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1.
This study presents the results from precipitation experiments carried out to investigate the partitioning of the alkaline earth cations Mg2+, Ca2+, Sr2+, and Ba2+ between abiogenic aragonite and seawater as a function of temperature. Experiments were carried out at 5 to 75 °C, using the protocol of Kinsman and Holland [Kinsman, D.J.J., Holland, H.D., 1969. The coprecipitation of cations with CaCO3 IV. The coprecipitation of Sr2+ with aragonite between 16 and 96 °C. Geochim. Cosmochim. Acta33, 1-17.] The concentrations of Mg Sr and Ba were determined in the fluid from each experiment by inductively coupled plasma-mass spectrometry, and in individual aragonite grains by secondary ion mass spectrometry. The experimentally produced aragonite grains are enriched in trace components (“impurities”) relative to the concentrations expected from crystal-fluid equilibrium, indicating that kinetic processes are controlling element distribution. Our data are not consistent with fractionations produced kinetically in a boundary layer adjacent to the growing crystal because Sr2+, a compatible element, is enriched rather than depleted in the aragonite. Element compatibilities, and the systematic change in partitioning with temperature, can be explained by the process of surface entrapment proposed by Watson and Liang [Watson, E.B., Liang, Y., 1995. A simple model for sector zoning in slowly grown crystals: implications for growth rate and lattice diffusion, with emphasis on accessory minerals in crustal rocks. Am. Mineral.80, 1179-1187] and Watson [Watson, E.B., 1996. Surface enrichment and trace-element uptake during crystal growth. Geochim. Cosmochim. Acta60, 5013-5020; Watson, E.B., 2004. A conceptual model for near-surface kinetic controls on the trace-element and stable isotope composition of abiogenic calcite crystals. Geochim. Cosmochim. Acta68, 1473-1488]. This process is thought to operate in regimes where the competition between crystal growth rate and diffusivity in the near-surface region limits the extent to which the solid can achieve partitioning equilibrium with the fluid. A comparison of the skeletal composition of Diploria labyrinthiformis (brain coral) collected on Bermuda with results from precipitation calculations carried out using our experimentally determined partition coefficients indicate that the fluid from which coral skeleton precipitates has a Sr/Ca ratio comparable to that of seawater, but is depleted in Mg and Ba, and that there are seasonal fluctuations in the mass fraction of aragonite precipitated from the calcifying fluid (“precipitation efficiency”). The combined effects of surface entrapment during aragonite growth and seasonal fluctuations in “precipitation efficiency” likely forms the basis for the temperature information recorded in the aragonite skeletons of Scleractinian corals. 相似文献
2.
E.Bruce Watson 《Geochimica et cosmochimica acta》1996,60(24):5013-5020
Adsorption or enrichment of trace elements in the near-surface or interfacial regions of minerals has been documented in systems ranging from low-temperature aqueous environments to magmas. Under static conditions, this surface enrichment results from chemical equilibrium between the host medium of the crystal and the surface layer, which may exhibit diversity or flexibility in the types of atomic sites present. If the crystal is growing, any trace elements bound in the surface layer may be buried and trapped in the newly-formed lattice, resulting in lattice concentrations that deviate substantially from those predicted by equilibrium partitioning between the crystal and its growth medium. The effectiveness of this growth entrapment process depends upon the interplay between the growth rate, V, of the crystal (which can be thought of as the burial rate of surface-enriched element i) and the diffusivity, Di , in the near-surface region of the crystal (which determines how efficiently i can escape to the surface by diffusion). The competition can be quantified in terms of the dimensionless number Vl/Di; (termed the growth Péclet number, Pe), where l is the half-thickness of the surface-enriched layer. Depending upon the degree of surface enrichment, some growth entrapment is possible if Pe > 0.1, and the process is highly efficient if Pe > 10. An assessment of Pe for a wide variety of geological situations suggests that growth entrapment is common in diagenetic and metamorphic environments but limited to slow lattice diffusants in silicic igneous systems. It is probably rare to nonexistent in basaltic systems except at laboratory growth rates. 相似文献
3.
Like most other minerals, titanite rarely if ever forms perfect crystals. In addition to the point defects that might affect lattice diffusion, there may be extended line- or planar defects along which fast diffusion could occur. During the course of an experimental study of oxygen lattice diffusion in titanite, we found that almost all of the 18O uptake profiles produced in natural titanite crystals departed from the complementary error function solution expected for simple lattice diffusion with a constant surface concentration. Instead, they exhibited “tails” extending deeper into the samples than expected for simple lattice diffusion. The purpose of this contribution is to report on these features—described as “fast-paths” for oxygen diffusion—and outline a method for coping with them in extracting information from diffusion profiles.For both dry and hydrothermal experiments in which the “fast paths” are observed, 18O was used as the diffusant. In dry experiments, the source material was 18O-enriched SiO2 powder, while 18O-enriched water was used for the hydrothermal experiments. Diffusive uptake profiles of 18O were measured in all cases by nuclear reaction analysis (NRA) using the 18O (p,α)15N reaction [see Zhang X. Y., Cherniak D. J., and Watson E. B. (2006) Oxygen diffusion in titanite: lattice and fast-path diffusion in single crystals. Chem. Geol.235 105-123].In our experiments, different sizes of “tails” (with varying 18O concentrations) were observed. Theoretically, under the same temperature and pressure conditions, the sizes of tails should be affected by two factors: the diffusion duration and the defect density. For the same experiment duration, the higher the defect density, the larger the “tail”; for the same defect densities, the longer the diffusion duration, the larger the “tail.”The diffusion “tails” could be a result of either planar defects or one-dimensional “pipe” diffusion. AFM imaging of HF etched titanite surfaces confirmed that the etched features might be caused by either parallel planar defects or parallel pipe defects, but could not differentiate between these possibilities. Through theoretical calculations simulating the tailed diffusion profiles using reasonable assumptions of lattice diffusivities and fast-path diffusivities, and comparing these with tail features measured in our samples, it can be concluded that the “tails” observed in our experiments are caused by planar defects rather than pipe defects.A new method was developed for separating the “fast-path” contribution from the overall composite diffusion profile consisting of both “fast-path” and lattice diffusion. Through this process, the lattice diffusion coefficient could be determined, which is required to analyze the tail. The oxygen diffusion rates in the fast-paths were obtained by traditional graphical analysis methods, using the Whipple-Le Claire equation (for 2-D defects) assuming that the width of the fast-path is 1 nm. Two Arrhenius relations were obtained for the fast-path diffusion phenomenon, one for experiments under dry conditions, and the other for hydrothermal conditions:
4.
Richard J. Reeder Evert J. Elzinga K.D. Rector David E. Morris 《Geochimica et cosmochimica acta》2004,68(23):4799-4808
Spatially resolved luminescence spectra from U(VI) co-precipitated at the (101?4) growth surface of synthetic calcite single crystals confirm heterogeneous incorporation corresponding to the distribution of structurally non-equivalent steps composing the vicinal surfaces of spiral growth hillocks. Spectral structure from U(VI) luminescence at the “-” vicinal regions and featureless, weak luminescence at the “+” vicinal regions are consistent with previously reported observations of enrichment at the former sites during calcite growth. Luminescence spectra differ between the non-equivalent regions of the crystal, with the spectral features from the “-” vicinal region corresponding to those observed in bulk calcite samples. Subtle spectral shifts are observed from U(VI) co-precipitated with microcrystalline calcite synthesized by a different method, and all of the U(VI)-calcite sample spectra differ significantly from that of U(VI) co-precipitated with aragonite.The step-selective incorporation of U(VI) can be explained by a proposed model in which the allowed orientation for adsorption of the dominant calcium uranyl triscarbonate species is controlled by the atomic arrangement at step edges. Differences in the tilt angles of carbonate groups between non-equivalent growth steps favor adsorption of the calcium uranyl triscarbonate species at “-” steps, as observed in experiments. 相似文献
5.
Patrick J. Mickler Jay L. Banner Yemane Asmerom Emi Ito 《Geochimica et cosmochimica acta》2004,68(21):4381-4393
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
6.
Calcite Mg/Ca is usually assumed to vary linearly with solution Mg/Ca, that a constant partition coefficient describes the relationship between these two ratios. Numerous published empirical datasets suggests that this relationship is better described by a power function. We provide a compilation of these literature data for biotic and abiotic calcite in the form of Calcite Mg/Ca = F(Solution Mg/Ca)H, where F and H are empirically determined fitting parameters describing the slope and deviation from linearity, respectively, of the function. This is equivalent to Freundlich sorption behavior controlling Mg incorporation in calcite. Using a power function, instead of a partition coefficient, lowers Phanerozoic seawater Mg/Ca estimates based on echinoderm skeletal material by, on average, 0.5 mol/mol from previous estimates.These functions can also be used to model the primary skeletal calcite Mg/Ca of numerous calcite phases through geologic time. Such modeling suggests that the Mg/Ca of all calcite precipitated from seawater has varied through the Phanerozoic in response to changing seawater Mg/Ca and that the overall range in Mg/Ca measured among various calcite phases would be greatest when seawater Mg/Ca was also high (e.g., “aragonite seas”) and lowest when seawater Mg/Ca was low (e.g., “calcite seas”). It follows that, during times of “calcite seas” when the seawater Mg/Ca is presumed to have been lower, deposition of calcite with low Mg contents would have resulted in a depressed drive for diagenetic stabilization of shelfal carbonate and, in turn, lead to greater preservation of crystal and skeletal microfabrics and primary chemistries in biotic and abiotic calcites. 相似文献
7.
Ca isotope fractionation during inorganic calcite formation was experimentally studied by spontaneous precipitation at various precipitation rates (1.8 < log R < 4.4 μmol/m2/h) and temperatures (5, 25, and 40 °C) with traces of Sr using the CO2 diffusion technique.Results show that in analogy to Sr/Ca [see Tang J., Köhler S. J. and Dietzel M. (2008) Sr2+/Ca2+ and 44Ca/40Ca fractionation during inorganic calcite formation: I. Sr incorporation. Geochim. Cosmochim. Acta] the 44Ca/40Ca fractionation during calcite formation can be followed by the Surface Entrapment Model (SEMO). According to the SEMO calculations at isotopic equilibrium no fractionation occurs (i.e., the fractionation coefficient αcalcite-aq = (44Ca/40Ca)s/(44Ca/40Ca)aq = 1 and Δ44/40Cacalcite-aq = 0‰), whereas at disequilibrium 44Ca is fractionated in a primary surface layer (i.e., the surface entrapment factor of 44Ca, F44Ca < 1). As a crystal grows at disequilibrium, the surface-depleted 44Ca is entrapped into the newly formed crystal lattice. 44Ca depletion in calcite can be counteracted by ion diffusion within the surface region. Our experimental results show elevated 44Ca fractionation in calcite grown at high precipitation rates due to limited time for Ca isotope re-equilibration by ion diffusion. Elevated temperature results in an increase of 44Ca ion diffusion and less 44Ca fractionation in the surface region. Thus, it is predicted from the SEMO that an increase in temperature results in less 44Ca fractionation and the impact of precipitation rate on 44Ca fractionation is reduced.A highly significant positive linear relationship between absolute 44Ca/40Ca fractionation and the apparent Sr distribution coefficient during calcite formation according to the equation
Δ44/40Cacalcite-aq=(−1.90±0.26)·logDSr−2.83±0.28 相似文献
8.
Rolf S. Arvidson Inci Evren Ertan Andreas Luttge 《Geochimica et cosmochimica acta》2003,67(9):1623-1634
A comparison of published calcite dissolution rates measured far from equilibrium at a pH of ∼ 6 and above shows well over an order of magnitude in variation. Recently published AFM step velocities extend this range further still. In an effort to understand the source of this variation, and to provide additional constraint from a new analytical approach, we have measured dissolution rates by vertical scanning interferometry. In areas of the calcite cleavage surface dominated by etch pits, our measured dissolution rate is 10−10.95 mol/cm2/s (PCO2 10−3.41 atm, pH 8.82), 5 to ∼100 times slower than published rates derived from bulk powder experiments, although similar to rates derived from AFM step velocities. On cleavage surfaces free of local etch pit development, dissolution is limited by a slow, “global” rate (10−11.68 mol/cm2/s). Although these differences confirm the importance of etch pit (defect) distribution as a controlling mechanism in calcite dissolution, they also suggest that “bulk” calcite dissolution rates observed in powder experiments may derive substantial enhancement from grain boundaries having high step and kink density. We also observed significant rate inhibition by introduction of dissolved manganese. At 2.0 μM Mn, the rate diminished to 10−12.4 mol/cm2/s, and the well formed rhombic etch pits that characterized dissolution in pure solution were absent. These results are in good agreement with the pattern of manganese inhibition in published AFM step velocities, assuming a step density on smooth terraces of ∼9 μm−1. 相似文献
9.
M. Baudrand G. Aloisi C. Lécuyer F. Martineau F. Fourel G. Escarguel M.-M. Blanc-Valleron J.-M. Rouchy V. Grossi 《Applied Geochemistry》2012
A semi-automatic, on-line method was developed to determine the δ13C and δ18O values of coexisting calcite and dolomite. An isotopic mass balance is used to calculate the compositions of dolomite after having measured that of calcite and of the “bulk” sample. The limit of validity of this method is established by performing isotopic measurements of artificial mixtures made of precisely weighted and isotopically-characterised dolomite and calcite. The accuracy and repeatability of the calculation of dolomite δ13C and δ18O are statistically determined with a Monte-Carlo procedure of error propagation. Stable isotope ratios are determined by using an automated MultiPrep™ system on-line with an isotope-ratio mass-spectrometer (IRMS). The reaction time and the temperature of reaction were optimised by comparing the results with the isotopic composition of known mixtures. The best results were obtained by phosphoric acid digestion after 20 min at 40 °C for calcite and 45 min at 90 °C for dolomite. This procedure allows an accurate determination of the isotopic ratios from small samples (300 μg). Application of this protocol to natural mixtures of calcite and dolomite requires the accurate determination of the relative abundance of calcite and dolomite by combining Mélières manocalcimetry (MMC) and X-ray diffractometry (XRD). 相似文献
10.
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
11.
Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solutions 总被引：1，自引：0，他引：1
Donald J. DePaolo 《Geochimica et cosmochimica acta》2011,75(4):1039-253
A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (Rp) to the gross forward precipitation rate (Rf), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of Rp has been experimentally measured under varying conditions, but the magnitude of Rf is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, Rf can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (Rb or kb), since at equilibrium Rf = Rb, and Rp = 0. Hence it can be inferred that Rf ≈ Rp + Rb. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when Rp (=Rf − Rb) ? Rb. For precipitation rates high enough that Rp ? Rb, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near Rp ≈ Rb for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate Rf for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence Rp. Allowing Rb to vary as , consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where Rb is constant. This model can account for most of the experimental data in the literature on the dependence of 44Ca/40Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for 18O/16O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of Rb on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that require hyper-fast diffusivity in near-surface layers of the solid. 相似文献
12.
Speleothem oxygen isotopes and growth rates are valuable proxies for reconstructing climate history. There is debate, however, about the conditions that allow speleothems to grow in oxygen isotope equilibrium, and about the correct equilibrium fractionation factors. We report results from a series of carbonate growth experiments in karst-analogue conditions in the laboratory. The setup closely mimics natural processes (e.g. precipitation driven by CO2-degassing, low ionic strength solution, thin solution film) but with a tight control on growth conditions (temperature, pCO2, drip rate, calcite saturation index and the composition of the initial solution). Calcite is dissolved in water in a 20,000 ppmV pCO2 environment. This solution is dripped onto glass plates (coated with seed-carbonate) in a lower pCO2 environment (<2500 ppmV), where degassing leads to calcite growth. Experiments were performed at 7, 15, 25 and 35 °C. At each temperature, calcite was grown at three drip rates (2, 6 and 10 drips per minute) on separate plates. The mass of calcite grown in these experiments varies with temperature (T in K) and drip rate (d_r in drips min−1) according to the relationship daily growth mass = 1.254 + 1.478 ∗ 10−9 ∗ e0.0679T + (e0.00248T − 2) ∗ (−0.779d_r2 + 10.05d_r + 11.69). This relationship indicates a substantial increase of growth mass with temperature, a smaller influence of drip rate on growth mass at low temperature and a non-linear relationship between drip rate and growth mass at higher temperatures. Low temperature, fast dripping conditions are found to be the most favourable for reducing effects associated with evaporation and rapid depletion of the dissolved inorganic carbon reservoir (rapid DIC-depletion). The impact of evaporation can be large so caves with high relative humidity are also preferable for palaeoclimate reconstruction. Even allowing for the maximum offsets that may have been induced by evaporation and rapid DIC-depletion, δ18O measured in some of our experiments remain higher than those predicted by Kim and O’Neil (1997). Our new results are well explained by equilibrium at a significantly higher αcalcite-water, with a kinetic-isotope effect that favours 16O incorporation as growth rate increases. This scenario agrees with recent studies by
[Coplen, 2007] and [Dietzel et al., 2009]. Overall, our results suggest that three separate processes cause δ18O to deviate from true isotope equilibrium in the cave environment. Two of these drive δ18O to higher values (evaporation and rapid DIC-depletion) while one drives δ18O to lower values (preferential incorporation of 16O in the solid carbonate at faster growth rates). While evaporation and DIC-depletion can be avoided in some settings, the third may be inescapable in the cave environment and means that any temperature to δ18O relationship is an approximation. The controlled conditions of the present experiments also display limitations in the use of the Hendy test to identifying equilibrium growth. 相似文献
13.
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
14.
Elizabeth M. Griffith Edwin A. Schauble Adina Paytan 《Geochimica et cosmochimica acta》2008,72(23):5641-5658
The mineral barite (BaSO4) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (δ44/40Ca = −2.01 ± 0.15‰) but are different from hydrothermal and cold seep barite samples (δ44/40Ca = −4.13 to −2.72‰). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, Δ44/40Ca = −3.42 to −2.40‰. Temperature, saturation state, , and aCa2+/aBa2+ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower 44Ca/40Ca than calcite, by −9‰ at 0 °C and −8‰ at 25 °C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower δ44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca2+ substitution for Ba2+ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca2+ and other elements in inorganic and biogenic minerals. 相似文献
15.
We have measured δ44/42Ca of laboratory-precipitated calcite grown in an experimental setup that closely replicates stalagmite formation. Calcium solutions were dripped onto two different substrates in tightly-controlled conditions and calcite precipitated due to rapid CO2 degassing. With seeded glass slides as the substrate, we observe a Ca isotope ratio in the calcite which is ∼0.5‰ per amu lower than that in the growth solution. This fractionation is generally almost twice that observed in previously published calcite growth experiments and indicates a large kinetic effect on Ca isotopes in the stalagmite growth environment. The precipitate forming near the spot where the drip lands shows slightly greater solution-to-precipitate fractionation than calcite further from the drip reflecting a decrease in this kinetic fractionation as precipitation continues. We interpret these results in the context of the model of Fantle and DePaolo (2007) which involves surface entrapment of light Ca isotopes to decrease calcite δ44/42Ca, and depletion of Ca from the solution in the direct vicinity of the growing calcite to increase calcite δ44/42Ca. In the stalagmite setting, the second of these effects is minimized so that calcite Ca isotope ratios are unusually light. This interpretation suggests that stalagmite Ca isotope ratios should decrease with the saturation state of the drip water (i.e. with the growth rate of calcite). Ca isotopes might therefore allow reconstruction of surface entrapment of trace metals and isotopes more generally and might, for instance, allow an assessment of the appropriate relationship between oxygen isotope fractionation and temperature for periods of past growth in stalagmites. 相似文献
16.
The role of the grain boundary at chemical and isotopic fronts in marble during contact metamorphism
Hideki Wada Takamaru Ando Masayuki Suzuki 《Contributions to Mineralogy and Petrology》1998,132(4):309-320
Carbon and oxygen isotopic profiles around a low pressure metasomatic wollastonite reaction front in a marble of the Hida
metamorphic terrain, central Japan, display typical metamorphic fluid-enhanced isotopic zonations. Isotopic profiles obtained
from detailed microscale analyses perpendicular to the chemical reaction front in calcite marble show that diffusion-enhanced
isotopic exchange may control these profiles. Carbon and oxygen isotopic behaviour in grain boundaries is remarkably different.
Oxygen isotopic troughs (18O depleted rims) around the calcite-grain boundaries are widely observed in this contact aureole, demonstrating that diffusion
of oxygen in calcite grain boundary dominates over lattice diffusion in calcite. In contrast, no difference is observed in
carbon isotopic profiles obtained from grain cores and rims. There is thus no specific role of the grain boundary for diffusion
of carbonic species in the metamorphic fluid during transportation. Carbon chemical species such as CO2 and CO3 ions in metamorphic fluid migrate mainly through lattice diffusion. The carbon and oxygen isotope profiles may be modelled
by diffusion into a semi-infinite medium. Empirically lattice diffusion of oxygen isotopes is almost six times faster than
that of carbon isotopes, and oxygen grain-boundary diffusion is ten times faster than oxygen lattice diffusion. Oxygen isotopic
results around the wollastonite vein indicate that migration of the metamorphic fluid into calcite marble was small and was
parallel to the aquifer. From the stability of wollastonite and the attainment of oxygen isotopic equilibrium, we suggest
that diffusion of oxygen occurred through an aqueous fluid phase. The timescale of formation of the oxygen isotopic profile
around the wollastonite vein is calculated to be about 0.76 × 106 years using the experimentally determined diffusion constant.
Received: 14 January 1997 / Accepted: 23 April 1998 相似文献
17.
Inhibition of calcite precipitation by orthophosphate: Speciation and thermodynamic considerations 总被引：1，自引：0，他引：1
The inhibition of heterogeneous calcite precipitation by orthophosphate was investigated under four different solution compositions using a pH-stat system. The system composition was designed to maintain a constant degree of supersaturation with respect to calcite, but with different carbonate/calcium ratios and pH values during precipitation. Inhibition in the presence of orthophosphate was found to be more effective at lower carbonate/calcium ratios and lower pH values. With the assumption that the calcite precipitation rate is proportional to the surface concentration of active crystal-growth sites, the reduction in the rate of calcite precipitation by phosphate can be explained by a Langmuir adsorption model using a conditional equilibrium constant and total phosphate concentration. Through a detailed analysis of chemical speciation in the solution phase and calcite surface speciation using chemical equilibrium computer modeling, the “conditional” equilibrium constants obtained at different solution compositions were found to converge to a single “non-conditional” value if only was considered in the adsorption reaction. This suggests that is the responsible species for inhibition of calcite precipitation because it adsorbs to the surface and blocks the active crystal-growth sites. The standard enthalpy change (ΔH0) and standard entropy change (TΔS0) of the adsorption reaction, determined by experiments performed from 15 to 45 °C, were 58.5 and 98.3 kJ/mol, respectively. The high positive values of the standard enthalpy change and the standard entropy change suggest that the adsorption reaction is an endothermic reaction, chemisorptive in nature, and driven by the entropy change, most likely resulting from the dehydration process that accompanies the adsorption of onto the calcite surface. 相似文献
18.
Chemically induced grain boundary migration in calcite: temperature dependence,phenomenology, and possible applications to geologic systems 总被引：3，自引：0，他引：3
Chemically induced grain boundary migration (CIGM) is a solid-state reaction mechanism which involves grain boundary migration. Initially straight grain boundaries in calcite bicrystals exhibit CIGM when exposed to a SrCO3 or BaCO3-rich melt at temperatures of 680–840° C in a 1-bar CO2 atmosphere. Under these conditions, CIGM is apparently a much more efficient way to form solid-solutions than lattice diffusion. The maximum observed rate of migration, 1×10–9 m/s, occurred at about 760° C. Below that temperature, migration was thermally activated, but above it, the process was thermally inhibited. Some portions of the boundary swept through a given crystal volume more than once. In the (Ca, Sr) CO3 system, the solute concentrations incorporated during a single pass of the boundary were far less than values expected at chemical equilibrium, and departed further from equilibrium at higher temperatures. CIGM may be geologically important when the distances characteristic of grain boundary migration and diffusion are much larger than those characteristic of lattice diffusion. The great similarity between results in ionic calcite and metals systems suggests CIGM is a very general process which may be expected to occur in a large number of geologic systems. 相似文献
19.
Uptake of cadmium ions from solution by a natural Mg-containing calcite was investigated in stirred flow-through reactor experiments. Input NaCl solutions were pre-equilibrated with calcite (pH 8.0) or not (pH 6.0), prior to being spiked with CdCl2. For water residence times in the reactor less than 0.5 h, irreversible uptake of Cd by diffusion into the bulk crystal had a minor effect on the measured cadmium breakthrough curves, hence allowing us to quantify “fast” Cd2+ adsorption. At equal aqueous activities of Cd2+, adsorption was systematically lower for the pre-equilibrated input solutions. The effect of variable solution composition on Cd2+ adsorption was reproduced by a Ca2+-Cd2+ cation exchange model and by a surface complexation model for the calcite-aqueous solution interface. For the range of experimental conditions tested, the latter model predicted binding of aqueous Ca2+ and Cd2+ to the same population of carbonate surface sites. Under these circumstances, both adsorption models were equivalent. Desorption released 80 to 100% of sorbed cadmium, confirming that fast uptake of Cd2+ was mainly due to binding at surface sites. Slow, irreversible cadmium uptake by the solid phase was measured in flow-through reactor experiments with water residence times exceeding 0.7 h. The process exhibited first-order kinetics with respect to the concentration of adsorbed Cd2+, with a linear rate constant at 25°C of 0.03 h−1. Assuming that diffusion into the calcite lattice was the mechanism of slow uptake, a Cd2+ solid-state diffusion coefficient of 8.5×10−21 cm2 s−1 was calculated. Adsorbed Cd2+ had a pronounced effect on the dissolution kinetics of calcite. At maximum Cd2+ surface coverage (∼10−5 mol m−2), the calcite dissolution rate was 75% slower than measured under initially cadmium-free conditions. Upon desorption of cadmium, the dissolution rate increased again but remained below its initial value. Thus, the calcite surface structure and reactivity retained a memory of the adsorbed Cd2+ cations after their removal. 相似文献
20.
K. Wainer D. Genty D. Blamart M. Daëron M. Bar-Matthews H. Vonhof Y. Dublyansky E. Pons-Branchu L. Thomas P. van Calsteren Yves Quinif N. Caillon 《Quaternary Science Reviews》2011,30(1-2):130-146
The Vil-car-1 flowstone core from Villars cave (SW France) provides one of the first European speleothem records extending back to 180 ka, based on U–Th TIMS and MC-ICP-MS measurements. The core offers a continuous record of Termination II and the Last Interglacial. The penultimate deglaciation is characterized by a prominent 5‰ depletion in calcite δ18O. Determining which specific environmental factors controlled such a large oxygen isotopic shift offers the opportunity to assess the impact of various factors influencing δ18O variations in speleothem calcite.Oxygen isotope analyses of fluid inclusions indicate that drip water δ18O remained within a very narrow range of ±1‰ from Late MIS6 to the MIS5 δ18O optimum. The possibility of such a stable behaviour is supported by simple calculations of various effects influencing seepage water δ18O.Although this could suggest that the isotopic shift in calcite is mainly driven by temperature increase, attempts to quantify the temperature shift from Late MIS6 to the MIS5 δ18O optimum by assuming an equilibrium relationship between calcite and fluid inclusion δ18O yield unreasonably high estimates of ～20 °C warming and Late MIS6 cave temperatures below 0 °C; this suggests that the flowstone calcite precipitated out of thermodynamic equilibrium at this site.Using a method proposed by Guo et al. (submitted for publication) combining clumped isotope measurements, fluid inclusion and modern calcite δ18O analyses, it is possible to quantitatively correct for isotopic disequilibrium and estimate absolute paleotemperatures. Although the precision of these absolute temperature reconstructions is limited by analytical uncertainties, the temperature rise between Late MIS6 and the MIS5 optimum can be robustly constrained between 13.2 ± 2.6 and 14.6 ± 2.6 °C (1σ), consistent with existing estimates from Western Europe pollen and sea-surface temperature records. 相似文献