenstone Belts as an Indicator of a Possible Source of Fluids in Precambrian Granulite Complexes: An Example from the Giyani Greenstone Belt and the Limpopo Granulite Complex, South Africa

Data on the carbon and oxygen isotopic composition of carbonates from the rocks of the Giyani greenstone belt, Kaapvaal craton, South Africa are presented. This belt is immediately adjacent to the Hout River Shear Zone, along which the Southern Marginal Zone (SMZ) of the Limpopo granulite complex is overthrusted onto the Kaapvaal craton. The δ13C values are –2.1 and –2.2‰ for carbonates from two metapelite samples, –5.1‰ for a meta ultrabasite sample, and –7.1 and –7.7‰ for two metabasite samples, respectively. The δ18О values are 17.1 and 17.5‰ for carbonates from the metapelites, 14.3‰ for carbonates from the metaultrabasite, and 12.9 and 13.0‰ for carbonates from the metabasites. The comparison of the data obtained to the published data on the isotopic composition of carbonates from the rocks of the different greenstone belts indicates both hydrothermal (in the metabasites and the metaultrabasite) and sedimentary (in the metapelites) origins of the carbonate material in the rocks studied. Based on the comparison of these data to δ13C of magnesite that formed in ultrabasic granulites during the interaction of the Limpopo complex with the craton, the graphite and fluid inclusions in leucocratic garnet-bearing granitoids that transported fluids, and the carbon isotopic composition of graphite from metapelites of the SMZ, it is concluded that the carbon source was located outside the SMZ and represented a heterogeneous carbonate-bearing lithologies. It could be carbonate-bearing volcanogenic–sedimentary sequences of the greenstone belts of the Kaapvaal craton, which underwent prograde metamorphism during the interaction with the SMZ granulites.

Sr-Nd-Pb isotopic systematic and geochronology of ultramafic alkaline magmatism of the southwestern margin of the Siberian Craton: Metasomatism of the sub-continental lithospheric mantle related to subduction and plume events

To provide new insights into the origin and evolution of ultramafic lamprophyres (UMLs) and their mantle source, we examined two UML (aillikite and damtjernite) occurrences of different ages in the western portion of the Siberian Craton (Ilbokich and Chadobets). New age, mineral and rock geochemistry, along with Sr–Nd–Pb–C–O isotope data was obtained. Our new 206Pb/238U perovskite age (399 ± 4 Ma) confirms the previously published Early Devonian age of the Ilbokich aillikite. RbSr isochron and 40Ar/39Ar dating yielded a Middle Triassic age (243 ± 3 Ma and 241 ± 1 Ma, respectively) for the Chadobets aillikites, indicating post-Trap emplacement of these rocks.Both UMLs are characterized by incompatible elements, including light rare earth element (LREE) enrichments (La is up to ×200 chondrite concentration), and strong fractionation of REEs ((La/Yb)n: 33–84). Despite the close geochemical affinity of both UMLs, the Nd isotopic compositions of aillikites, as well as the Pb isotopic composition of Chadobets and Ilbokich UMLs, do not overlap and are distinctly different from each other. The initial Sr and Nd isotopic compositions of the Ilbokich UMLs fall in within a narrow 87Sr/86Sr0 range (0.7032–0.7042) and εNd(T) (4.03–3.97). Chadobets UMLs have a similar Sr isotopic signature (87Sr/86Sr0: 0.7031–0.7043) and a more depleted Nd isotopic signature (εNd(T) 4.09–5.08). The initial Pb isotope compositions of the Chadobets UMLs are moderately radiogenic, ranging between 206Pb/204Pb = 18.4–19.0, 208Pb/204Pb = 38.3–38.8, and are characterized by a narrow 207Pb/204Pb ratio between 15.5 and 15.6. The Ilbokich Pb isotope compositions are less variable and range between 206Pb/204Pb = 18.0–18.4, 208Pb/204Pb = 37.8–38.4 and 207Pb/204Pb ratios between 15.5 and 15.6. The oxygen isotopic composition of carbonate from both UMLs is characterized by highly variable δ18O values from +12.1 and up to +20.5‰ (SMOW). The isotopic composition of δ13C values range from −1.3‰ to −7.1.Based on the minor impact of crustal contamination in both aillikites, it is inferred that their radiogenic isotope composition reflects a mantle source signature. The mantle source of the Chadobets aillikites is likely to include carbonatitic magma as a metasomatic agent. In contrast, phlogopite-rich metasomes within the lithospheric mantle could have contributed more significantly to the Ilbokich aillikites. These metasomes could be formed during the Caledonian orogeny, which did not only affect the southwestern boundary of the Siberian Craton, but also expanded to the craton interior. This study provides additional support for the evolution of the south-western portion of the Siberian SCLM, ranging from mantle containing phlogopite enrichment domains during the Early Devonian to hydrous-phase reduced mantle in the Triassic due to the thermal impact of the Siberian Traps.

Development, distribution and palaeoenvironmental significance of terrestrial carbonates in the Petra region, southern Jordan

Terrestrial carbonate deposits are common in both natural and human-modified landscapes in Petra and its surroundings.Three broad genetic categories are recognized: cementations of pre-existing clastics (veins, crusts, cemented cobbles); free-water deposits (Massive Laminated Deposits (MLD), rhizoliths, carbonate blisters, coatings on archaeological water delivery systems), and pedogenic deposits (nodules, calcrete).The oxygen isotopic composition of carbonates suggests mainly precipitation from stored water that reflects the weighted isotopic average of rainfall in the area. Oxygen and carbon isotope data indicate that a combination of evaporation and CO2 degassing are the mechanisms for precipitation, depending on the setting and climate at the time of deposition. Strontium isotopes of carbonates point to an aeolian source (from adjacent sources) for the calcium. The cementations of pre-existing clasts are both markers of previous base levels in the case of cemented cobbles, and the presence of soil above impermeable bedrock in the case of crusts and veins. These types of deposits help to discover previously terraced sites.The open water deposits reflect humid Pleistocene conditions, and their presence inform on the extent and distribution of water resources that may have been available in the Late Pleistocene and early Holocene.

The Lukoganskoe Au–Cu Skarn Deposit (Eastern Transbaikalia): Mineral Composition, Age, and Formation Conditions

Abstract —The Lugokanskoe deposit is located in southeastern Transbaikalia and has been studied for a long time by many researchers. However, the type of its formation is still debatable. In this paper we study the mineral composition of ores by modern methods, recognize and describe the main gold mineral assemblages, and present detailed data on the chemical composition of native gold and sulfide minerals and their isotope composition. We have established that gold–pyrite–chalcopyrite–arsenopyrite and gold–bismuth parageneses localized in skarn deposits are the main productive assemblages. Study of the sulfur isotope composition of sulfide minerals has shown an endogenous source of sulfur of the ore minerals. The carbon and oxygen isotope compositions of carbonates of ore-bearing veins indicate the participation of a magmatic fluid. The established age of the gold mineralization and igneous rocks of the Shakhtama complex, together with direct geological observations, points to their spatial, temporal, and genetic relationships. According to their petrochemical and geochemical characteristics, the igneous rocks of the Shakhtama complex are I-type ilmenite (reduced) granitoids. Study of fluid inclusions by heating and cooling and Raman spectroscopy has shown that the mineral formation was accompanied by a gradual decrease in the content of salts in the ore-forming fluids and by a decrease in their homogenization temperatures. Optical observations demonstrate that the fluid was heterogeneous at the early stages of the mineral formation. The evolution of the ore system was accompanied by a change in the gas phase composition of fluid inclusions from predominantly nitrogen–carbon dioxide to essentially aqueous, with carbon dioxide impurity (H2O + CO2 ± N2 → H2O ± CO2). The research data testify to the magmatic nature of fluids and the participation of meteoric waters at the late stages of the ore-forming process. The data obtained have led to the conclusion that the Lugokanskoe gold deposit is related to reduced intrusions formed at a shallow depth.

Stable isotope analyses of the carbonate component of bones and teeth: The need for method standardization

In addition to the collagen and phosphate components of bones and teeth, the stable carbon and oxygen isotope compositions of skeletal carbonate are frequently measured to determine diet, environmental conditions, and populational or individual migration in bioarchaeological research. A standardized method for the stable isotopic analysis of skeletal carbonate has not yet been established, despite the importance of these data. In this study, significant differences in the stable oxygen isotope values of bones and dental enamel were observed, which arose due to instrument- and methodology-based differences. The same target archaeological samples were analyzed in three laboratories, and the stable isotope analyses were supplemented by Fourier Transformation Infrared Spectroscopy (FTIR) measurements, which detected a strong OH− concentration-dependence in the stable oxygen isotopic shifts measured between the three laboratories. Laboratory experiments were conducted to quantify the effects of reaction temperature and phosphoric acid (H3PO4) concentration on the oxygen isotopic composition of carbonate, both of which resulted in significant, though smaller δ18O changes than the OH-related δ18O change. As such, we suggest that the δ18O values of bone structural carbonate should not be included in anthropological interpretation and that the analysis of tooth enamel should be conducted at 70 °C using 102% H3PO4, in order to make the results comparable. Furthermore, carbonated hydroxylapatite (CHAP) reference materials with varied isotopic compositions should be developed in the near future.

Carbon and oxygen isotope composition of carbonate in bulk sediment in the southwest Taiwan Basin, South China Sea: Methane hydrate decomposition history and its link to mud volcano eruption

Abstract Anaerobic oxidation of methane (AOM) coupled with sulfate reduction (SR) generates authigenic carbonate which has the unique carbon and oxygen isotope composition in sulfate methane transition zone (SMTZ). The carbon and oxygen isotope composition of carbonate in sediments, which can be used to revel the variable methane flux, is affected by the percentage of AOM-driven carbonate in sediments. To investigate the methane hydrate decomposition history in the southwest Taiwan Basin, we analyzed a 13 m-long sediment core for grain size, carbonate and elemental carbon contents and stable carbon and oxygen isotopes composition of carbonate (δ13Ccarb and δ18Ocarb). The AMS 14C dating results and carbonate content reveal that a turbidity current occurred at around 14 ka B.P., which reversed sediment accumulation between 455 and 885 cm in depth. Combining the chronological framework and δ13Ccarb values, we identified that the methane hydrate decomposition scale began to decrease at 14 ka B.P. Moreover, we discovered that three transiently enhanced methane hydrate decomposition events occurred from then on. Although the δ13Ccarb and δ18Ocarb variability are as expected, the low δ18Ocarb values are inconsistent with the previous theory which favors 18O-enriched in AOM-driven authigenic carbonate. Thus, we suggest that a large amount of 18O-depleted water which originally migrated from southwest Taiwan island was injected into surface sediment along with the eruption of mud volcanos. As the terminal electron accepter of AOM-SR reaction, the exogenous 18O-depleted water leads its special oxygen isotope to be inherited by the authigenic AOM-driven carbonate. The proposed theory provides new insights on the authigenic carbonate in methane hydrate area and the association between methane hydrates and mud volcanoes.

Seasonality of Holocene hydroclimate in the Eastern Mediterranean reconstructed using the oxygen isotope composition of carbonates and diatoms from Lake Nar, central Turkey

A positive shift in the oxygen isotope composition (δ18O) of lake carbonates in the Eastern Mediterranean from the early to late Holocene is usually interpreted as a change to drier (reduced P/E) conditions. However, it has also been suggested that changes in the seasonality of precipitation could explain these trends. Here, Holocene records of δ18O from both carbonates and diatom silica, from Lake Nar in central Turkey, provide insights into palaeoseasonality. We show how Δδ18Olakewater (the difference between spring and summer reconstructed δ18Olakewater) was minimal in the early Holocene and for most of the last millennium, but was greater at other times. For example, between ~4,100-1,600 years BP we suggest that increased Δδ18Olakewater could have been the result of relatively more spring/summer evaporation, amplified by a decline in lake level. In terms of change in annual mean δ18O, isotope mass balance modelling shows that this can be influenced by changes in seasonal P/E as well as inter-annual P/E, but lake level falls inferred from other proxies confirm there was a mid Holocene transition to drier climatic conditions in central Turkey.

Isotopic characterization of late Neogene travertine deposits at Barrancas Blancas in the eastern Atacama Desert, Chile

Here we explore the potential of spring-related, surface and subsurface carbonates as an archive of paleoenvironmental change at Barrancas Blancas, located in the broadest and driest sector of the Atacama Desert at 24.5°S. From these deposits we present a new stable isotopic record of paleoenvironmental conditions over portions of the past ~11.5Ma. U-Pb dates from the carbonates, both surface and subsurface, demonstrate that springs have discharged at this location over much of the last 11.5Ma, attesting to the exceptional geomorphic stability of the central Atacama. Many of the sampled vein systems line vertical fissures, and formed within the aquifer before groundwater discharged at the surface. Carbonates in such circumstances should not undergo off-gassing and kinetic fractionation prior to formation, simplifying the interpretation of their isotopic composition. Oxygen isotopic compositions of carbonates are generally high (>−5‰VPDB), and using paleospring water temperatures of 3–13°C reconstructed from clumped isotopes, point to strongly (up to 50%) evaporated water isotope values, like those associated with the hyperarid core of the Atacama Desert today. Carbon isotopic compositions are also high (≥+3‰ PDB), reflecting a recharge area essentially devoid of plants and dominated by volcanic CO2, as is the case today. Our isotopic results are very similar to those from the Calama Basin to the north, suggesting that the western face of the Andes between 21 and 25°S has been highly evaporative and nearly plantless when these springs discharged over the last 11.5Ma. The spring carbonates at Barrancas Blancas strongly resemble those found at Devils Hole and Furnace Creek in Death Valley, USA, and as such warrant further exploration as potential archives of climate change.

The impact of organic fluids on the carbon isotopic compositions of carbonate-rich reservoirs: Case study of the Lucaogou Formation in the Jimusaer Sag, Junggar Basin, NW China

The processes involved in the interaction between organic fluids and carbonates, and the resulting effect on reservoir quality during the evolution and maturation of organic matter remain unclear despite the fact that these processes influence the carbon and oxygen isotopic compositions of carbonates. Here, we provide new insights into these processes using data obtained from a detailed analysis of a mixed dolomitic–clastic and organic-rich sedimentary sequence within the middle Permian Lucaogou Formation in the Junggar Basin of NW China. The techniques used during this study include drillcore observations, thin section petrography, scanning electron microscopy (SEM) and electron probe microanalysis, and carbon and oxygen isotope analyses. Oil grades and total organic carbon (TOC) contents represent the amount of oil charging and the abundance of organic fluids within a reservoir, respectively, and both negatively correlate with the whole-rock δ13C and δ18O of the carbonates in the study area, indicating that organic fluids have affected the reservoir rocks. Secondary carbonates, including sparry calcite and dolomite overgrowths and cements, are common within the Lucaogou Formation. Well-developed sparry calcite is present within dark mudstone whereas the other two forms of secondary carbonates are present within the dolomite-rich reservoir rocks in this formation. Comparing thin section petrology with δ13C compositions suggests that the carbon isotopic composition of matrix carbonates varies little over small distances within a given horizon but varies significantly with stratigraphic height as a result of the development of secondary carbonates. The net change in whole-rock δ13C as a result of these secondary carbonates ranges from 1.8‰ to 4.6‰, with the secondary carbonates having calculated δ13C compositions from −18.6‰ to −8.5‰ that are indicative of an organic origin. The positive correlation between the concentration of Fe within matrix and secondary carbonates within one of the samples suggests that the diagenetic system within the Lucaogou Formation was relatively closed. The correlation between δ13C and δ18O in carbonates is commonly thought to be strengthened by the influence of meteoric water as well as organic fluids. However, good initial correlation between δ13C and δ18O of whole rock carbonates within the Lucaogou Formation (resulted from the evaporitic sedimentary environment) was reduced by organic fluids to some extent. Consequently, the δ13C–δ18O covariations within these sediments are not always reliable indicators of diagenetic alteration by organic fluids or meteoric water.The characteristics and δ13C compositions of the sparry calcite within the formation is indicative of a genetic relationship with organic acids as a result of the addition of organic CO2 to the reservoir. Further analysis suggests that both carbonate and feldspar were dissolved by interaction with organic CO2. However, dissolved carbonate reprecipitated as secondary carbonates, meaning that the interaction between organic fluids and dolomites did not directly improve reservoir quality, although this process did enhance the dissolution of feldspar and increase porosity. This indicates that the δ13C and δ18O of secondary carbonates and their influence on whole-rock carbonate isotopic values can be used to geochemically identify the effect of organic fluids on closed carbonate-rich reservoir systems.

Fluid evolution in CM carbonaceous chondrites tracked through the oxygen isotopic compositions of carbonates

The oxygen isotopic compositions of calcite grains in four CM carbonaceous chondrites have been determined by NanoSIMS, and results reveal that aqueous solutions evolved in a similar manner between parent body regions with different intensities of aqueous alteration. Two types of calcite were identified in Murchison, Mighei, Cold Bokkeveld and LaPaz Icefield 031166 by differences in their petrographic properties and oxygen isotope values. Type 1 calcite occurs as small equant grains that formed by filling of pore spaces in meteorite matrices during the earliest stages of alteration. On average, the type 1 grains have a δ18O of ∼32–36‰ (VSMOW), and Δ17O of between ∼2‰ and −1‰. Most grains of type 2 calcite precipitated after type 1. They contain micropores and inclusions, and have replaced ferromagnesian silicate minerals. Type 2 calcite has an average δ18O of ∼21–24‰ (VSMOW) and a Δ17O of between ∼−1‰ and −3‰. Such consistent isotopic differences between the two calcite types show that they formed in discrete episodes and from solutions whose δ18O and δ17O values had changed by reaction with parent body silicates, as predicted by the closed-system model for aqueous alteration. Temperatures are likely to have increased over the timespan of calcite precipitation, possibly owing to exothermic serpentinisation. The most highly altered CM chondrites commonly contain dolomite in addition to calcite. Dolomite grains in two previously studied CM chondrites have a narrow range in δ18O (∼25–29‰ VSMOW), with Δ17O ∼−1‰ to −3‰. These grains are likely to have precipitated between types 1 and 2 calcite, and in response to a transient heating event and/or a brief increase in fluid magnesium/calcium ratios. In spite of this evidence for localised excursions in temperature and/or solution chemistry, the carbonate oxygen isotope record shows that fluid evolution was comparable between many parent body regions. The CM carbonaceous chondrites studied here therefore sample either several parent bodies with a very similar initial composition and evolution or, more probably, a single C-type asteroid.

A multi-proxy record of MIS 11–12 deglaciation and glacial MIS 12 instability from the Sulmona basin (central Italy)

A multi-proxy record (lithology, XRF, CaCO3 content, carbonate δ18O and δ13C) was acquired from a sediment core drilled in the intermountain Sulmona basin (central Italy). Tephrostratigraphic analyses of three volcanic ash layers ascribe the investigated succession to the MIS 12-MIS 11 period, spanning the interval ca. 500–410 ka. Litho-pedo facies assemblage indicates predominant lacustrine deposition, interrupted by a minor sub-aerial and lake low stand episode. Variations in major and minor elements concentrations are related to changes in the clastic input to the lake. The oxygen isotopic composition of carbonate (δ18Oc) intervals is interpreted mainly as a proxy for the amount of precipitation in the high-altitude catchment of the karst recharge system. The record shows pronounced hydrological variability at orbital and millennial time-scales, which appears closely related to the Northern Hemisphere summer insolation pattern and replicates North Atlantic and west Mediterranean Sea Surface Temperature (SST) fluctuations. The MIS 12 glacial inception is marked by an abrupt reduction of precipitation, lowering of the lake level and enhanced catchment erosion. A well-defined and isotopically prominent interstadial with increased precipitation maybe related to insolation maxima-precession minima at ca. 465 ka. This interstadial ends abruptly at ca. 457 ka and it is followed by a phase of strong short-term instability. Drastic lake-level lowering and enhanced clastic flux characterized the MIS 12 glacial maximum. Lacustrine deposition restarted about 440 ka ago. The MIS 12–MIS 11 transition is characterized by a rapid increase in the precipitation, lake-level rise and reduction in the clastic input, interrupted by a short and abrupt return to drier conditions. Comparison with marine records from the Iberian margin and western Mediterranean suggests that major events of ice rafted debris deposition, related to southward migrations of the polar front, match the harshest periods in central Italy. This indicates strong teleconnections between Northern hemisphere ice sheet dynamics, North Atlantic oceanic conditions and Mediterranean continental hydrology.

Record of Early Toarcian carbon cycle perturbations in a nearshore environment: the Bascharage section (easternmost Paris Basin)

Abstract. In order to understand the significance of the worldwide deposition of black shale facies in the Early Toarcian (~ 183 Ma), considerable attention has been drawn to this Early Jurassic sub-stage over the last 3 decades. The discovery of a pronounced negative carbon isotope excursion (CIE) within the black shales disrupting the generally positive trend in carbon isotopes has stimulated many studies, particularly with a view to establish the local versus global nature of this major geochemical phenomenon. Here we document the sedimentological and chemostratigraphic evolution of a proximal environment in the Luxembourgian sedimentary area. At Bascharage, Lower Toarcian sediments record the isotopic signature of the Early Toarcian oceanic anoxic event (OAE) by a pronounced positive trend that testifies for widespread anoxia. The expression of the carbon isotope perturbation in this section, however, is unusual compared to adjacent NW European sections. A first −7‰ negative CIE, whose onset is recorded at the top of the tenuicostatum zone, can be assigned to the well-documented and potentially global Toarcian carbon isotope excursion (T-CIE) with confidence using the well-constrained ammonite biostratigraphic framework for this section. In this interval, facies contain only a limited amount of carbonate as a result of intense detrital supply in such a proximal and shallow environment. Stratigraphically higher in the section, the serpentinum zone records a subsequent CIE (−6‰) expressed as four negative steps, each being accompanied by positive shifts in the oxygen isotopic composition of carbonate. The preservation state of coccoliths and calcareous dinoflagellates in the second CIE is excellent and comparable to that observed in under- and overlying strata, so this cannot be an artefact of diagenesis. Considering the nature of this record, and the lack of such a pronounced event in the serpentinum zone in coeval sections in Europe, we hypothesise that this second CIE was caused by local factors. The geochemical record of carbonate with a relatively light carbon and relatively heavy oxygen isotopic composition is compatible with the so-called Küspert model, by which a CIE can be explained by an influx of 12C-rich and cold waters due to upwelling bottom water masses.

Dynamics of the last four glacial terminations recorded in Lake Van, Turkey

A well-dated suite of Lake Van climate-proxy data covering the last 360 ka documents environmental changes over 4 glacial/interglacial cycles in Eastern Anatolia, Turkey. The picture of cold and dry glacials and warm and wet interglacials emerging from pollen, organic carbon, authigenic carbonate content, elemental profiling by XRF and lithological analyses is inconsistent with classical interpretation of oxygen isotopic composition of carbonates pointing to a more complex pattern in Lake Van region. Detailed analysis of glacial terminations allows for the constraining of a depositional model explaining different patterns observed in all the proxies. We hypothesize that variations in relative contribution of rainfall, snowmelt and glacier meltwater recharging the basin have a very important role for all sedimentary processes in Lake Van. Lake level of glacial Lake Van, predominantly fed by snowmelt, was low, the water column was oxic, and carbonates precipitating in the epilimnion recorded the light isotopic signature of inflow. During terminations, increasing rainfall and significant supply of mountain glaciers' meltwater contributed to lake level rise. Increased rainfall enhanced density gradients in the water column, and hindered mixing leading to development of bottom-water anoxia. Carbonates precipitating during terminations show large fluctuations in their isotopic composition. Full interglacial conditions in Lake Van are characterized by high or slowly falling lake level. Rainfall and snowmelt feed the lake but due to re-established mixing, the isotopic composition of authigenic carbonates is heavier and closer to that of evaporation-influenced lake water than that of runoff representing snowmelt and atmospheric precipitation.

Environmental evolution recorded by multi-proxy evidence in Lake Chenghai sediments, Yunnan Province during recent 100 years

Lacustrine sediments can provide potential information about environmental changes in the past. On the basis of high-resolution multi-proxy analysis including carbon and nitrogen contents of organic matter, C/N ratios, inorganic carbon contents, and carbon and oxygen isotopic composition of carbonate, together with precise 137Cs dating, the environmental evolution of Lake Chenghai, Yunnan Province, during the past 100 years has been investigated. It is shown that the carbonate in Lake Chenghai is authigenic, and the organic matter is mainly derived from aquatic plants and algae, instead of terrestrial-source materials. The environmental evolution of Lake Chenghai can be diverged into three periods with the contrasting characteristics during the past 100 years. Before 1940, the stable carbon and oxygen isotope values, the poor correlation between them and the lower carbon and nitrogen contents of organic matter suggested that Lake Chenghai was open, and the lake water was oligotrophic during that period. During 1940–1993, the negative δ13C values and the gradual increase of carbon and nitrogen contents of organic matter and C/N ratios indicated that the eutrophication was aggravated. The closeness of Lake Chenghai and human activities may be responsible for this eutrophication. After 1993, notable increases in carbon and oxygen isotopic values of carbonate, carbon and nitrogen contents of organic matter, C/N ratios and inorganic carbon contents demonstrated that the increase of lacustrine productivity and the serious eutrophication were resulted from strong human activities. Therefore, the multi-proxy in Lake Chenghai sediments has reliably recorded the natural environmental evolution and the impacts from human activities.