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1.
δ18O was determined at high spatial resolution (beam diameter ∼30 μm) by secondary ion mass spectrometry (SIMS) across 1-2 year sections of 2 modern Porites lobata coral skeletons from Hawaii. We observe large (>2‰) cyclical δ18O variations that typically cover skeletal distances equivalent to periods of ∼20-30 days. These variations do not reflect seawater temperature or composition and we conclude that skeletal δ18O is principally controlled by other processes. Calcification site pH in one coral record was estimated from previous SIMS measurements of skeletal δ11B. We model predicted skeletal δ18O as a function of calcification site pH, DIC residence time at the site and DIC source (reflecting the inputs of seawater and molecular CO2 to the site). We assume that oxygen isotopic equilibration proceeds at the rates observed in seawater and that only the aqueous carbonate ion is incorporated into the precipitating aragonite. We reproduce successfully the observed skeletal δ18O range by assuming that DIC is rapidly utilised at the calcification site (within 1 h) and that ∼80% of the skeletal carbonate is derived from seawater. If carbonic anhydrase catalyses the reversible hydration of CO2 at the calcification site, then oxygen isotopic equilibration times may be substantially reduced and a larger proportion of the skeletal carbonate could be derived from molecular CO2. Seasonal skeletal δ18O variations are most pronounced in the skeleton deposited from late autumn to winter (and coincide with the high density skeletal bands) and are dampened in skeleton deposited from spring to summer. We observed no annual pattern in sea surface temperature or photosynthetically active radiation variability which could potentially correlate with the coral δ18O. At present we are unable to resolve an environmental cue to drive seasonal patterns of short term skeletal δ18O heterogeneity.  相似文献   

2.
We present ion microprobe measurements of oxygen isotopic compositions in the deep-sea coral Lophelia pertusa. Compared to bulk skeletal aragonite fibres, the EMZ (early mineralization zone), near the inside of the calyx, was systematically depleted in 18O. Rayleigh fractionation from a semi-closed fluid reservoir does not explain this and other geochemical differences. Furthermore, pH values estimated from skeletal δ11B data are inconsistent with the idea that EMZ (or centres of calcification) 18O depletion reflects a more alkaline calcification environment. Our data, combined with microstructural and geochemical observations, indicate that the aragonitic fibres and EMZ are formed by a compartmentalized mineralization calicoblastic ectoderm, which exerts strong biological control on the composition of the skeleton. Hence, we propose a new model whereby amorphous calcium carbonates (ACC) are precursors to the EMZ, whereas the fibre precipitation is probably governed by kinetic processes.  相似文献   

3.
We tested the effectiveness of stable isotopes as recorders of physiological changes that occur during coral bleaching and recovery. Montipora capitata and Porites compressa fragments were bleached in outdoor tanks with seawater temperature raised to 30 °C (treatment corals) for one month. Additional fragments were maintained at 27 °C in separate tanks (control corals). After one month, (0 months recovery), buoyant weight was measured and a subset of fragments was frozen. Remaining fragments were returned to the reef for recovery. After 1.5, 4, and 8 months, fragments were collected, measured for buoyant weight, and frozen. Fragments were analyzed for stable carbon and oxygen isotopic compositions of the skeleton (δ13Cs; δ18Os) and nitrogen and carbon isotopic compositions of the host tissue (δ15Nh; δ13Ch) and zooxanthellae (δ15Nz; δ13Cz). δ13Cs decreased immediately after bleaching in M. capitata, but not in P. compressa. δ18Os of both species failed to record the warming event. During the remaining months of recovery, δ13Cs and δ18Os were more enriched in treatment than control corals due to decreases in calcification and metabolic fractionation during that time. Increased δ15Nh of treatment P. compressa may be due to expelled zooxanthellae during bleaching and recovery. Increased δ15Nz at 1.5 months in treatment fragments of both species reflects the increased incorporation of dissolved inorganic nitrogen to facilitate mitotic cell division and/or chl a/cell recovery. Changes in δ13Ch and δ13Cz at 1.5 months in treatment M. capitata indicated a large increase in heterotrophically acquired carbon relative to photosynthetically fixed carbon. We experimentally show that isotopes in coral skeleton, host tissue and zooxanthellae can be used to verify physiological changes during bleaching and recovery, but their use as a proxy for past bleaching events in the skeletal record is limited.  相似文献   

4.
The formation of authigenic Ca-rich rhodochrosite (ACR) in sapropelic sediments of the Gotland Basin, Baltic Sea, is governed by deepwater renewal processes whereby saline water from the North Atlantic flushes the brackish anoxic Baltic Deeps. The carbon and oxygen isotopic compositions of these Mn-carbonates suggest that ACR formation takes place just below the sediment surface and that dissolved compounds from the deepwater column, such as water and bicarbonate molecules, were incorporated in ACR during authigenesis. Porewaters near the sediment surface display δ18O values of −5.4‰ (VSMOW) and are generally depleted in 18O, compared to the oxygen isotopic composition of water in equilibrium with Mn-carbonate solid solutions (ACR δ18O values are −4.6‰). This suggests that early burial diagenetic processes significantly modify the initial isotopic composition of water during Mn-carbonate formation. The reduction of sulfate having δ18O values of +8.4‰ accounts for a permanent enrichment of porewater 18O and observed δ18O values at depth equal to −4.6‰. However, this process does not explain the observed disequilibrium in the oxygen isotopic composition between water and ACR close to the sediment surface where Mn-carbonate formation takes place. Based on isotopic mass balance calculations, we suggest that MnO2 with δ18O values of +8.9‰ released oxygen enriched in 18O into the anoxic porewaters close below the sediment surface. This process should occur after oxygenation events during deepwater renewal when MnO2 accumulates at the surface of anoxic sediments. Manganese carbonates formed in these waters display δ18O values of ∼1.0‰ heavier than values expected solely from the initial deepwater composition. This quantitatively explains the discrepancy between paleosalinities calculated from ACR δ18O based on Mn-carbonate/water isotopic equilibrium fractionation and direct observations for the same period. Our results emphasize the important role of microbial MnO2 reduction during rhodochrosite authigenesis and suggest that Mn(II) activity, rather than alkalinity, is the limiting component for sedimentary Mn-carbonate formation.  相似文献   

5.
The South Asian Summer Monsoon induces vertical mixing in the surface Arabian Sea, leading to a reduction in the Sea Surface Temperature (SST) of the order of 3–4°C. This reduction in temperature is recorded by modern corals (Porites) that grow in the Lakshadweep Islands (coralline islands located at about 350 km off the south-west coast of India) in their stable oxygen isotope ratios (denoted by δ18O). As large coral colonies of this genus are available, our results show that palaeomonsoon records for a few centuries back in time, a crucial input for climatic models aimed at predicting the Asian Monsoon, can be obtained from these corals. We also show that two corals separated by ? 60 km show similar (518O variations as does a giant clam (Tridacna maximus) that grew near one end of the coral colonies. As this clam is known to precipitate CaCO3 in isotopic equilibrium with the ambient sea-water, it is possible to estimate the isotopic offset of coralline δ18O from that of the CaCO3 precipitated in isotopic equilibrium. This ‘disequilibrium effect’ appears to be constant around 4.5±0.2%0. Our calculations show that SST (t, °C) is related to the coral δ18O (δc) and the sea-water δ18O (δw) by the equation t = 3.0–4.68 (δc - δw), which is in good agreement with such relationships for corals from the Pacific and Atlantic.  相似文献   

6.
Uptake of anthropogenic CO2 by the oceans is altering seawater chemistry with potentially serious consequences for coral reef ecosystems due to the reduction of seawater pH and aragonite saturation state (Ωarag). The objectives of this long-term study were to investigate the viability of two ecologically important reef-building coral species, massive Porites sp. and Stylophora pistillata, exposed to high pCO2 (or low pH) conditions and to observe possible changes in physiologically related parameters as well as skeletal isotopic composition. Fragments of Porites sp. and S. pistillata were kept for 6-14 months under controlled aquarium conditions characterized by normal and elevated pCO2 conditions, corresponding to pHT values of 8.09, 7.49, and 7.19, respectively. In contrast with shorter, and therefore more transient experiments, the long experimental timescale achieved in this study ensures complete equilibration and steady state with the experimental environment and guarantees that the data provide insights into viable and stably growing corals. During the experiments, all coral fragments survived and added new skeleton, even at seawater Ωarag < 1, implying that the coral skeleton is formed by mechanisms under strong biological control. Measurements of boron (B), carbon (C), and oxygen (O) isotopic composition of skeleton, C isotopic composition of coral tissue and symbiont zooxanthellae, along with physiological data (such as skeletal growth, tissue biomass, zooxanthellae cell density, and chlorophyll concentration) allow for a direct comparison with corals living under normal conditions and sampled simultaneously. Skeletal growth and zooxanthellae density were found to decrease, whereas coral tissue biomass (measured as protein concentration) and zooxanthellae chlorophyll concentrations increased under high pCO2 (low pH) conditions. Both species showed similar trends of δ11B depletion and δ18O enrichment under reduced pH, whereas the δ13C results imply species-specific metabolic response to high pCO2 conditions. The skeletal δ11B values plot above seawater δ11B vs. pH borate fractionation curves calculated using either the theoretically derived αB value of 1.0194 (Kakihana et al. (1977) Bull. Chem. Soc. Jpn.50, 158) or the empirical αB value of 1.0272 (Klochko et al. (2006) EPSL248, 261). However, the effective αB must be greater than 1.0200 in order to yield calculated coral skeletal δ11B values for pH conditions where Ωarag ? 1. The δ11B vs. pH offset from the seawater δ11B vs. pH fractionation curves suggests a change in the ratio of skeletal material laid down during dark and light calcification and/or an internal pH regulation, presumably controlled by ion-transport enzymes. Finally, seawater pH significantly influences skeletal δ13C and δ18O. This must be taken into consideration when reconstructing paleo-environmental conditions from coral skeletons.  相似文献   

7.
The δC13 and δO18 values of skeletons of shallow water, ahermatypic scleractinian corals from Jamaica show an excellent correlation over a wide range of isotopic composition. Within individual specimens there are large differences in the isotopic composition of separate skeletal elements. Some of these ahermatypes are enriched in O18 relative to equilibrium precipitates of calcium carbonate from Jamaican sea water. Therefore our data do not support a two-reservoir mixing model for calcification if one of these reservoirs consists of dissolved marine (inorganic) bicarbonate. As some of these ahermatypic species are enriched in both C13 and O18 relative to hermatypic corals from the same reefs, calcification models based on withdrawal of metabolic CO2 by photosynthesizing zooxanthellae must also be modified.  相似文献   

8.
The oxygen and hydrogen isotopic composition of Eocene and Miocene freshwater cherts in the western United States records regional climatic variation in the Cenozoic. Here, we present isotopic measurements of 47 freshwater cherts of Eocene and Miocene age from the Great Basin of the western United States at two different sites and interpret them in light of regional climatic and tectonic history. The large range of δ18O of terrestrial cherts measured in this study, from 11.2‰ to 31.2‰ (SMOW: Standard Mean Ocean), is shown to be primarily the result of variations in δ18O of surface water. The following trends and patterns are recognized within this range of δ18O values. First, in Cenozoic rocks of northern Nevada, chert δ18O records the same shift observed in authigenic calcite between the Eocene and Miocene that has been attributed to regional surface uplift. The consistent covariation of proxies suggests that chert reliably records and retains a signal of ancient meteoric water isotopic composition, even though our analyses show that chert formed from warmer waters (40°C) than coexisting calcite (20°C). Second, there is a strong positive correlation between δ18O and δD in Eocene age chert from Elko, Nevada and Salina, Utah that suggests large changes in lake water isotopic composition due to evaporation. Evaporative effects on lake water isotopic composition, rather than surface temperature, exert the primary control on the isotopic composition of chert, accounting for 10‰ of the 16‰ range in δ18O measured in Eocene cherts. From authigenic mineral data, we calculate a range in isotopic composition of Eocene precipitation in the north-central Great Basin of −10 to −14‰ for δ18O and −70 to −100‰ for δD, which is in agreement with previous estimates for Eocene basins of the western United States. Due to its resistance to alteration and record of variations in both δ18O and δD of water, chert has the potential to corroborate and constrain the cause of variations in isotope stratigraphies.  相似文献   

9.
High-resolution δ18O and δ13C records obtained from seven cores were drilled from ledges of the reef builder gastropod Dendropomapetreaum and used to reconstruct variations in the Levantine basin sea surface temperature, hydrology and productivity during the past 500 years. The δ18O of the aragonite shell of living D. petreaum indicate that skeletal deposition occurs under isotopic equilibrium and faithfully record the temperature and surface water δ18O during summer and autumn. The mean down core δ18O record clearly captures global and local climatic events, such as the Little Ice Age (LIA) and the recent warming of surface waters in the Eastern Mediterranean. Comparison to the Western Mediterranean vermetid δ18O record reveals changes in the freshwater/evaporation budgets of the two basins during cold and warm periods. The Eastern basin had lower surface temperatures and excess evaporation during the LIA and experienced a relatively larger warming and/or a decrease in freshwater/evaporation during the past 70 years. The D. petraeum δ13C is strongly related to δ13C of dissolved inorganic carbon and to the primary productivity of the surface water. The mean down core δ13C record exhibits enrichment during the LIA maximum and a strong depletion trend during the last century. The LIA δ13C enrichment is attributed to an increase in primary production and high nutrient levels which resulted from increased vertical mixing and upwelling. The last century δ13C depletion is mostly related to the increased anthropogenic emissions of 13C depleted carbon dioxide and to a certain decrease in primary production. The data indicate that D. petraeum isotopic signatures are unique proxies for last 500 years high-resolution reconstruction of paleo-oceanographic environments in the Mediterranean and potentially in the sub-tropical Atlantic regions.  相似文献   

10.
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 (δ18OSMOW=+24.4 to +26.5‰δ13CPDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ18OSMOW=+18.4 to +25.8‰; δ13CPDB=?2.1 to +0.2‰), and calcite (δ18OSMOW=+21.3 to +32.6‰; δ13CPDB=?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.  相似文献   

11.
The oxygen and carbon stable isotope compositions of cave speleothems provide a powerful method for understanding continental climate change. Here, we examine the question of the regionality of this isotopic record and its linkage with the marine isotopic record in the Eastern Mediterranean (EM) region. The study presents a new, accurately dated 250-kyr δ18O and δ13C record determined from speleothems of the Peqiin Cave, Northern Israel. Its comparison with the continuous 185-kyr isotopic record of the Soreq Cave speleothems from Central Israel reveals striking similarities. Thus, a strong regional climatic signal, brought about by variations in temperature and rainfall amount, is reflected in both cave records. Low δ18O minima in the Peqiin profile for the last 250- to 185-kyr period (interglacial marine isotopic stage 7) match the timing of sapropels 9 to 7 and are indicative of high rainfall in the EM region at these times. The combined Soreq and Peqiin δ18O record for the last 250 kyr excellently matches the published Globigerinoides ruber (G. ruber) marine δ18O record for the EM Sea, with the isotopic compositional difference ΔG.ruber-speleothems remaining relatively constant at −5.6 ± 0.7‰, thus establishing for the first time a robust, exploitable link between the land and the marine isotopic records. The correspondence of low δ18O speleothem values and high cave water stands with low G. ruber δ18O values during interglacial sapropel events indicates that these periods were characterized by enhanced rainfall in the EM land and sea regions. By use of sea surface temperatures derived from alkenone data as a proxy for land temperatures at the Soreq Cave, we calculate the paleorainfall δ18O values and its amounts. Maximum rainfall and lowest temperature conditions occurred at the beginning of the sapropel events and were followed by decrease in rainfall and increase in temperatures, leading to arid conditions. The record for the last 7000 yr shows a trend toward increasing aridity and agrees well with climatic and archeological data from North Africa and the Middle East.  相似文献   

12.
The Columbia River Flood Basalts (CRB) of the northwestern USA are coeval with eruptions of several thousand km3 of rhyolite. A broad survey of major phenocryst oxygen isotopes and of O and Hf isotopes in zircons from these rhyolites reveals significant diversity in inferred δ18Omelt values, ranging from +1.9 to +10.5‰ (SMOW), and in zircon Hf isotope compositions, which range from εHf = ?39 to +9. This newly identified isotopic diversity shows that the syn‐CRB rhyolites were derived from high‐percentage melting of the crust. Low‐δ18O rhyolites, which fingerprint the melting of hydrothermally altered crust, are concentrated at the edge of the North American craton. This suggests that the conditions of crustal heating, faulting, and hydrothermal alteration required for the production of these rhyolites were concentrated there by the contrasts in crustal thickness and rheology associated with the boundary between the North American craton and younger accreted terranes.  相似文献   

13.
Eight pectinid shells were collected and subjected to quantitative study using δ18O and δ13C isotopic analysis in order to study the paleoenvironment which prevailed during their calcification. The scalerochronological variations in δ18O and δ13C values, among these shells are also discussed. The Early Miocene pectinid shells display highly depleted δ18O and δ13C signature as a result of paleo-meteoric water with heavy rainfall that was produced by Tropical Cyclones when the Mediterranean Sea was open. The Early Pliocene pectinid shells reveal depleted δ18O values, related to the influx of fresh water influenced by monsoonal activity following the formation of the Tibetan Plateau. Their enrichment in the δ13C isotopic excursion is referred to high productivity of the Indian Ocean, which was the main source of the Red Sea water. The Pleistocene pectinid shell shows highly depleted δ18O and δ13C signature with obvious diagenetic shell structure, indicating that a wetter humid climate prevailed during the Early–Middle Pleistocene and long sub-arial exposure of the shell. The Recent Mediterranean pectinid shell displays slight enrichment in δ18O and δ13C values referring to deeper inhabitation of this species with a low temperature and high salinity environment. The scalerochronological variations in both δ18O and δ13C values, along these shells is referred to seasonal variations or kinetic effects.  相似文献   

14.
The oxygen and carbon isotopic compositions of minerals from banded iron formations (BIFs) and high-grade ore in the region of the Kursk Magnetic Anomaly (KMA) were determined in order to estimate the temperature of regional metamorphism and the nature of rock-and ore-forming solutions. Magnetite and hematite of primary sedimentary or diagenetic origin have δ18O within the range from +2 to 6‰. During metamorphism, primary iron oxides, silicates, and carbonates were involved in thermal dissociation and other reactions to form magnetite with δ18O = +6 to +11‰. As follows from a low δ18Oav = ?3.5‰ of mushketovite (magnetite pseudomorphs after hematite) in high-grade ore, this mineral was formed as a product of hematite reduction by organic matter. The comparison of δ18O of iron oxides, siderite, and quartz from BIFs formed at different stages of the evolution of the Kursk protogeosyncline revealed specific sedimentation (diagenesis) conditions and metamorphism of the BIFs belonging to the Kursk and Oskol groups. BIF of the Oskol Group is distinguished by a high δ18O of magnetite compared to other Proterozoic BIFs. Martite ore differs from host BIF by a low δ18O = ?0.2 to ?5.9‰. This implies that oxygen from infiltration water was incorporated into the magnetite lattice during the martite formation. Surface water penetrated to a significant depth through tectonic faults and fractures.  相似文献   

15.
Evidence for ocean acidification in the Great Barrier Reef of Australia   总被引：1，自引：0，他引：1  
Geochemical records preserved in the long-lived carbonate skeleton of corals provide one of the few means to reconstruct changes in seawater pH since the commencement of the industrial era. This information is important in not only determining the response of the surface oceans to ocean acidification from enhanced uptake of CO2, but also to better understand the effects of ocean acidification on carbonate secreting organisms such as corals, whose ability to calcify is highly pH dependent. Here we report an ∼200 year δ11B isotopic record, extracted from a long-lived Porites coral from the central Great Barrier Reef of Australia. This record covering the period from 1800 to 2004 was sampled at yearly increments from 1940 to the present and 5-year increments prior to 1940. The δ11B isotopic compositions reflect variations in seawater pH, and the δ13C changes in the carbon composition of surface water due to fossil fuel burning over this period. In addition complementary Ba/Ca, δ18O and Mg/Ca data was obtained providing proxies for terrestrial runoff, salinity and temperature changes over the past 200 years in this region. Positive thermal ionization mass spectrometry (PTIMS) method was utilized in order to enable the highest precision and most accurate measurements of δ11B values. The internal precision and reproducibility for δ11B of our measurements are better than ±0.2‰ (2σ), which translates to a precision of better than ±0.02 pH units. Our results indicate that the long-term pre-industrial variation of seawater pH in this region is partially related to the decadal-interdecadal variability of atmospheric and oceanic anomalies in the Pacific. In the periods around 1940 and 1998 there are also rapid oscillations in δ11B compositions equivalent changes in pH of almost 0.5 U. The 1998 oscillation is co-incident with a major coral bleaching event indicating the sensitivity of skeletal δ11B compositions to loss of zooxanthellate symbionts. Importantly, from the 1940s to the present-day, there is a general overall trend of ocean acidification with pH decreasing by about 0.2-0.3 U, the range being dependent on the value assumed for the fractionation factor α(B3-B4) of the boric acid and borate species in seawater. Correlations of δ11B with δ13C during this interval indicate that the increasing trend towards ocean acidification over the past 60 years in this region is the result of enhanced dissolution of CO2 in surface waters from the rapidly increasing levels of atmospheric CO2, mainly from fossil fuel burning. This suggests that the increased levels of anthropogenic CO2 in atmosphere has already caused a significant trend towards acidification in the oceans during the past decades. Observations of surprisingly large decreases in pH across important carbonate producing regions, such as the Great Barrier Reef of Australia, raise serious concerns about the impact of Greenhouse gas emissions on coral calcification.  相似文献   

16.
《Geochimica et cosmochimica acta》1999,63(11-12):1787-1804
Rift-related lavas of the North Shore Volcanic Group (NSVG) are intruded by plutonic rocks of the Duluth Complex along the unconformity between the NSVG and the underlying Proterozoic metasedimentary rocks (Animikie Group) and Archean volcano-sedimentary and plutonic rocks. Heat associated with the emplacement of the mafic intrusions generated fluid flow in the overlying plateau lavas. δ18O values for whole rocks from the NSVG and hypabyssal sills range from 5.5 to 17.7‰ and 5.3 to 11.5‰, respectively, and most values are higher than those considered “normal” for basaltic rocks (5.4 to 6.0‰). In general, there is a positive correlation between whole rock δ18O and water content, which suggests that elevated δ18O values are related primarily to secondary mineral growth and isotopic exchange during hydrothermal alteration and metamorphism. δ18OH2O values computed from amygdule-filling minerals such as smectite, chlorite, and epidote found in low- to high-temperature metamorphic zones range from ∼−1 to 6‰ with an average value of ∼3‰. Smectite in the lower-grade zones gives computed δDH2O values between −26 and −83‰, whereas epidote in the higher-grade zones gives δDH2O values of −15 to 6‰. Fluid isotopic compositions computed from epidote and smectite values are suggestive of the involvement of at least two fluids during the early stages of amygdule filling. Fluid δD and δ18O values determined from epidote at the higher metamorphic grades indicate that seawater dominated the deeper portions of the system where greenschist facies assemblages and elevated δ18O values were produced in flow interiors, as well as margins. Smectite isotopic compositions suggest that meteoric water was predominant in the shallower portions of the system. The increase in δ18O values of massive flow interiors with depth is interpreted as a result of rock interaction with a fluid of constant oxygen isotopic composition with increasing temperature. The stable isotopic data are supportive of previous suggestions that seawater was involved in the hydrothermal system associated with the Midcontinent Rift. Although the origin of the seawater remains problematic, it appears that marine incursions may have occurred during the late stages of Portage Lake volcanism, and periodically thereafter.  相似文献   

17.
《Geochimica et cosmochimica acta》1999,63(13-14):1981-1989
In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in Central Switzerland. Comparisons between calculated equilibrium isotope values, using the fractionation equation of Friedman and O’Neil, (1977) and measured oxygen isotope ratios of calcite in the sediment-traps reveal that oxygen isotopic values of autochthonous calcite (δ18O) are in isotopic equilibrium with ambient water during most of the spring and summer, when the majority of the calcite precipitates. In contrast, small amounts of calcite precipitated in early-spring and again in late-autumn are isotopically depleted in 18O relative to the calculated equilibrium values, by as much as 0.8‰. This seasonally occurring apparent isotopic nonequilibrium is associated with times of high phosphorous concentrations, elevated pH (∼8.6) and increased [CO32−] (∼50 μmol/l) in the surface waters. The resulting weighted average δ18O value for the studied period is −9.6‰, compared with a calculated equilibrium δ18O value of −9.4‰. These data convincingly demonstrate that δ18O of calcite are, for the most part, a very reliable proxy for temperature and δ18O of the water.  相似文献   

18.
The relationship between molluscan shell growth rate and skeletal δ18O and δ13C was investigated in a detailed field study for the scallop, Pecten maximus. Seasonal variation in shell growth rate was found to be a governing factor influencing shell δ18O and δ13C. At low shell growth rates, shell δ18O were more positive (of the order +0.4‰) and δ13C more negative (up to −2‰) as compared with predicted values for precipitation of inorganic calcite in isotopic equilibrium with seawater. The deviations in δ18O were hypothesized as reflecting possible differences in solution carbonate chemistry at the site of mineralization in the extrapallial fluid as compared with that of the external seawater medium. The deviations in shell δ13C were consistent with incorporation of isotopically depleted respiratory 13C (i.e., a metabolic effect). A trend toward more depleted shell δ18O and δ13C values occurred at higher shell growth rates, with negative δ18O values as compared with predicted equilibrium at shell growth rates above 0.13 mm per day. These simultaneous negative deviations in skeletal δ18O and δ13C were interpreted as resulting from a kinetic effect. The implications for environmental reconstruction from molluscan isotopic records are discussed in light of a model of isotopic behavior based on the findings of the study.  相似文献   

19.
Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ13C=?28·7‰ PDB and δ18O=?1·6‰ PDB through to δ13C=?6·9‰ PDB and δ18O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ13C=?12·0 to ?10·1‰ PDB and δ18O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ34S=+24·8‰ CDT and δ18O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ34S=+6 to +11‰ CDT and δ18O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.  相似文献   

20.
Offsets from isotopic equilibrium in biogenic carbonates have complicated paleoclimate reconstructions for decades. A new archive of climate, deep-sea corals, is used to evaluate the calcification processes, independent of photosynthesis, that contribute to these offsets. Carbon and oxygen stable isotope data from six modern deep-sea corals show strong linear trends between δ13C and δ18O. Slopes of these trends between samples are similar and range between 1.9 to 2.6 for Δδ13C/Δδ18O. Linear trends intersect isotopic equilibrium for δ18O and are slightly depleted for δ13C. Variations in the isotopic ratios are strongly correlated with the density banding structure. Isotopically depleted aragonite is associated with light, quickly precipitating bands, whereas isotopically enriched points correspond to slowly accumulating, less dense aragonite. The densest white band at the trabecular center is furthest from isotopic equilibrium for both carbon and oxygen. Data from this region fall off the linear trend between δ18O and δ13C. This deviation, where δ13C remains constant while the δ18O continues to decrease, does not support “vital effect” mechanisms that call upon kinetic fractionation to explain offsets from isotopic equilibrium. We propose a new mechanism for vital effects in these deep-sea corals that is based on a thermodynamic response to a biologically induced pH gradient in the calcifying region.  相似文献   

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