Geochemische und 13C/12C-isotopenchemische Untersuchung zur Herkunft der Kohlensäure in mineralhaltigen Wässern Nordhessens (Deutschland)

Geochemical and ¹³C/¹²C-isotopical Investigation of Mineral Waters in Northern Hessia (Germany) and the Origin of their CO₂ Content The dissolved carbonate originates from three sources: 1. biogenetic soil-CO₂, 2. volcanic CO₂ related to the evaporites of the Zechstein formation, and 3. carbonate derived from the dissolution of limestones and dolomites. Miocenic basaltic melts penetrated the evaporites of the Zechstein, and the related CO₂ was trapped in the intra- and intergranulars of the salt minerals. Circulating meteoric waters dissolve the salt minerals releasing CO₂ gas. Thus, the occurrence of basalt is related to the CO₂ contents of the evaporites, and the dissolution of only small amounts of salts rich in CO₂ may result in a high concentration of carbonic acid. In waters rich in carbonate, where volcanic CO₂ dominates over the other two sources of carbon, a δ¹³C-value of “salt-CO₂” of about –1‰ (PDB) is obtained. Water with less dissolved carbonate species have smaller quantities of salt-CO₂ down to about 20%.     

13C/12C ratios of rocks and inclusions in popping rocks of the Mid-Atlantic Ridge and their bearing on the problem of isotopic composition of deep-seated carbon

CO₂-rich inclusions recovered from “popping” and related tholeiitic rocks from the Mid-Atlantic Ridge have δ¹³C values of ?7.6 ± 0.5%. relative to PDB. δ¹³C values of total carbon in the same rocks range from ?12 to ?13.7‰. These values are discussed in the light of the known δ¹³C variations in rocks of deep-seated origin. The ?7.6‰ value is interpreted as a reasonable estimate of the primary value of δ¹³C of deep-seated carbon in the ridge area.     

Biomass effects on stalagmite growth and isotope ratios: A 20th century analogue from Wiltshire, England

Increases in calcite deposition rates combined with decreases in δ¹³C and δ¹⁸O in three modern stalagmites from Brown's Folly Mine, Wiltshire, England, are correlative with a well-documented re-vegetation above the mine. Increased soil P_CO2 resulted in greater amounts of dissolved CaCO₃ in the drip waters, which consequently increased annual calcite deposition rates. The absence of deposition prior to 1916 (28 years after the mine was closed) indicates that vegetation had not yet sufficiently developed to allow higher P_CO2 values to form in the soil. Lower δ¹³C values through time may reflect the increased input of isotopically light biogenic carbon to the total dissolved inorganic carbon (DIC). δ¹⁸O decreased synchronously with δ¹³C, reflecting the increased importance of isotopically light winter recharge due to greater biomass-induced summer evapotranspiration. This is the first empirical demonstration that vegetation density can control stalagmite growth rates, δ¹³C, and δ¹⁸O, contributing critical insights into the interpretation of these climate proxies in ancient stalagmites.     

Two modes of climatic control in the Holocene stalagmite record from the Japan Sea side of the Japanese islands

The Holocene stalagmite FG01 collected at the Fukugaguchi Cave in Itoigawa, central Japan provides a unique high‐resolution record of the East Asian winter monsoon. Because of the climate conditions on the Japan Sea side of the Japanese islands, the volume of precipitation during the winter is strongly reflected in the stalagmite δ¹⁸O signal. Examination of the carbon isotopes and the Mg/Ca ratio of FG01 provided additional information on the Holocene climate in Itoigawa, which is characterized by two different modes separated at 6.4 ka. Dripwater composition and the correlation between the δ¹³C and Mg/Ca data of FG01 indicate the importance of prior calcite precipitation (PCP), a process that selectively eliminated ¹²C and calcium ions from infiltrating water from CO₂ degassing and calcite precipitation. In an earlier period (10.0–6.4 ka), an increase in soil pCO₂ associated with warming and wetting climate trends was a critical factor that enhanced PCP, and resulted in an increasing trend in the Mg/Ca and δ¹³C data and a negative correlation between the δ¹³C and δ¹⁸O profiles. A distinct peak in the δ¹³C age profile at 6.8 ka could be a response to an increase of approximately 10% in C4 plants in the recharge area. At 6.4 ka, the climate mode changed to another, and correlation between δ¹⁸O and δ¹³C became positive. In addition, a millennial‐scale variation in δ¹⁸O and pulsed changes in δ¹³C and Mg/Ca became distinct. Assuming that δ¹⁸O and PCP were controlled by moisture in the later period, the volume of precipitation was high during 6.0–5.2, 4.4–4.0, and 3.0–2.0 ka. In contrast, the driest interval in Itoigawa was during 0.2–0.4 ka, and broadly corresponds to the Little Ice Age.     

Carbon isotopic compositions of Recent planktonic foraminifera of the Indian Ocean

Carbon and oxygen isotopic determinations have been made of 29 species of Recent Indian Ocean planktonic foraminifera. Fourteen core-top samples were used and as many as 18 species were chosen from a single core-top sample. The δ¹³C of the foraminifera was compared with that of total dissolved CO₂ (ΣCO₂) and of calcite precipitated in isotopic equilibrium with ΣCO₂. The foraminiferal calcite is always at least 1.2‰ less than the value estimated for equilibrium calcite. This carbon isotopic disequilibrium suggests the partial utilization of¹³C-depleted metabolic CO₂. The calcite tests of several species, however, have δ¹³C values which are similar to the δ¹³C of ΣCO₂ in seawater. This relationship suggests that important paleohydrographic information may be obtained from carbon isotope records based on analyses of several foraminiferal species from single deep-sea sediment samples.     

The δ13C–δ18O variations in marble in the Hida Belt,Japan

Marble has a great potential to understand a history of various geological events occurring during tectonic processes. In order to decode metamorphic–metasomatic records on C–O isotope compositions of marble at mid-crustal conditions, we conducted a C–O–Sr isotope study on upper amphibolite-facies marbles and a carbonate–silicate rock from the Hida Belt, which was once a part of the crustal basement of the East Asian continental margin. Carbon and oxygen isotope analyses of calcite from marbles (Kamioka area) and a carbonate–silicate rock (Wadagawa area) show a large variation of δ¹³C [VPDB] and δ¹⁸O [VSMOW] values (from −4.4 to +4.2 ‰ and +1.6 to +20.8 ‰, respectively). The low δ¹³C values of calcites from the carbonate–silicate rock (from −4.4 to −2.9 ‰) can be explained by decarbonation (CO₂ releasing) reactions; carbon–oxygen isotope modeling suggests that a decrease of δ¹³C strongly depends on the amount of silicate reacting with carbonates. The occurrence of metamorphic clinopyroxene in marbles indicates that all samples have been affected by decarbonation reactions. All δ¹⁸O values of calcites are remarkably lower than the marine-carbonate values. The large δ¹⁸O variation can be explained by the isotope exchange via interactions between marble, external fluids, and/or silicates. Remarkably low δ¹⁸O values of marbles that are lower than mantle value (~+5 ‰) suggest the interaction with meteoric water at a later stage. Sr isotope ratios (⁸⁷Sr/⁸⁶Sr = 0.707255–0.708220) might be close to their protolith values. One zircon associated with wollastonite in a marble thin-section yields a U–Pb age of 222 ± 3 Ma, which represents the timing of the recrystallization of marble, triggered by H₂O-rich fluid infiltration at a relatively high-temperature condition. Our isotope study implies that the upper amphibolite-facies condition, like the Hida Belt, might be appropriate to cause decarbonation reactions which can modify original isotope compositions of marble if carbonates react with silicates.     

Relationship between13C and18O fractionation and changes in major element composition in a recent calcite-depositing spring — A model of chemical variations with inorganic CaCO3 precipitation

A theoretical model is derived in which isotopic fractionations can be calculated as a function of variations in dissolved carbonate species on CO₂ degassing and calcite precipitation. This model is tested by application to a calcite-depositing spring system near Westerhof, Germany. In agreement with the model,¹³C of the dissolved carbonate species changes systematically along the flow path. The difference in δ values between the upper and lower part of the stream is about 1‰. The¹³C content of the precipitated calcite is different from that expected from the theoretical partitioning. The isotopic composition of the solid CaCO₃ is similar to that of the dissolved carbonate, though in theory it should be isotopically heavier by about 2.4‰. The¹⁸O composition of dissolved carbonate and H₂O is constant along the stream. Calculated calcite-water temperatures differ by about +5°C from the observed temperatures demonstrating isotopic disequilibrium between the water and precipitated solid. This is attributed to kinetic effects during CaCO₃ deposition from a highly supersaturated solution, in which precipitation is faster than equilibration with respect to isotopes.Plant populations in the water have virtually no influence on CO₂ degassing, calcite saturation and isotopic fractionation. Measurements of P_CO2, S_C and¹³C within a diurnal cycle demonstrate that metabolic effects are below the detection limit in a system with a high supply-rate of dissolved carbonate species. The observed variations are due to differences in CO₂ degassing and calcite precipitation, caused by continuously changing hydrodynamic conditions and carbonate nucleation rates.     

Methane-derived authigenic carbonates from the Ulleung basin sediments,East Sea of Korea

Authigenic carbonates were sampled in methane-enriched piston core sediments collected from gas venting sites on the western continental slope of the Ulleung Basin, East Sea of Korea. Multidisciplinary investigations on these carbonates, including the scanning electronic microscope (SEM) observations and mineralogical-geochemical compositions, were carried out to identify the carbon and oxygen sources and the forming mechanism of these carbonates. The authigenic carbonates from the study area correspond to semi-consolidated, compact concretions or nodules ranging from 2 to 9 cm in size. X-ray diffraction and electron microprobe analyses showed that most of the sampled carbonate concretions were composed of almost purely authigenic high-Mg calcite (10.7–14.3 mol% MgCO₃). Characteristically, microbial structures such as filaments and rods, which were probably associated with the authigenic minerals, were abundantly observed within the carbonate matrix. The carbonates were strongly depleted in δ¹³C (−33.85‰ to −39.53‰ Peedee Belemnite (PDB)) and were enriched in δ¹⁸O (5.16–5.60‰ PDB), indicating that the primary source of carbon is mainly derived from the anaerobic oxidation of methane. Such methane probably originated from the destabilization of the underlying gas hydrates as strongly supporting from the enriched ¹⁸O levels. Furthermore, the strongly depleted δ¹³C values (−60.7‰ to −61.6‰ PDB) of the sediment void gases demonstrate that the majority of the gas venting at the Ulleung Basin is microbial methane by CO₂ reduction. This study provides another example for the formation mechanism of methane-derived authigenic carbonates associated with gas-hydrate decomposition in gas-seeping pockmark environments.     

Massive barite deposits and carbonate mineralization in the Derugin Basin, Sea of Okhotsk: precipitation processes at cold seep sites

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (∼1%) in the barite fabric imply the presence of H₂S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative δ¹³C values of these carbonates (>−43.5‰ PDB) indicate methane as major carbon source; δ¹⁸O values between 4.04 and 5.88‰ PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with ¹⁴C-ages ranging from 20?680 to >49?080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO₄^2- concentrations and a parallel increase of H₂S with depth. Additionally, S and O isotope data of barite sulfate (δ³⁴S: 21.0-38.6‰ CDT; δ¹⁸O: 9.0-17.6‰ SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with ‘normal’ seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49?000 yr.     

Upper Eocene travertine-lacustrine carbonate in the Jianchuan basin,southeastern Tibetan Plateau: Reappraisal of its origin and implication for the monsoon climate

The Asian monsoon is one of the largest climatic systems in the world, but age of its onset has been estimated differently ranging from the late Eocene to the Quaternary. We investigated the sedimentology and stable isotopic compositions of the upper Eocene Jiuziyan Formation, a terrestrial limestone unit in the Jianchuan basin, Yunnan Province in China. This limestone formation is restricted in several localities in the central part of the basin. Previously, this has been characterized as palustrine carbonate and the transition to the sublacustrine deposit of the overlying Shuanghe Formation was interpreted as the appearance of wetter climate during the late Eocene. Our observations of macro- and microfacies revealed sedimentary fabrics indicating rapid CaCO₃ precipitation, such as dendritic calcite and calcified reed stems, which are unlikely to develop in a simple lacustrine setting. High carbonate content (mostly >90 %) and restricted distribution of the Jiuziyan limestone indicate a depositional setting spatially limited and isolated from clastic influx. These findings, together with clearly higher δ¹³C values (−0.7 ‰ to +6.9 ‰) and lower δ¹⁸O values (−14.6 ‰ to −10.5 ‰) than those of the Shuanghe Formation, indicate that the limestone was mainly travertine, carbonate formed from endogenic spring water. The elevated δ¹³C resulted from a large amount of CO₂ degassing from spring water with high pCO₂. In addition, the occurrence of centimeter-scale lamination coupled with cyclic changes in δ¹³C and δ¹⁸O is almost identical with the modern annually-laminated travertine reported from Baishuitai in northern Yunnan Province, implying comparable amplitude of seasonal temperature and precipitation changes to the record of the modern travertine at Baishuitai. Our results do not contradict the previous interpretation of late Eocene wetting and additionally suggest the existence of the late Eocene monsoon climate in the Jianchuan basin.     

Groundwater evolution and mean water age inferred from hydrochemical and isotopic tracers in a tropical confined aquifer

The coastal confined aquifer in the Gulf of Urabá (Colombia) is an important water source for the banana agro‐industry as well as for urban and rural communities. However, the main processes controlling recharge and mixing in the aquifer are still poorly understood. Hydrochemical analyses and stable isotope monitoring were conducted to (a) determine groundwater recharge origin, mean groundwater age, and the main processes governing groundwater chemistry and the potential mixing of marine water and the influence of diffusive processes from the two surrounding aquitard layers. Hydrochemical data indicate that the main processes affecting the dissolved chemical composition include cation exchange, dissolution of carbonated and CO₂, and silicate weathering. δ¹⁸O and δ²H compositions combined with ¹⁴C data highlight the differences in climatic conditions between the recharge zone and the confined section of the aquifer, which is close to the Atlantic Ocean. Groundwater samples with ¹⁴C ages from recent to 28,300 years BP show a depleted isotopic trend ranging from ?6.43‰ to ?9.14‰ in δ¹⁸O and from ?43.2‰ to ?65.7‰ in δ²H. The most depleted δ¹⁸O and δ²H compositions suggest a cooler recharge climate than the current conditions (corresponding to the last glacial period of the late Pleistocene). Depleted δ¹³C values in the total dissolved inorganic carbon indicate the existence of organic material oxidation processes within the geologic formation. These results can be used or transferred to enhance groundwater modelling efforts in other confined coastal aquifers of South America where scarcity of long‐term monitoring data limits water resources planification under a changing climate.     

Tectonic control of bioalteration in modern and ancient oceanic crust as evidenced by carbon isotopes

Abstract We review the carbon‐isotope data for finely disseminated carbonates from bioaltered, glassy pillow rims of basaltic lava flows from in situ slow‐ and intermediate‐spreading oceanic crust of the central Atlantic Ocean (CAO) and the Costa Rica Rift (CRR). The δ¹³C values of the bioaltered glassy samples from the CAO show a large range, between ?17 and +3‰ (Vienna Peedee belemnite standard), whereas those from the CRR define a much narrower range, between ?17‰ and ?7‰. This variation can be interpreted as the product of different microbial metabolisms during microbial alteration of the glass. In the present study, the generally low δ¹³C values (less than ?7‰) are attributed to carbonate precipitated from microbially produced CO₂ during oxidation of organic matter. Positive δ¹³C values >0‰ likely result from lithotrophic utilization of CO₂ by methanogenic Archaea that produce CH₄ from H₂ and CO₂. High production of H₂ at the slow‐spreading CAO crust may be a consequence of fault‐bounded, high‐level serpentinized peridotites near or on the sea floor, in contrast to the CRR crust, which exhibits a layer‐cake pseudostratigraphy with much less faulting and supposedly less H₂ production. A comparison of the δ¹³C data from glassy pillow margins in two ophiolites interpreted to have formed at different spreading rates supports this interpretation. The Jurassic Mirdita ophiolite complex in Albania shows a structural architecture similar to that of the slow‐spreading CAO crust, with a similar range in δ¹³C values of biogenic carbonates. The Late Ordvician Solund–Stavfjord ophiolite complex in western Norway exhibits structural and geochemical evidence for evolution at an intermediate‐spreading mid‐ocean ridge and displays δ¹³C signatures in biogenic carbonates similar to those of the CRR. Based on the results of this comparative study, it is tentatively concluded that the spreading rate‐dependent tectonic evolution of oceanic lithosphere has a significant control on the evolution of microbial life and hence on the δ¹³C biosignatures preserved in disseminated biogenic carbonates in glassy, bioaltered lavas.     

Isotope shifts in the Late Permian of the Delaware Basin,Texas, precisely timed by varved sediments

Closely spaced samples (285 in number) of varved sediments from the Upper Permian in Delaware Basin, Texas, have been analyzed for δ¹³C_carb, δ¹³C_org, δ¹⁸O_carb, C_org, C_carb, and calcite/dolomite. δ¹³C records a dramatic rise from ?2.8 to +5.7‰ in only 4400 years, detected in three sections across the basin, extrapolating smoothly through a 600-year interruption by a local (west side of the basin) fresh-water inflow evidenced by low δ¹⁸O. This continuity and low C_org within the basin, both indicate that the excess net deposition of C_org, necessary to generate the rise in δ¹³C, took place in the ocean external to the Delaware Basin. Correlation with similar records from the Zechstein Basin suggest that the event was world-wide, although this poses obvious difficulties for the carbon cycle. The rate of rise of δ¹³C, and its sustained high level, must imply conversions of oxidized carbon to reduced carbon that are very large depending on which reservoirs were involved.     

Light carbon isotope events of foraminifera attributed to methane release from gas hydrates on the continental slope,northeastern South China Sea

In 2013, the China Geological Survey and Guangzhou Marine Geological Survey conducted the second Chinese gas hydrate expedition in the northern South China Sea(SCS) and successfully obtained visible gas hydrate samples. Five of the thirteen drilling sites were cored for further research. In this work, Site GMGS2-08 is selected for the stable isotopic analysis of foraminifera present in the boreholes in order to reveal the carbon isotopic characteristics of the foraminifera and their response to methane release in the gas hydrate geological system. Our results show that the methane content at Site GMGS2-08 is extremely high, with headspace methane concentrations up to 39300 μmol L~(-1). The hydrocarbon δ~(13)C values, ranging from-69.4‰ to-72.3‰ PDB, distinctly indicate biogenic generation. Based on the δD analytical results(~(-1)83‰ to~(-1)85‰ SMOW), headspace methane is further discriminated to be microbial gas, derived from CO_2 reduction. By isotopic measurement, five light δ~(13)C events are found in the boreholes from Site GMGS2-08, with foraminiferal δ~(13)C values being apparently lower than the normal variation range found in the glacial-interglacial cycles of the SCS. The δ~(13)C values of benthic Uvigerina peregrina are extremely depleted(as low as~(-1)5.85‰ PDB), while those of planktonic Globigerinoides ruber reach-5.68‰ PDB. Scanning electron micrograph(SEM) studies show that foraminiferal tests have experienced post-depositional alteration, infilled with authigenic carbonate, and the diagenetic mineralization is unlikely to be related to the burial depths. The correlation calculation suggests that the anaerobic oxidation of organic matter has only weak influences on the δ~(13)C composition of benthic foraminifera. This means that the anomalous δ~(13)C depletions are predominantly attributed to the overprinting of secondary carbonates derived from the anaerobic oxidation of methane(AOM). Furthermore, the negative δ~(13)C anomalies, coupled with the positive δ18O anomalies observed at Site GMGS2-08, are most likely the critical pieces of evidence for gas hydrate dissociation in the geological history of the study area.     

Carbon isotope fractionation of dissolved inorganic carbon (DIC) due to outgassing of carbon dioxide from a headwater stream

The stable isotopic composition of dissolved inorganic carbon (δ¹³C‐DIC) was investigated as a potential tracer of streamflow generation processes at the Sleepers River Research Watershed, Vermont, USA. Downstream sampling showed δ¹³C‐DIC increased between 3–5‰ from the stream source to the outlet weir approximately 0·5 km downstream, concomitant with increasing pH and decreasing PCO₂. An increase in δ¹³C‐DIC of 2·4 ± 0·1‰ per log unit decrease of excess PCO₂ (stream PCO₂ normalized to atmospheric PCO₂) was observed from downstream transect data collected during snowmelt. Isotopic fractionation of DIC due to CO₂ outgassing rather than exchange with atmospheric CO₂ may be the primary cause of increased δ¹³C‐DIC values downstream when PCO₂ of surface freshwater exceeds twice the atmospheric CO₂ concentration. Although CO₂ outgassing caused a general increase in stream δ¹³C‐DIC values, points of localized groundwater seepage into the stream were identified by decreases in δ¹³C‐DIC and increases in DIC concentration of the stream water superimposed upon the general downstream trend. In addition, comparison between snowmelt, early spring and summer seasons showed that DIC is flushed from shallow groundwater flowpaths during snowmelt and is replaced by a greater proportion of DIC derived from soil CO₂ during the early spring growing season. Thus, in spite of effects from CO₂ outgassing, δ¹³C of DIC can be a useful indicator of groundwater additions to headwater streams and a tracer of carbon dynamics in catchments. Copyright © 2007 John Wiley & Sons, Ltd.     

δO of carbonate, quartz and phosphate from belemnite guards: implications for the isotopic record of old fossils and the isotopic composition of ancient seawater

Belemnite guards of Cretaceous and Jurassic age were found to contain varying amounts of quartz deposited both on the external surface and inside the rostrum. The oxygen isotopic composition of coexisting carbonate, quartz and phosphate from the same rostrum was measured according to well-established techniques. None of these compounds showed isotopic values in equilibrium with one another. Assuming δ¹⁸O values of the diagenetic water within the range of meteoric waters, the δ¹⁸O(SiO₂) yield temperatures in agreement with the apparent secondary origin of this phase. The δ¹⁸O(CO₃²⁻) range, with a certain continuity, between −10.8 and +0.97 PDB-1 with most of the intermediate values being within the range of the carbonate isotopic values of Mesozoic fossils. The most positive isotopic results obtained from phosphate are close to +23/+24‰ (V-SMOW). They can hardly be related to a secondary origin of the phosphate, or to the presence of diagenetic effects, since these results are among the most positive ever measured on phosphate. As far as we know there is no widespread diagenetic process determining an ¹⁸O enrichment of phosphate. The very low concentration of phosphate did not allow the determination of its mineralogical composition. All the available δ¹⁸O(PO₄³⁻) values from belemnite and non-belemnite fossils of marine origin of Tertiary and Mesozoic age are reported along with the newly measured belemnites. The following conclusions may be drawn from the data reported: (1) the pristine oxygen isotope composition of fossil marine organisms (either carbonate or phosphate) may easily undergo fairly large changes because of oxygen isotope exchange processes with diagenetic water; this process is apparent even in the case of geologically recent fossils; (2) the δ¹⁸O(PO₄³⁻) of belemnite rostra seems to be, at least in the case of the most positive results, in isotopic equilibrium with environmental water because of the similarity between the results from Cretaceous belemnites and the results from Cretaceous and Lower Tertiary pelecypods and fish teeth; 3) if so, the only feasible interpretation that can be suggested for the ¹⁸O enriched data is the possibility of a relatively large variation of the oxygen isotopic composition of ocean paleowater from Jurassic to recent time.     

Very high-frequency and seasonal cave atmosphere PCO2 variability: Implications for stalagmite growth and oxygen isotope-based paleoclimate records

Cave air P_CO2 at two Irish sites varied dramatically on daily to seasonal timescales, potentially affecting the timing of calcite deposition and consequently climate proxy records derived from stalagmites collected at the same sites. Temperature-dependent biochemical processes in the soil control CO₂ production, resulting in high summer P_CO2 values and low winter values at both sites. Large Large-amplitude, high-frequency variations superimposed on this seasonal cycle reflect cave air circulation. Here we model stalagmite growth rates, which are controlled partly by CO₂ degassing rates from drip water, by considering both the seasonal and high-frequency cave air P_CO2 variations. Modeled hourly growth rates for stalagmite CC-Bil from Crag Cave in SW Ireland reach maxima in late December (0.063 μm h^− 1) and minima in late June/early July (0.033 μm h^− 1). For well-mixed ‘diffuse flow’ cave drips such as those that feed CC-Bil, high summer cave air P_CO2 depresses summer calcite deposition, while low winter P_CO2 promotes degassing and enhances deposition rates. In stalagmites fed by well-mixed drips lacking seasonal variations in δ¹⁸O, integrated annual stalagmite calcite δ¹⁸O is unaffected; however, seasonality in cave air P_CO2 may influence non-conservative geochemical climate proxies (e.g., δ¹³C, Sr/Ca). Stalagmites fed by ‘seasonal’ drips whose hydrochemical properties vary in response to seasonality may have higher growth rates in summer because soil air P_CO2 may increase relative to cave air P_CO2 due to higher soil temperatures. This in turn may bias stalagmite calcite δ¹⁸O records towards isotopically heavier summer drip water δ¹⁸O values, resulting in elevated calcite δ¹⁸O values compared to the ‘equilibrium’ values predicted by calcite–water isotope fractionation equations. Interpretations of stalagmite-based paleoclimate proxies should therefore consider the consequences of cave air P_CO2 variability and the resulting intra-annual variability in calcite deposition rates.     

Evidence for a hypogene paleohydrogeological event at the prospective nuclear waste disposal site Yucca Mountain,Nevada, USA,revealed by the isotope composition of fluid-inclusion water

Secondary calcite residing in open cavities in the unsaturated zone of Yucca Mountain has long been interpreted as the result of downward infiltration of meteoric water through open fractures. In order to obtain information on the isotopic composition (δD and δ¹⁸O) of the mineral-forming water we studied fluid inclusions from this calcite. Water was extracted from inclusions by heated crushing and the δD values were measured using a continuous-flow isotope-ratio mass spectrometry method. The δ¹⁸O values were calculated from the δ¹⁸O values of the host calcite assuming isotopic equilibrium at the temperature of formation determined by fluid-inclusion microthermometry.The δD values measured in all samples range between ? 110 and ? 90‰, similar to Holocene meteoric water. Coupled δ¹⁸O–δD values plot significantly, 2 to 8‰, to the right of the meteoric water line. Among the various processes operating at the topographic surface and/or in the unsaturated zone only two processes, evaporation and water–rock exchange, could alter the isotope composition of percolating water. Our analysis indicates, however, that none of these processes could produce the observed large positive δ¹⁸O-shifts. The latter require isotopic interaction between mineral-forming fluid and host rock at elevated temperature (>100 °C), which is only possible in the deep-seated hydrothermal environment. The stable isotope data are difficult to reconcile with a meteoric origin of the water from which the secondary minerals at Yucca Mountain precipitated; instead they point to the deep-seated provenance of the mineral-forming waters and their introduction into the unsaturated zone from below, i.e. a hypogene origin.     

Land-air boundary environment as recorded by the18O/16O and13C/12C isotope ratios in the shells of land snails

A yearly cycle of carbon and oxygen isotope composition of shells of the Israeli land snailXeropicta vestalis is presented. The¹⁸O/¹⁶O values indicate that the snails use water from the land-air boundary zone. The¹⁸O/¹⁶O ratio of the shells is in isotopic equilibrium with the water condensate from the vapour during the winter months. During the summer months a contribution to the above water from soil water migrating upwards due to evaporation is noticeable. The δ¹³C values indicate that as in marine molluscs, the carbon isotopic composition in land snails is controlled mainly by the aqueous carbonate compound which is in equilibrium with the land-air boundary CO₂.     

Biogeochemical processes involving dissolved CO2 and CH4 at Albano, Averno, and Monticchio meromictic volcanic lakes (Central–Southern Italy)

This paper focuses on the chemical and isotopic features of dissolved gases (CH₄ and CO₂) from four meromictic lakes hosted in volcanic systems of Central–Southern Italy: Lake Albano (Alban Hills), Lake Averno (Phlegrean Fields), and Monticchio Grande and Piccolo lakes (Mt. Vulture). Deep waters in these lakes are characterized by the presence of a significant reservoir of extra-atmospheric dissolved gases mainly consisting of CH₄ and CO₂. The δ¹³C-CH₄ and δD-CH₄ values of dissolved gas samples from the maximum depths of the investigated lakes (from ?66.8 to ?55.6?‰ V-PDB and from ?279 to ?195?‰ V-SMOW, respectively) suggest that CH₄ is mainly produced by microbial activity. The δ¹³C-CO₂ values of Lake Grande, Lake Piccolo, and Lake Albano (ranging from ?5.8 to ?0.4?‰ V-PDB) indicate a significant CO₂ contribution from sublacustrine vents originating from (1) mantle degassing and (2) thermometamorphic reactions involving limestone, i.e., the same CO₂ source feeding the regional thermal and cold CO₂-rich fluid emissions. In contrast, the relatively low δ¹³C-CO₂ values (from ?13.4 to ?8.2?‰ V-PDB) of Lake Averno indicate a prevalent organic CO₂. Chemical and isotopic compositions of dissolved CO₂ and CH₄ at different depths are mainly depending on (1) CO₂ inputs from external sources (hydrothermal and/or anthropogenic); (2) CO₂–CH₄ isotopic exchange; and (3) methanogenic and methanotrophic activity. In the epilimnion, vertical water mixing, free oxygen availability, and photosynthesis cause the dramatic decrease of both CO₂ and CH₄ concentrations. In the hypolimnion, where the δ¹³C-CO₂ values progressively increase with depth and the δ¹³C-CH₄ values show an opposite trend, biogenic CO₂ production from CH₄ using different electron donor species, such as sulfate, tend to counteract the methanogenesis process whose efficiency achieves its climax at the water–bottom sediment interface. Theoretical values, calculated on the basis of δ¹³C-CO₂ values, and measured δ¹³C_TDIC values are not consistent, indicating that CO₂ and the main carbon-bearing ion species (HCO₃ ^?) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO₂ and CH₄. This study demonstrates that the vertical patterns of the CO₂/CH₄ ratio and of δ¹³C-CO₂ and δ¹³C-CH₄ are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO₂ input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes.