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1.
Carbon isotopes in speleothems can vary in response to a number of complex processes active in cave systems that are both directly and indirectly related to climate. Progressing downward from the soil zone overlying the cave, these processes include soil respiration, fluid-rock interaction in the host limestone, degassing of CO2 and precipitation of calcite upflow from the speleothem drip site, and calcite precipitation at the drip site. Here we develop a new approach to independently constrain the roles of water-rock interaction and soil processes in controlling stalagmite δ13C. This approach uses the dead carbon proportion (dcp) estimated from coupled 14C and 230Th/U measurements, in conjunction with Sr isotope analyses on stalagmite calcite from a central Sierra Nevada foothills cave in California, a region characterized by a highly seasonal Mediterranean-type climate, to determine the roles of water-rock interaction and soil processes in determining stalagmite δ13C. Increases in stalagmite dcp between 16.5 and 8.8 ka are coincident with decreased δ13C, indicating a varying yet substantial contribution from the soil organic matter (SOM) reservoir, likely due to significantly increased average age of SOM in the soil veneer above the cave during wet climatic intervals.We use geochemical and isotope mixing models to estimate the host-carbonate contribution throughout the δ13C time series and determine the degree of degassing and calcite precipitation that occurred prior to precipitation of stalagmite calcite. The degree of degassing and prior calcite precipitation we calculate varies systematically with other climate indicators, with less degassing and prior calcite precipitation occurring during wetter climatic intervals and more during drier intervals. Modeled δ13C values and degassing calculations suggest that some degree of prior calcite precipitation is necessary at all time intervals to explain measured stalagmite δ13C values, even during relatively wet intervals. These results illustrate the importance of constraining degassing and prior calcite precipitation in the interpretation of speleothem δ13C records, particularly those from caves that formed in seasonal semi-arid to arid environments.  相似文献   

2.
Applications of speleothem calcite geochemistry in climate change studies require the evaluation of the accuracy and sensitivity of speleothem proxies to correctly infer paleoclimatic information. The present study of Harrison’s Cave, Barbados, uses the analysis of the modern climatology and groundwater system to evaluate controls on the C and O isotopic composition of modern speleothems. This new approach directly compares the δ18O and δ13C values of modern speleothems with the values for their corresponding drip waters in order to assess the degree to which isotopic equilibrium is achieved during calcite precipitation. If modern speleothems can be demonstrated to precipitate in isotopic equilibrium, then ancient speleothems, suitable for paleoclimatic studies, from the same cave environment may also have been precipitated in isotopic equilibrium. If modern speleothems are precipitated out of isotopic equilibrium, then the magnitude and direction of the C and O isotopic offsets may allow specific kinetic and/or equilibrium isotopic fractionation mechanisms to be identified.Carbon isotope values for the majority of modern speleothem samples from Harrison’s Cave fall within the range of equilibrium values predicted from the combined use of (1) calcite-water fractionation factors from the literature, (2) measured temperatures, and (3) measured δ13C values of the dissolved inorganic carbon of drip waters. Calcite samples range from ∼0.8‰ higher to ∼1.1‰ lower than predicted values. The 13C depletions are likely caused by kinetically driven departures in the fractionation between HCO3− (aq) and CaCO3 from equilibrium conditions, caused by rapid calcite growth. 13C enrichments can be accounted for by Rayleigh distillation of the HCO3− (aq) reservoir during degassing of 13C-depleted CO2.Modern speleothems from Harrison’s Cave are not in O isotopic equilibrium with their corresponding drip waters and are 0.2‰ to 2.3‰ enriched in 18O relative to equilibrium values. δ18O variations in modern calcite are likely controlled by kinetically driven changes in the fractionation between HCO3− (aq) and CaCO3 from equilibrium conditions to nonequilibrium conditions, consistent with rapid calcite growth. In contrast to δ13C, δ18O values of modern calcite may not be affected by Rayleigh distillation during degassing because CO2 hydration and hydroxylation reactions will buffer the O isotopic composition of the HCO3− (aq) reservoir. If the effects of Rayleigh distillation manifest themselves in the O isotopic system, they will result in 18O enrichment in the HCO3− (aq) reservoir and ultimately in the precipitated CaCO3.  相似文献   

3.
Understanding the relationships between speleothem stable isotopes (δ13C δ18O) and in situ cave forcing mechanisms is important to interpreting ancient stalagmite paleoclimate records. Cave studies have demonstrated that the δ18O of inorganically precipitated (low temperature) speleothem calcite is systematically heavier than the δ18O of laboratory-grown calcite for a given temperature. To understand this apparent offset, rainwater, cave drip water, groundwater, and modern naturally precipitated calcite (farmed in situ) were grown at multiple locations inside Hollow Ridge Cave in Marianna, Florida. High resolution micrometeorological, air chemistry time series and ventilation regimes were also monitored continuously at two locations inside the cave, supplemented with periodic bi-monthly air gas grab sample transects throughout the cave.Cave air chemistry and isotope monitoring reveal density-driven airflow pathways through Hollow Ridge Cave at velocities of up to 1.2 m s−1 in winter and 0.4 m s−1 in summer. Hollow Ridge Cave displays a strong ventilation gradient in the front of the cave near the entrances, resulting in cave air that is a mixture of soil gas and atmospheric CO2. A clear relationship is found between calcite δ13C and cave air ventilation rates estimated by proxies pCO2 and 222Rn. Calcite δ13C decreased linearly with distance from the front entrance to the interior of the cave during all seasons, with a maximum entrance-to-interior gradient of Δδ13CCaCO3 = −7‰. A whole-cave “Hendy test” at multiple contemporaneous farming sites reveals that ventilation induces a +1.9 ± 0.96‰ δ13C offset between calcite precipitated in a ventilation flow path and calcite precipitated on the edge or out of flow paths. This interpretation of the “Hendy test” has implications for interpreting δ13C records in ancient speleothems. Calcite δ13CCaCO3 may be a proxy not only for atmospheric CO2 or overlying vegetation shifts but also for changes in cave ventilation due to dissolution fissures and ceiling collapse creating and plugging ventilation windows.Farmed calcite δ18O was found to exhibit a +0.82 ± 0.24‰ offset from values predicted by both theoretical calculations and laboratory-grown inorganic calcite. Unlike δ13CCaCO3, oxygen isotopes showed no ventilation effects, i.e. Δδ18OCaCO3 appears to be a function of growth temperature only although we cannot rule out a small effect of (unmeasured) gradients in relative humidity (evaporation) accompanying ventilation. Our results support the findings of other cave investigators that water-calcite fractionation factors observed in speleothem calcite are higher that those measured in laboratory experiments. Cave and laboratory calcite precipitates may differ mainly in the complex effects of kinetic isotope fractionation. Combining our data with other recent speleothem studies, we find a new empirical relationship for cave-specific water-calcite oxygen isotope fractionation across a range of temperatures and cave environments:
1000lnα=16.1(103T-1)-24.6  相似文献   

4.
‘Clumped isotope’ thermometry is based on analyzing mass 47 in CO2 extracted from carbonates and uses the tracer mass 47 anomaly (Δ47). Δ47 is defined as the deviation of R47 from that expected for a random distribution of isotopologues and reflects a temperature dependent preference of 13C and 18O to create a bond with each other in CO2 or in the carbonate lattice. Being an internal characteristic of the carbonate mineral, it is independent of the isotopic composition of the water in which equilibrium precipitation of the carbonate occurs and can therefore be used to independently determine carbonate growth temperatures. This work provides a first examination of the applicability of ‘clumped isotopes’ thermometry to reconstructing the growth temperatures of speleothems, by examining the glacial/interglacial variations of the Δ47 values of speleothem carbonates from Soreq cave, Israel. The results indicate that the last glacial maximum temperatures were 6-7 °C colder than modern day temperature and a sample at 56 Ky BP was 3 °C colder than the modern. Early Holocene temperatures were slightly above modern day, and late Holocene temperatures were slightly below modern day. These temperature variations are similar to those previously estimated for Eastern Mediterranean sea surface water. Cave water was 18O depleted in the Holocene compared to modern day (by 0.6-1‰) and 1.1‰ more enriched in the last glacial maximum. Comparison of these cave water δ18O values with fluid inclusion δD values indicated a late Holocene d-excess value within the range of modern rainfall, implying ∼45% relative humidity. Last glacial maximum and early Holocene d-excess values were significantly lower, suggesting relative humidity of ∼60% and ∼70%, respectively. The temperatures reported in this study were empirically corrected for a non-equilibrium artifact observed in a modern speleothem. The similarity of the temperature variations obtained here to other, independent, records in the region suggests that the Δ47-temperature calibration slope observed in inorganic synthetic calcite and marine organisms may also be applied in speleothems. But the offset observed in modern temperature suggests that the intercept is different so that a separate calibration is needed for accurate absolute temperature reconstruction using speleothem ‘clumped isotopes’. Similar examination of additional caves would be necessary to determine whether such empirical correction can be generally applied or is it a unique characteristic of Soreq cave.  相似文献   

5.
Understanding the relationship between stable isotope signals recorded in speleothems (δ13C and δ18O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO2.The water entering the cave flows as a thin film towards the drip site. CO2 degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scale of several 10-100 s. The δ13C value of the drip water is mainly determined by the isotopic composition of soil CO2. The evolution of the δ18O value of the carbonate species is determined by the long exchange time Tex, between oxygen in carbonate and water of several 10,000 s. Even if the oxygen of the CO2 in soil water is in isotopic equilibrium with that of the water, dissolution of limestone delivers oxygen with a different isotopic composition changing the δ18O value of the carbonate species. Consequently, the δ18O value of the rainwater will only be reflected in the drip water if it has stayed in the rock for a sufficiently long time.After the water has entered the cave, the carbon and oxygen isotope composition of the drip water may be altered by CO2-exchange with the cave air. Exchange times, , of about 3000 s are derived. Thus, only drip water, which drips in less than 3000 s onto the stalagmite surface, is suitable to imprint climatic signals into speleothem calcite deposited from it.Precipitation of calcite proceeds with time constants, τp, of several 100 s. Different rate constants and equilibrium concentrations for the heavy and light isotopes, respectively, result in isotope fractionation during calcite precipitation. Since Tex ? τp, exchange with the oxygen in the water can be neglected, and the isotopic evolution of carbon and oxygen proceed analogously. For drip intervals Td < 0.1τp the isotopic compositions of both carbon and oxygen in the solution evolve linearly in time. The calcite precipitated at the apex of the stalagmite reflects the isotopic signal of the drip water.For long drip intervals, when calcite is deposited from a stagnant water film, long drip intervals may have a significant effect on the isotopic composition of the DIC. In this case, the isotopic composition of the calcite deposited at the apex must be determined by averaging over the drip interval. Such processes must be considered when speleothems are used as proxies of past climate variability.  相似文献   

6.
Variations in speleothem oxygen-isotope values (δ18O) result from a complicated interplay of environmental controls and processes in the ocean, atmosphere, soil zone, epikarst, and cave system. As such, the controls on speleothem δ18O values are extremely complex. An understanding of the processes that control equilibrium and kinetic fractionation of oxygen isotopes in water and carbonate species is essential for the proper interpretation of speleothem δ18O as paleoclimate and paleoenvironmental proxies, and is best complemented by study of site-specific cave processes such as infiltration, flow routing, drip seasonality and saturation state, and cave microclimate, among others. This review is a process-based summary of the multiple controls on δ18O in the atmosphere, soil, epikarst, and speleothem calcite, illustrated with case studies. Primary controls of δ18O in the atmosphere include temperature and relative humidity through their role in the multiple isotope “effects”. Variability and modifications of water δ18O values in the soil and epikarst zones are dominated by evaporation, mixing, and infiltration of source waters. The isotopically effective recharge into a cave system consists of those waters that participate in precipitation of CaCO3, resulting in calcite deposition rates which may be biased to time periods with optimal dripwater saturation state. Recent modeling, experimental, and observational data yield insight into the significance of kinetic fractionation between dissolved carbonate phases and solid CaCO3, and have implications for the ‘Hendy’ test. To assist interpretation of speleothem δ18O time series, quantitative and semi-quantitative δ18O-climate calibrations are discussed with an emphasis on some of the difficulties inherent in using modern spatial and temporal isotope gradients to interpret speleothems as paleoclimate proxy records. Finally, several case studies of globally significant speleothem paleoclimate records are discussed that show the utility of δ18O to reconstruct past climate changes in regions that have been typically poorly represented in paleoclimate records, such as tropical and subtropical terrestrial locations. The new approach to speleothem paleoclimatology emphasizes climate teleconnections between regions and attribution of forcing mechanisms. Such investigations allow paleoclimatologists to infer regional to global-scale climate dynamics.  相似文献   

7.
High resolution δ13C and δ18O profiles recorded in precisely dated speleothems are widely used proxies for the climate of the past. Both δ13C and δ18O depend on several climate related effects including meteorological processes, processes occurring in the soil zone above the cave and isotope fractionation processes occurring in the solution layer on the stalagmite surface. Here we model the latter using a stalagmite isotope and growth model and determine the relationship between the stable isotope values in speleothem calcite and cave parameters, such as temperature, drip interval, water pCO2 and a mixing coefficient describing mixing processes between the solution layer and the impinging drop.The evolution of δ13C values is modelled as a Rayleigh distillation process and shows a pronounced dependence on the residence time of the solution on the stalagmite surface and the drip interval, respectively. The evolution of δ18O values, in contrast, is also influenced by buffering reactions between the bicarbonate in the solution and the drip water driving the δ18O value of the bicarbonate towards the value expected for equilibrium isotope fractionation between drip water and calcite. This attenuates the dependence of the δ18O values on drip interval. The temperature dependence of δ18O, however, is more pronounced than for δ13C and in a similar range as expected for fractionation under equilibrium conditions.We also investigate the isotopic enrichment of the δ13C and δ18O values along individual growth layers and, thus, the slopes expected for Hendy tests. The results show that a positive Hendy test is only possible if isotope fractionation occurred under disequilibrium conditions. However, a negative Hendy test does not exclude that isotope fractionation occurred under disequilibrium conditions. A more reliable indicator for disequilibrium fractionation is the enrichment of the δ13C values along an individual growth layer.  相似文献   

8.
We derive equations describing the evolution of the carbon and oxygen isotope composition of the bicarbonate in a calcite precipitating solution on the surface of a stalagmite using a classical Rayleigh approach. The combined effects of calcite precipitation, degassing of CO2 and the buffering effect of the water reservoir are taken into account. Whereas δ13C shows a progressive increase to a final constant value, δ18O shows an initial isotopic enrichment, which exponentially decays due to the buffering effect of the water reservoir. The calculated evolution is significantly different for both carbon and oxygen isotopes than derived in a recent paper [Dreybrodt W. (2008) Evolution of the isotopic composition of carbon and oxygen in a calcite precipitating H2O-CO2-CaCO3 solution and the related isotopic composition of calcite in stalagmites. Geochim. Cosmochim. Acta72, 4712-4724.].Furthermore, we discuss the isotopic evolution of the bicarbonate in the solution for long residence times on the stalagmite surface, i.e., for t→∞. The equilibrium isotope ratio of the bicarbonate is then determined by isotopic exchange between the cave atmosphere and the bicarbonate in the solution and can be calculated by equilibrium isotope fractionation. For strongly ventilated caves exchange with the cave atmosphere will result in higher δ13C and δ18O values than those observed in a pure Rayleigh distillation scenario, for sparsely ventilated caves it will result in lower δ13C and δ18O values.  相似文献   

9.
段福才  孔兴功 《中国岩溶》2011,30(1):101-104
作为古气候代用指标,石笋氧同位素为亚洲季风演化研究提供了一系列可靠的证据。然而,关于石笋氧同位素指示的气候意义一直存在争论。本文选取了位于神农架地区海拔1250～2250m的黑龙洞、青天洞和三宝洞3个洞穴进行对比分析,发现不同海拔洞穴石笋δ18O在波动形式上相同,但绝对值存在约-0.1‰/100m的系统差,而大气降水的在该地的海拔效应约为-0.2‰/100m。为此,我们认为,石笋δ18O除了受季风降雨的影响外,不同海拔的温度梯度也对石笋δ18O具有较大的贡献。结合洞穴年均温度,初步估算石笋δ18O的温度效应约为-0.25‰/℃,与O’Neil的同位素平衡分馏计算结果相同。   相似文献   

10.
Diverse interpretations have been made of carbon isotope time series in speleothems, reflecting multiple potential controls. Here we study the dynamics of 13C and 12C cycling in a particularly well-constrained site to improve our understanding of processes affecting speleothem δ13C values. The small, tubular Grotta di Ernesto cave (NE Italy) hosts annually-laminated speleothem archives of climatic and environmental changes. Temperature, air pressure, pCO2, dissolved inorganic carbon (DIC) and their C isotopic compositions were monitored for up to five years in soil water and gas, cave dripwater and cave air. Mass-balance models were constructed for CO2 concentrations and tested against the carbon isotope data. Air advection forces winter pCO2 to drop in the cave air to ca. 500 ppm from a summer peak of ca. 1500 ppm, with a rate of air exchange between cave and free atmosphere of approximately 0.4 days. The process of cave ventilation forces degassing of CO2 from the dripwater, prior to any calcite precipitation onto the stalagmites. This phase of degassing causes kinetic isotope fractionation, i.e. 13C-enrichment of dripwater whose δ13CDIC values are already higher (by about 1‰) than those of soil water due to dissolution of the carbonate rock. A subsequent systematic shift to even higher δ13C values, from −11.5‰ in the cave drips to about −8‰ calculated for the solution film on top of stalagmites, is related to degassing on the stalagmite top and equilibration with the cave air. Mass-balance modelling of C fluxes reveals that a very small percentage of isotopically depleted cave air CO2 evolves from the first phase of dripwater degassing, and shifts the winter cave air composition toward slightly more depleted values than those calculated for equilibrium. The systematic 13C-enrichment from the soil to the stalagmites at Grotta di Ernesto is independent of drip rate, and forced by the difference in pCO2 between cave water and cave air. This implies that speleothem δ13C values may not be simply interpreted either in terms of hydrology or soil processes.  相似文献   

11.
Fluid inclusions found trapped in speleothems (cave deposited travertine) are interpreted as samples of seepage water from which enclosing calcium carbonate was deposited. The inclusions are assumed to have preserved their D/H ratios since the time of deposition. Initial 18O/16O ratios can be inferred from δD because rain- and snow-derived seepage waters fall on the meteoric water line (δD = 8δ18O + 10). Estimates of temperature of deposition of the carbonate can be calculated from inclusion D/H ratios and δ18O of enclosing calcite in Pleistocene speleothems. For most speleothems investigated (0–200,000 yr old) δ18O of calcite appears to have decreased with increasing temperature of deposition indicating that the dominant cause of climate-dependent change in δ18O of calcite was the change in Kcw, the isotope fractionation equilibrium constant, with temperature; δ18O of meteoric precipitation generally increased with increasing temperature, but not sufficiently to compensate for the decrease in Kcw.  相似文献   

12.
The suitability of speleothems for interpreting palaeoclimate is typically determined by using either the Hendy Test, overlapping analysis or long‐term cave environment monitoring. However, in many cases, these methods are not applicable, because a speleothem lacks clearly traceable layers for the Hendy Test, it is difficult to obtain an overlapping speleothem nearby, or long‐term cave monitoring is impractical. The authors propose a multiple cave deposit approach to assess the suitability of speleothems for palaeoclimate study. Speleothems collected from two sites within Raccoon Mountain Cave, Tennessee (USA) exhibit remarkable spatial variation (δ13C: ?10·3‰ to ?2·2‰) over a relatively short distance (ca 260 m). Drip water δ18O values exhibit a seasonal precipitation signal at Site 1 and an annual signal at Site 2. Combining field observations, water isotope analysis and trace‐element data, the authors propose that the speleothem formation at Site 1 and Site 2 tapped distinct sources of CO2: (i) CO2 derived from overlying soils for Site 1; and (ii) limestone dissolved inorganic carbon induced by ground water dissolution for Site 2. Using fresh cave deposits (modern speleothem) δ13C (100% C3 vegetation) as an analogue, a simple model was developed to estimate land surface vegetation for speleothems. The speleothem formation temperature estimated using fresh cave deposit δ18O values generally reflects the mean annual temperature in this region. This study indicates that spatial variations in carbon isotopes could be caused by different carbon sources dominating in different parts of the cave, which should be taken into consideration by researchers when using speleothem δ13C values to reconstruct temporal palaeo‐vegetation changes. This study demonstrates a practical sampling strategy for verifying suitability of speleothems for palaeo‐vegetation and palaeo‐temperature reconstructions by analysing multiple cave deposits, especially for cases in which the Hendy Test, parallel sampling and long‐term monitoring of cave environment are not feasible.  相似文献   

13.
Plio‐Pleistocene speleothems from australopithecine‐bearing caves of South Africa have the potential to yield paleoenvironmental and geochronological information using isotope geochemistry. Prior to such studies it is important to assess the preservation of geochemical signals within the calcitic and aragonitic speleothems, given the tendency of aragonitic speleothems to recrystallize to calcite. This study documents the geochemical suitability of speleothems from the principal hominin‐bearing deposits of South Africa. We use petrography, together with stable isotope and trace element analysis, to identify the occurrence of primary aragonite, primary calcite, and secondary calcite. This study highlights the presence of diagenetic alteration at many of the sites, often observed as interbedded primary and secondary fabrics. Trace element and stable isotopic values distinguish primary calcite from secondary calcite and offer insights into geochemical aspects of the past cave environment. δ13C values of the primary and secondary calcites range from +6 to −9‰ and δ18O values range from −4 to −6‰. The data are thus typical of meteoric calcites with highly variable δ13C and relatively invariant δ18O. High carbon isotope values in these deposits are associated with the effects of recrystallization and rapid outgassing of CO2 during precipitation. Mg/Ca and Sr/Ca ratios differ between primary and secondary calcite speleothems, aiding their identification. Carbon and oxygen isotope values in primary calcite reflect the proportion of C3 and C4 vegetation in the local environment and the oxygen isotope composition of rainfall. Primary calcite speleothems preserve the pristine geochemical signals vital for ongoing paleoenvironmental and geochronological research. © 2009 Wiley Periodicals, Inc.  相似文献   

14.
Despite considerable work on other trace elements, the incorporation of dissolved silicon from cave waters into speleothems has not been previously investigated. In this study, the controls on dissolved Si in cave waters and on adsorbed Si in resulting speleothems are therefore investigated. Bedrock (dolomite), soil water, dripping water, and cave carbonates were retrieved from Heshang Cave situated in the central Yangtze valley of China and were subjected to analysis of dissolved Si content (plus accompanying Ca and Fe analyses). Soil waters have Si/Ca of 45.5 mmol/mol, compared to only 3.2 mmol/mol in the dolomite bedrock, demonstrating that >80% of the dissolved Si must come from dissolution of silicate minerals in the soil. Drip waters have a dissolved Si concentration of ≈4.2 μg/mL, similar to that in the overlying soil water. Actively growing cave carbonates have a Si/Ca of 0.075 mmol/mol suggesting a partition coefficient for incorporation of dissolved silicon of 0.0014, in good agreement with previous laboratory studies. Extrapolating the results of these laboratory studies to the cave environment suggests that changes in Si/Ca in cave carbonates are likely to be primarily controlled by changes in drip-water Si/Ca. The drip-water Si/Ca will, in turn, be controlled by the rate of wind-blown silicate supply; by soil weathering rates; by rainfall dilution; and by precipitation of calcite. The general expectation is that these effects combine to produce high Si/Ca in speleothems during times of low rainfall. A δ18O record from a Heshang Cave stalagmite which grew between 20 and 11 thousand years ago allows these controls to be tested. Correlation of high Si/Ca with high δ18O demonstrates that regional rainfall exerts significant (but not complete) control on speleothem Si/Ca. With further understanding, speleothem Si/Ca may provide a proxy for past rainfall to complement existing proxies such as δ18O and Mg/Ca.  相似文献   

15.
The Pleistocene speleothems of Sa Bassa Blanca cave, Mallorca, are excellent indicators of palaeoclimate variations, and are samples that allow evaluation of the products and processes of mixing‐zone diagenesis in an open‐water cave system. Integrated stratigraphic, petrographic and geochemical data from a horizontal core of speleothem identified two main origins for speleothem precipitates: meteoric‐marine mixing zone and meteoric‐vadose zone. Mixing‐zone precipitates formed at and just below the water–air interface of cave pools during interglacial times, when the cave was flooded as a result of highstand sea‐level. Mixing‐zone precipitates include bladed and dendritic high‐Mg calcite, microporous‐bladed calcite with variable Mg content, and acicular aragonite; their presence suggests that calcium‐carbonate cementation is significant in the studied mixing‐zone system. Fluid inclusion salinities, δ13C and δ18O compositions of the mixing‐zone precipitates suggest that mixing ratio was not the primary control on whether precipitation or dissolution occurred, rather, the proximity to the water table and degassing of CO2 at the interface, were the major controls on precipitation. Thus, simple two‐end‐member mixing models may apply only in mixing zones well below the water table. Meteoric‐vadose speleothems include calcite and high‐Mg calcite with columnar and bladed morphologies. Vadose speleothems precipitated during glacial stages when sea level was lower than present. Progressive increase in δ13C and δ18O of the vadose speleothems resulted from cooling temperatures and more positive seawater δ18O associated with glacial buildup. Such covariation could be considered as a valid alternative to models predicting invariant δ18O and highly variable δ13C in meteoric calcite. Glacio‐eustatic oscillations of sea‐level are recorded as alternating vadose and mixing‐zone speleothems. Short‐term climatic variations are recorded as alternating aragonite and calcite speleothems precipitated in the mixing zone. Fluid‐inclusion and stable‐isotope data suggest that aragonite, as opposed to calcite, precipitated during times of reduced meteoric recharge.  相似文献   

16.
In a semiarid climatic zone, such as the Eastern Mediterranean region, annual rainfall variations and fractionation processes in the epikarst zone exert a profound influence on the isotopic compositions of waters seeping into a cave. Consequently, the isotopic compositions of speleothems depositing from cave waters may show complex variations that need to be understood if they are to be exploited for paleoclimate studies. This is confirmed by a four-year study of the active carbonate-water system in the Soreq cave (Israel). The δ18O (SMOW) values of cave waters range from −6.3 to −3.5%.. The highest δ18O values occur at the end of the dry season in waters dripping from stalactites, and reflect evaporation processes in the epikarst zone, whereas the lowest values occur in rapidly dripping (fast-drip) waters at the peak of the rainy seasons. However, even fast-drip waters are about 1.5%. heavier than the rainfall above the cave, which is taken to reflect the mixing of fresh with residual evaporated water in the epikarst zone. δ13C (PDB) values of dissolved inorganic carbon (DIC) vary from −15.6 to −5.4%., with fast-drip waters having lower δ13C values (mostly −15.6 to −12%.) and higher DIC concentrations relative to pool and stalactite-drip water. The low δ13C values of fast-drip waters and their supersaturation with respect to calcium carbonate indicates that the seepage waters have dissolved both soil-CO2 derived from overlying C3-type vegetation and marine dolomite host rock.The δ18O (PDB) values of various types of present-day low-magnesium calcite (LMC) speleothems range from −6.5 to −4.3%. and δ13C values from −13 to −5.5%. and are not correlated with speleothem type. An analysis of δ18O values of present-day calcite rafts and pool waters shows that they form in oxygen isotope equilibrium. Similarly, the measured ranges of δ13C and δ18O values for all types of present-day speleothems are consistent with equilibrium deposition at cave temperatures. The δ13C–δ18O range of contemporary LMC thus reflects the variations in temperatures and isotopic compositions of the presentday cave waters. The 10%. variation in the δ13C values in waters can be modeled by a simple Rayleigh calculation of the carbon isotope fractionation accompanying CO2-degassing and carbonate precipitation. These variations may obscure the differences in the carbon isotopic composition of speleothems that could arise when vegetation cover changes from C3 to C4-type plants. This consideration emphasizes that it is necessary to characterize the full range of δ13C values associated with contemporaneous speleothems in order to clarify the effects of degassing from those due to differing vegetation types.Isotopic studies of a number of different types of fossil LMC speleothems show many of them to exhibit isotopic trends that are similar to those of present-day LMC, but others show both higher and lower δ18O ranges. In particular, the higher δ18O range has been shown by independent age-measurements to be associated with a period of drier conditions. The results of the study thus indicate that it is necessary to work on a well calibrated cave system in semiarid climates and that the fossil speleothem record should be obtained from different types of contemporaneous deposit in order to fully characterize the δ18O–δ13C range representative of any given climatic period.  相似文献   

17.
High‐resolution records of carbon isotope composition and grey level were analysed from a stalagmite, BW‐1, from Beijing, China, deposited between c. 14 and 10.5 ka BP, the δ18O profile of which has been used to discuss the timing and structure of the Younger Dryas (YD) event in north China. The high grey level and low δ13C match the milk‐white coloured locations on the polished stalagmite surface and coincide with enhanced luminescent bands within which the concentration of both impurities and the total organic carbon (TOC) are high. Additionally, the fluorescence of speleothems was derived from organic acids that have been flushed onto the stalagmite surface along with impurities from the overlying soil by heavy summer rain and co‐precipitated with the speleothem calcite. Thus, predominantly low δ13C and high grey level values indicate increased summer precipitation that supports abundant vegetation and robust biological productivity. Consequently, three distinct time intervals are defined by the palaeoenvironmental conditions expressed in the δ13C and grey level records of stalagmite BW‐1: (i) a warm‐humid stage (Pre‐YD, 13.97 to 12.85 ka BP, including a hiatus from 12.99 to 13.21 ka BP reported before); (ii) a cool‐arid stage (YD, 12.85 to 11.56 ka BP); and (iii) a warm‐humid stage (Post‐YD, 11.56 to 10.39 ka BP). The inferences based on our research are generally consistent with other regional vegetation and climatic records.  相似文献   

18.
To understand oxygen and carbon stable isotopic characteristics of aragonite stalagmites and evaluate their applicability to paleoclimate, the isotopic compositions of active and fossil aragonite speleothems and water samples from an in situ multi-year (October 2005-July 2010) monitoring program in Furong Cave located in Chongqing of China have been examined. The observations during October 2005-June 2007 show that the meteoric water is well mixed in the overlying 300-500-m bedrock aquifer, reflected by relatively constant δ18O, ±0.11-0.14‰ (1σ), of drip waters in the cave, which represents the annual status of rainfall water. Active cave aragonite speleothems are at oxygen isotopic equilibrium with drip water and their δ18O values capture the surface-water oxygen isotopic signal. Aragonite-to-calcite transformation since the last glaciation is not noticeable in Furong stalagmites. Our multi-year field experiment approves that aragonite stalagmite δ18O records in this cave are suitable for paleoclimate reconstruction. With high U, 0.5-7.2 ppm, and low Th, 20-1270 ppt, the Furong aragonite stalagmites provide very precise chronology (as good as ±20s yrs (2σ)) of the climatic variations since the last deglaciation. The synchroneity of Chinese stalagmite δ18O records at the transition into the Bølling-Allerød (t-BA) and the Younger Dryas from Furong, Hulu and Dongge Caves supports the fidelity of the reconstructed East Asian monsoon evolution. However, the Furong record shows that the cold Older Dryas (OD) occurred at 14.0 thousand years ago, agreeing with Greenland ice core δ18O records but ∼200 yrs younger than that in the Hulu record. The OD age discrepancy between Chinese caves can be attributable to different regionally climatic/environmental conditions or chronological uncertainty of stalagmite proxy records, which is limited by changes in growth rate and subsampling intervals in absolute dating. Seasonal dissolved inorganic carbon δ13C variations of 2-3‰ in the drip water and 5-7‰ in the pool and spring waters are likely attributed to variable degrees of CO2 degassing in winter and summer. The variable δ13C values of active deposits from −11‰ to 0‰ could be caused by kinetically mediated CO2 degassing processes. The complicated nature of pre-deposition kinetic isotopic fractionation processes for carbon isotopes in speleothems at Furong Cave require further study before they can be interpreted in a paleoclimatic or paleoenvironmental context.  相似文献   

19.
Limestone cave deposits (speleothems) provide archives for past changes in regional climates over a range of timescales. While δ18O and δ13C in speleothem calcite have been commonly used for reconstruction of paleoclimates, we report here further efforts in the use of 87Sr/86Sr and Sr/Ca signals in speleothem calcite to deduce paleomonsoon variability near the Loess Plateau of central China. A two end-member mass-balance model of concentration and isotopic composition of strontium in a cave system is used to estimate variation of the 87Sr/86Sr ratio in sediments overlying a limestone cave. We show that this ratio reflects climate-driven variations in the provenance and the extent of chemical weathering of the epikarstic sediments. The measurements of 87Sr/86Sr made on a well-dated stalagmite, SFL, from Buddha Cave (33o40N′ 109o05′E) show ratios of 0.71092 to 0.71133 (±0.00001 as 2σ) during relatively cold periods (e.g., Marine Isotope Stage (MIS) 5b, 5d, and 8), lower than ratios of 0.71133 to 0.71194 during relatively warm periods (e.g., MIS 5a, 5c, 5e, and 7). As changes in the Sr/Ca ratio may affect speleothem 87Sr/86Sr, we show that the direct use of speleothem 87Sr/86Sr is less ideal than our modeled 87Sr/86Sr for the exogenic Sr source above the cave as a paleomonsoon proxy. Using the δ18O, δ13C, Sr/Ca, and 87Sr/86Sr records of the stalagmite, we reconstruct the variability of the East Asian monsoon for the time period between 70 and 280 kyr ago. The results show that summer monsoons were more intense during interglacial periods than during glacial periods.  相似文献   

20.
There are very few process studies that demonstrate the annual variation in cave environments depositing speleothems. Accordingly, we initiated a monitoring program at the Obir Caves, an Austrian dripstone cave system characterized by a seasonally changing air flow that results in a predictable pattern of high pCO2 during summer and low pCO2 in winter. Although similar seasonal changes in soil pCO2 occur, they are not directly connected with the changes in the subsurface since the dripwaters are fed from a well-mixed source showing little seasonal variation. Cold season flushing by relatively CO2-poor air enhances degassing of CO2 in the cave and leads to a high degree of supersaturation of dripwater with regard to calcite. Forced calcite deposition during the cold season also gives rise to a pronounced pattern of synchronous seasonal variations in electrical conductivity, alkalinity, pH, Ca and δ13CDIC which parallel variations recorded in δ13Ccave air. Chemical components unaffected by calcite precipitation (e.g., δD, δ18O, SiO2, SO4) lack a seasonal signal attesting to a long residence in the karst aquifer. Modeling shows that degassing of CO2 from seepage waters results in kinetically-enhanced C isotopic fractionation, which contrasts with the equilibrium degassing shown from the Soreq cave in Israel. The Obir Caves may serve as a case example of a dripstone cave whose seepage waters (and speleothems) show intra-annual geochemical variability that is primarily due to chemical modification of the groundwater by a dynamic, bidirectional subsurface air circulation.  相似文献   

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