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1.
Liquid phase diffusion experiments were carried out to determine whether diffusive isotopic fractionation of a major chemical element (Ca) varies with chemical composition in high-temperature molten silicates. The objective was to determine how differences in silicate liquid structure, such as the ratio of bridging to non-bridging oxygen atoms, as well as bulk transport properties such as viscosity, relate to isotope discrimination during diffusion. This information, in turn, may relate to the lifetimes and sizes of multi-atom structures in the liquid. Diffusion couples consisting of juxtaposed natural mafic and felsic liquids were held at T = 1450 °C and P = 1.0 GPa for durations of 12-24 h in a standard piston-cylinder assembly. Experiments were done using different mafic endmember compositions (two tholeiitic basalts and a ugandite) and a single rhyolite composition. Major-element diffusion profiles and Ca isotope profiles were measured on the recovered quenched glasses. The starting materials were isotopically indistinguishable, but 44Ca/40Ca variations of ca. 5‰ arose due to a mass dependence of the Ca diffusion coefficients. Results indicate that the mass dependence of Ca diffusion coefficients varies with the magnitude and direction of aluminum gradients and the viscosity of the liquid. Some Ca fractionations result mainly from Al gradients.A simplified multicomponent diffusion model was used to model the experimental results. The model allows for diffusion of Ca in response to gradients in the concentrations of both CaO as well as Al2O3, and the model results are consistent with the inferred existence of at least two distinct species of Ca. The magnitude of isotopic discrimination during diffusion also appears to be stronger on the rhyolite versus the basalt/ugandite side of diffusion couples. The results can largely be accounted for by an adaptation of the model of Dingwell (1990), whereby in high silica liquids, Ca diffuses largely by site hopping through a quasi-stationary aluminosilicate matrix, producing strong isotopic effects because the Ca diffusion is not strongly correlated with the movement of the framework atoms. In low-silica liquids, Ca diffusion is correlated with the movement of the other components and there is less mass discrimination. Combining our Ca results with Ca, Mg, and Li data from previous studies, we show that this model can explain most of the cation- and composition-dependence of diffusive isotopic fractionations observed thus far. A key parameter controlling isotopic discrimination is the ratio of the elemental (Ca, Mg, Li) diffusivity to the Eyring (or Si) diffusivity. However, all experiments done so far also exhibit isotopic features that are not yet fully explained; some of these may relate to small temperature gradients in the capsules, or to more complex coupling effects that are not captured in simplified diffusion models.  相似文献   

2.
Calcium and magnesium concentrations in seawater have varied over geological time scales. On short time scales, variations in the major ion composition of seawater influences coccolithophorid physiology and the chemistry of biogenically produced coccoliths. Validation of those changes via controlled laboratory experiments is a crucial step in applying coccolithophorid based paleoproxies for the reconstruction of past environmental conditions. Therefore, we examined the response of two species of coccolithophores, Emiliania huxleyi and Coccolithus braarudii, to changes in the seawater Mg/Ca ratio (≈0.5 to 10 mol/mol) by either manipulating the magnesium or calcium concentration under controlled laboratory conditions. Concurrently, seawater Sr/Ca ratios were also modified (≈2 to 40 mmol/mol), while keeping salinity constant at 35. The physiological response was monitored by measurements of the cell growth rate as well as the production rates of particulate inorganic and organic carbon, and chlorophyll a. Additionally, coccolithophorid calcite was analyzed for its elemental composition (Sr/Ca and Mg/Ca) as well as isotope fractionation of calcium and magnesium (Δ44/40Ca and Δ26/24Mg). Our results reveal that physiological rates were substantially influenced by changes in seawater calcium rather than magnesium concentration within the range estimated to have occurred over the past 250 million years when coccolithophores appear in the fossil record. All physiological rates of E. huxleyi decreased at a calcium concentration above 25 mmol L−1, whereas C. braarudii displayed a higher tolerance to increased seawater calcium concentrations. Partition coefficient of Sr was calculated as 0.36 ± 0.04 (±2σ) independent of species. Partition coefficient of Mg2+ increased with increasing seawater Ca2+ concentrations in both coccolithophore species. Calcium isotope fractionation was constant at 1.1 ± 0.1‰ (±2σ) and not altered by changes in seawater Mg/Ca ratio. There is a well-defined inverse linear relationship between calcium isotope fractionation and partition coefficient of Sr2+ in all experiments, suggesting similar controls on both proxies in the investigated species. Magnesium isotope ratios were relatively stable for seawater Mg/Ca ratios ranging from 1 to 5, with a higher degree of fractionation in Emiliania huxleyi (by ≈0.2‰ in Δ26/24Mg). Although Mg/Ca ratios in the calcite of coccolithophores and foraminifera are similar, the former have considerably higher Δ26/24Mg (by >+3‰), presumably due to differences in calcification mechanisms between the two taxa. These observations suggest, a physiological control over magnesium elemental and isotopic fractionation during the process of calcification in coccolithophores.  相似文献   

3.
Samples produced in piston cylinder experiments were used to document the thermal isotopic fractionation of all the major elements of basalt except for aluminum and the fractionation of iron isotopes by chemical diffusion between a natural basalt and rhyolite. The thermal isotopic fractionations are summarized in terms of a parameter Ωi defined as the fractionation in per mil per 100 °C per atomic mass units difference between the isotopes. For molten basalt we report ΩCa = 1.6, ΩFe = 1.1, ΩSi = 0.6, ΩO = 1.5. In an earlier paper we reported ΩMg = 3.6. These fractionations represent a steady state balance between thermal diffusion and chemical diffusion with the mass dependence of the thermal diffusion coefficient being significantly larger than the mass dependence of the chemical diffusion coefficients for isotopes of the same element. The iron isotopic measurements of the basalt-rhyolite diffusion couple showed significant fractionation that are parameterized in terms of a parameter βFe = 0.03 when the ratio of the diffusion coefficients D54 and D56 of 54Fe and 56Fe is expressed in terms of the atomic mass as D54/D56 = (56/54)βFe. This value of βFe is smaller than what we had measured earlier for lithium, magnesium and calcium (i.e., βLi = 0.215, βCa = 0.05, βMg = 0.05) but still significant when one takes into account the high precision with which iron isotopic compositions can be measured (i.e., ±0.03‰) and that iron isotope fractionations at magmatic temperatures from other causes are extremely small. In a closing section we discuss technological and geological applications of isotopic fractionations driven by either or both chemical and thermal gradients.  相似文献   

4.
An 18 million year record of the Ca isotopic composition (δ44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. δ44/42Ca in this record averages +0.37 ± 0.05 (1σ SD) and ranges from +0.21‰ to +0.52‰. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25‰ lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their δ44/42Ca (i.e., by 0.06 ± 0.06‰ (n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in δ44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (δ44/42Caw) and for isotope fractionation associated with the production of carbonate sediments (Δsed) results in unrealistically large variations in the total mass of Ca2+ in the oceans over the Neogene. Alternatively, variations of ±0.05‰ in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in δ44/42Caw of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in Δsed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in δ44/42Caw and Δsed have been established, modeling the Ca2+ content of seawater from Ca isotope curves should be approached cautiously.  相似文献   

5.
This survey of magnesium stable isotope compositions in marine biogenic aragonite and calcite includes samples from corals, sclerosponges, benthic porcelaneous and planktonic perforate foraminifera, coccolith oozes, red algae, and an echinoid and brachiopod test. The analyses were carried out using MC-ICP-MS with an external repeatability of ±0.22‰ (2SD for δ26Mg; n = 37), obtained from a coral reference sample (JCp-1).Magnesium isotope fractionation in calcitic corals and sclerosponges agrees with published data for calcitic speleothems with an average Δ26Mgcalcite-seawater = −2.6 ± 0.3‰ that appears to be weakly related to temperature. With one exception (Vaceletia spp.), aragonitic corals and sclerosponges also display uniform Mg isotope fractionations relative to seawater with Δ26Mgbiogenic aragonite-seawater = −0.9 ± 0.2.Magnesium isotopes in high-Mg calcites from red algae, echinoids and perhaps some porcelaneous foraminifera as well as in all low-Mg calcites (perforate foraminifera, coccoliths and brachiopods) display significant biological influences. For planktonic foraminifera, the Mg isotope data is consistent with the fixation of Mg by organic material under equilibrium conditions, but appears to be inconsistent with Mg removal from vacuoles. Our preferred model, however, suggests that planktonic foraminifera synthesize biomolecules that increase the energetic barrier for Mg incorporation. In this model, the need to remove large quantities of Mg from vacuole solutions is avoided. For the high-Mg calcites from echinoids, the precipitation of amorphous calcium carbonate may be responsible for their weaker Mg isotope fractionation.Disregarding superimposed biological effects, it appears that cation light isotope enrichments in CaCO3 principally result from a chemical kinetic isotope effect, related to the incorporation of cations at kink sites. In this model, the systematics of cation isotope fractionations in CaCO3 relate to the activation energy required for cation incorporation, which probably reflects the dehydration of the cation and the crystal surface and bond formation at the incorporation site. This kinetic incorporation model predicts (i) no intrinsic dependence on growth rate, unless significant back reaction upon slow growth reduces the isotope fractionation towards that characteristic for equilibrium isotope partitioning (this may be observed for Ca isotopes in calcites), (ii) a small decrease of isotope fractionation with increasing temperature that may be amplified if higher temperatures promote back reaction and (iii) a sensitivity to changes in the activation barrier caused by additives such as anions or biomolecules or by the initial formation of amorphous CaCO3.  相似文献   

6.
We measured Ca stable isotope ratios (δ44/40Ca) in an ancient (2 My), hyperarid soil where the primary source of mobile Ca is atmospheric deposition. Most of the Ca in the upper meter of this soil (3.5 kmol m−2) is present as sulfates (2.5 kmol m−2), and to a lesser extent carbonates (0.4 kmol m−2). In aqueous extracts of variably hydrated calcium sulfate minerals, δ44/40CaE values (vs. bulk Earth) increase with depth (1.4 m) from a minimum of −1.91‰ to a maximum of +0.59‰. The trend in carbonate-δ44/40Ca in the top six horizons resembles that of sulfate-δ44/40Ca, but with values 0.1-0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ44/40Ca values observed on Earth. Linear correlation among δ44/40Ca, δ34S and δ18O values indicates either (a) a simultaneous change in atmospheric input values for all three elements over time, or (b) isotopic fractionation of all three elements during downward transport. We present evidence that the latter is the primary cause of the isotopic variation that we observe. Sulfate-δ34S values are positively correlated with sulfate-δ18O values (R2 = 0.78) and negatively correlated with sulfate δ44/40CaE values (R2 = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ44/40Ca fractionation factor of −0.4‰ in CaSO4. The overall depth trend in Ca isotopes is reproduced by a model of isotopic fractionation during downward Ca transport that considers small and infrequent but regularly recurring rainfall events. Near surface low Ca isotope values are reproduced by a Rayleigh model derived from measured Ca concentrations and the Ca fractionation factor predicted by the relationship with S isotopes. This indicates that the primary mechanism of stable isotope fractionation in CaSO4 is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events.  相似文献   

7.
Experiments specifically designed to measure the ratio of the diffusivities of ions dissolved in water were used to determine . The measured ratio of the diffusion coefficients for Li and K in water (DLi/DK = 0.6) is in good agreement with published data, providing evidence that the experimental design being used resolves the relative mobility of ions with adequate precision to also be used for determining the fractionation of isotopes by diffusion in water. In the case of Li, we found measurable isotopic fractionation associated with the diffusion of dissolved LiCl (D7Li/D6Li=0.99772±0.00026). This difference in the diffusion coefficient of 7Li compared to 6Li is significantly less than that reported in an earlier study, a difference we attribute to the fact that in the earlier study Li diffused through a membrane separating the water reservoirs. Our experiments involving Mg diffusing in water found no measurable isotopic fractionation (D25Mg/D24Mg=1.00003±0.00006). Cl isotopes were fractionated during diffusion in water (D37Cl/D35Cl=0.99857±0.00080) whether or not the co-diffuser (Li or Mg) was isotopically fractionated. The isotopic fractionation associated with the diffusion of ions in water is much smaller than values we found previously for the isotopic fractionation of Li and Ca isotopes by diffusion in molten silicate liquids. A major distinction between water and silicate liquids is that water surrounds dissolved ions with hydration shells, which very likely play an important but still poorly understood role in limiting the isotopic fractionation associated with diffusion.  相似文献   

8.
In order to investigate the incorporation of Sr, Mg, and U into coral skeletons and its temperature dependency, we performed a culture experiment in which specimens of the branching coral (Porites cylindrica) were grown for 1 month at three seawater temperatures (22, 26, and 30 °C). The results of this study showed that the linear extension rate of P. cylindrica has little effect on the skeletal Sr/Ca, Mg/Ca, and U/Ca ratios. The following temperature equations were derived: Sr/Ca (mmol/mol) = 10.214(±0.229) − 0.0642(±0.00897) × T (°C) (r2 = 0.59, p < 0.05); Mg/Ca (mmol/mol) = 1.973(±0.302) + 0.1002(±0.0118) × T (°C) (r2 = 0.67, p < 0.05); and U/Ca (μmol/mol) = 1.488(±0.0484) − 0.0212(±0.00189) × T (°C) (r2 = 0.78, p < 0.05). We calculated the distribution coefficient (D) of Sr, Mg, and U relative to seawater temperature and compared the results with previous data from massive Porites corals. The seawater temperature proxies based on D calibrations of P. cylindrica established in this study are generally similar to those for massive Porites corals, despite a difference in the slope of DU calibration. The calibration sensitivity of DSr, DMg, and DU to seawater temperature change during the experiment was 0.64%/°C, 1.93%/°C, and 1.97%/°C, respectively. These results suggest that the skeletal Sr/Ca ratio (and possibly the Mg/Ca and/or U/Ca ratio) of the branching coral P. cylindrica can be used as a potential paleothermometer.  相似文献   

9.
Diffusive isotopic fractionation factors are important in order to understand natural processes and have practical application in radioactive waste storage and carbon dioxide sequestration. We determined the isotope fractionation factors and the effective diffusion coefficients of chloride and bromide ions during aqueous diffusion in polyacrylamide gel. Diffusion was determined as functions of temperature, time and concentration. The effect of temperature is relatively large on the diffusion coefficient (D) but only small on isotope fractionation. For chlorine, the ratio, D35Cl/D37Cl varied from 1.00128 ± 0.00017 (1σ) at 2 °C to 1.00192 ± 0.00015 at 80 °C. For bromine, D79Br/D81Br varied from 1.00098 ± 0.00009 at 2 °C to 1.0064 ± 0.00013 at 21 °C and 1.00078 ± 0.00018 (1σ) at 80 °C. There were no significant effects on the isotope fractionation due to concentration. The lack of sensitivity of the diffusive isotope fractionation to anything at the most common temperatures (0 to 30 °C) makes it particularly valuable for application to understanding processes in geological environments and an important natural tracer in order to understand fluid transport processes.  相似文献   

10.
Ontogenetic (developmental stage) measurements of Mg/Ca and Sr/Ca were made on the benthic foraminifer Bulimina aculeata, which were cultured under controlled physicochemical conditions of temperature, pH, alkalinity, salinity, and trace- and minor-element concentrations. We utilized two methods of ontogenetic sampling—whole specimens progressively increasing in length and laser microdissection of a single specimen with subsequent analysis of dissected portions. A novel high-resolution laser-microdissection (HRLM) method allowed for precise (10 μm) cuts of the foraminiferal tests (shells) along the geometrically complex sutures distinguishing individual chambers. This new microdissection method limited sample loss and cross-contamination between foraminiferal chambers. Little or no variation in DSr was observed at different foraminiferal developmental stages. Conversely, DMg was enriched during a mid-developmental stage of whole-specimen samples (150-225 μm DMg = 1.6 × 10−3) compared to earlier and later stages (<150 μm, >225 μm DMg = 8.3 × 10−4). Further analysis of HRLM ontogenetic samples showed a larger, age-dependent DMg signature variation. This increase in shell Mg/Ca may contribute substantially to the measured inter-individual variability in Mg/Ca temperature prediction for cultured B. aculeata. Due to relatively large Mg/Ca inter- and intra-individual variability, measuring similar-size foraminiferal samples may improve the precision of paleotemperature prediction. Additionally, partial dissolution of the highest ontogenetically Mg-enriched calcite (DMg = 1.3 × 10−2-1.6 × 10−2) may occur in undersaturated bottom-water environments or during reductive cleaning procedures. Thus, the calcite phases remaining after partial dissolution by either natural or laboratory cleaning processes may not accurately represent the calcification environment.  相似文献   

11.
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   

12.
Two types of laboratory experiments were used to quantify magnesium isotopic fractionations associated with chemical and thermal (Soret) diffusion in silicate liquids. Chemical diffusion couples juxtaposing a molten natural basalt (SUNY MORB) and a molten natural rhyolite (Lake County Obsidian) were run in a piston cylinder apparatus and used to determine the isotopic fractionation of magnesium as it diffused from molten basalt to molten rhyolite. The thermal diffusion experiments were also run in a piston cylinder apparatus but with a sample made entirely of molten SUNY MORB displaced from the hotspot of the assembly furnace so that the sample would have a temperature difference of about 100-200 °C from one end to the other. The chemical diffusion experiments showed fractionations of 26Mg/24Mg by as much as 7‰, which resulted in an estimate for the mass dependence of the self-diffusion coefficients of the magnesium isotopes corresponding to D26Mg/D24Mg=(24/26)β with β = 0.05. The thermal diffusion experiments showed that a temperature difference of about 100 °C resulted in the MgO, CaO, and FeO components of the basalt becoming slightly enriched by about 1 wt% in the colder end while SiO2 was enriched by several wt% in the hotter end. The temperature gradient also fractionated the magnesium isotopes. A temperature difference of about 150 °C produced an 8‰ enrichment of 26Mg/24Mg at the colder end relative to the hotter end. The magnesium isotopic fractionation as a function of temperature in molten basalt corresponds to 3.6 × 10−2‰/°C/amu.  相似文献   

13.
The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ26Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ26Mg values of loess-derived soil above the cave (−1.0 ± 0.5‰), soil water (−1.2 ± 0.5‰), the carbonate hostrock (−3.8 ± 0.5‰), dripwater in the cave (−1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; −4.3 ± 0.6‰), cave loam (−0.6 ± 0.1‰) and runoff water (−1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000lnαMg-cc-Mg(aq) = −2.4‰. A similar Mg-isotope fractionation (1000lnαMg-cc-Mg(aq) ≈ −2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, 26Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg2+ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for inorganic precipitation experiments.  相似文献   

14.
Mercury isotope fractionation during liquid-vapor evaporation experiments   总被引：2，自引：0，他引：2  
Liquid-vapor mercury isotope fractionation was investigated under equilibrium and dynamic conditions. Equilibrium evaporation experiments were performed in a closed glass system under atmospheric pressure between 0 and 22 °C, where vapor above the liquid was sampled at chemical equilibrium. Dynamic evaporation experiments were conducted in a closed glass system under 10−5 bar vacuum conditions varying (1) the fraction of liquid Hg evaporated at 22 °C and (2) the temperature of evaporation (22-100 °C). Both, residual liquid and condensed vapor fractions were analyzed using stannous chloride CV-MC-ICP-MS.Equilibrium evaporation showed a constant liquid-vapor fractionation factor (α202/198) of 1.00086 ± 0.00022 (2SD, n = 6) within the 0-22 °C range. The 22 °C dynamic evaporations experiments displayed Rayleigh distillation fractionation behavior with liquid-vapor α202/198 = 1.0067 ± 0.0011 (2SD), calculated from both residual and condensed vapor fractions. Our results confirm historical data (1920s) from Brönsted, Mulliken and coworkers on mercury isotopes separation using evaporation experiments, for which recalculated δ202Hg′ showed a liquid-vapor α202/198 of 1.0076 ± 0.0017 (2SD). This liquid-vapor α202/198 is significantly different from the expected kinetic α202/198 value ((202/198)0.5 = 1.0101). A conceptual evaporation model of back condensation fluxes within a thin layer at the liquid-vapor interface was used to explain this discrepancy. The δ202Hg′ of condensed vapor fractions in the 22-100 °C temperature range experiments showed a negative linear relationship with 106/T2, explained by increasing rates of exchange within the layer with the increase in temperature.Evaporation experiments also resulted in non-mass-dependent fractionation (NMF) of odd 199Hg and 201Hg isotopes, expressed as Δ199Hg′ and Δ201Hg′, the deviation in ‰ from the mass fractionation relationship with even isotopes. Liquid-vapor equilibrium yielded Δ199Hg′/Δ201Hg′ relationship of 2.0 ± 0.6 (2SE), which is statistically not different from the one predicted for the nuclear field shift effect (Δ199Hg/Δ201Hg ≈ 2.47). On the other hand, evaporation under dynamic conditions at 22 °C led to negative anomalies in the residual liquid fractions that are balanced by positive anomalies in condensed vapors with lower Δ199Hg′/Δ201Hg′ ratios of 1.2 ± 0.4 (2SD). This suggests that either magnetic isotope effects may have occurred without radical chemistry or an unknown NMF process on odd isotopes operated during liquid mercury evaporation.  相似文献   

15.
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   

16.
We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45′N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]HydEnd) and thereby adopts a δ44/40CaHydEnd of −0.95 ± 0.07‰ relative to seawater (SW) and a 87Sr/86Sr isotope ratio of 0.7034(4). We demonstrate that δ44/40CaHydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a δ44/40Ca of −1.17 ± 0.04‰ (SW) for the host-rocks in the reaction zone and −1.45 ± 0.05‰ (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed δ44/40Ca for Bulk Earth of −0.92 ± 0.18‰ (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about Δ44/40Ca = −0.5‰ relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average δ44/40Ca of −1.54 ± 0.08‰ (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.  相似文献   

17.
The two most abundant network-modifying cations in magmatic liquids are Ca2+ and Mg2+. To evaluate the influence of melt structure on exchange of Ca2+ and Mg2+ with other geochemically important divalent cations (m-cations) between coexisting minerals and melts, high-temperature (1470-1650 °C), ambient-pressure (0.1 MPa) forsterite/melt partitioning experiments were carried out in the system Mg2SiO4-CaMgSi2O6-SiO2 with ?1 wt% m-cations (Mn2+, Co2+, and Ni2+) substituting for Ca2+ and Mg2+. The bulk melt NBO/Si-range (NBO/Si: nonbridging oxygen per silicon) of melt in equilibrium with forsterite was between 1.89 and 2.74. In this NBO/Si-range, the NBO/Si(Ca) (fraction of nonbridging oxygens, NBO, that form bonds with Ca2+, Ca2+-NBO) is linearly related to NBO/Si, whereas fraction of Mg2+-NBO bonds is essentially independent of NBO/Si. For individual m-cations, rate of change of KD(m−Mg) with NBO/Si(Ca) for the exchange equilibrium, mmelt + Mgolivine ? molivine + Mgmelt, is linear. KD(m−Mg) decreases as an exponential function of increasing ionic potential, Z/r2 (Z: formal electrical charge, r: ionic radius—here calculated with oxygen in sixfold coordination around the divalent cations) of the m-cation. The enthalpy change of the exchange equilibrium, ΔH, decreases linearly with increasing Z/r2 [ΔH = 261(9)-81(3)·Z/r2 (Å−2)]. From existing information on (Ca,Mg)O-SiO2 melt structure at ambient pressure, these relationships are understood by considering the exchange of divalent cations that form bonds with nonbridging oxygen in individual Qn-species in the melts. The negative ∂KD(m−Mg)/∂(Z/r2) and ∂(ΔH)/∂(Z/r2) is because increasing Z/r2 is because the cations forming bonds with nonbridging oxygen in increasingly depolymerized Qn-species where steric hindrance is decreasingly important. In other words, principles of ionic size/site mismatch commonly observed for trace and minor elements in crystals, also govern their solubility behavior in silicate melts.  相似文献   

18.
Over the last decade, sea surface temperature (SST) reconstructed from the Mg/Ca ratio of foraminiferal calcite has increasingly been used, in combination with the δ18O signal measured on the same material, to calculate the δ18Ow, a proxy for sea surface salinity (SSS). A number of studies, however, have shown that the Mg/Ca ratio is also sensitive to other parameters, such as pH or , and salinity. To increase the reliability of foraminiferal Mg/Ca ratios as temperature proxies, these effects should be quantified in isolation. Individuals of the benthic foraminifera Ammonia tepida were cultured at three different salinities (20, 33 and 40 psu) and two temperatures (10-15 °C). The Mg/Ca and Sr/Ca ratios of newly formed calcite were analyzed by Laser Ablation ICP-MS and demonstrate that the Mg concentration in A. tepida is overall relatively low (mean value per experimental condition between 0.5 and 1.3 mmol/mol) when compared to other foraminiferal species, Sr being similar to other foraminiferal species. The Mg and Sr incorporation are both enhanced with increasing temperatures. However, the temperature dependency for Sr disappears when the distribution factor DSr is plotted as a function of calcite saturation state (Ω). This suggests that a kinetic process related to Ω is responsible for the observed dependency of Sr incorporation on sea water temperature. The inferred relative increase in DMg per unit salinity is 2.8% at 10 °C and 3.3% at 15 °C, for the salinity interval 20-40 psu. This implies that a salinity increase of 2 psu results in enhanced Mg incorporation equivalent to 1 °C temperature increase. The DSr increase per unit salinity is 0.8% at 10 °C and 1.3% at 15 °C, for the salinity interval 20-40 psu.  相似文献   

19.
The equilibrium Mg isotope fractionation factor between epsomite and aqueous MgSO4 solution has been measured using the three isotope method in recrystallization experiments conducted at 7, 20, and 40 °C. Complete or near-complete isotopic exchange was achieved within 14 days in all experiments. The Mg isotope exchange rate between epsomite and MgSO4 solution is dependent on the temperature, epsomite seed crystal grain size, and experimental agitation method. The Mg isotope fractionation factors (Δ26Mgeps-sol) at 7, 20, and 40 °C are 0.63 ± 0.07‰, 0.58 ± 0.16‰, and 0.56 ± 0.03‰, respectively. These values are indistinguishable within error, indicating that the Mg isotope composition of epsomite is relatively insensitive to temperature. The magnitude of the isotope fractionation factor (Δ26Mgeps-sol = ca. 0.6‰ between 7 and 40 °C) indicates that significant Mg isotope variations can be produced in evaporite sequences, and Mg isotopes may therefore, constrain the degree of closed-system behavior, paleo-humidity, and hydrological history of evaporative environments.  相似文献   

20.
The calcium isotopic compositions (δ44Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (αs−f) between calcite and dissolved Ca2+ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of αs−f at equilibrium in the marine sedimentary section is 1.0000 ± 0.0001, which is significantly different from the value (0.9987 ± 0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ∼14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30-40%/Myr, and decreases with age to about 2%/Myr in 2-3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in δ44Ca of +0.15‰ for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.  相似文献   

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