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1.
The Sr/Ca and Ba/Ca ratios in inorganic apatite are strongly dependent on the temperature of the aqueous medium during precipitation. If valid in biogenic apatite, these thermometers would offer the advantage of being more resistant to diagenesis than those calibrated on biogenic calcite and aragonite. We have reared seabreams (Sparus aurata) in tanks with controlled conditions during experiments lasting for more than 2 years at 13, 17, 23 and 27 °C, in order to determine the variations in Sr and Ba partitioning relative to Ca (DSr and DBa, respectively) between seawater and fish apatitic hard tissues (i.e. teeth and bones), as a function of temperature. The sensitivity of the Sr and Ba thermometers (i.e. ∂DSr/∂T and ∂DBa/∂T, respectively), are similar in bone (/∂T = 0.0036 ± 0.0003 and /∂T = 0.0134 ± 0.0026, respectively) and enamel (/∂T = 0.0037 ± 0.0005 and /∂T = 0.0107 ± 0.0026, respectively). The positive values of ∂DSr/∂T and ∂DBa/∂T in bone and enamel indicate that DSr and DBa increase with increasing temperature, a pattern opposite to that observed for inorganic apatite. This distinct thermodependent trace element partitioning between inorganic and organic apatite and water highlights the contradictory effects of the crystal-chemical and biological controls on the partitioning of Ca, Sr and Ba in vertebrate organisms. Taking into account the diet Sr/Ca and Ba/Ca values, it is shown that the bone Ba/Ca signature of fish can be explained by Ca-biopurification and inorganic apatite precipitation, whereas both of these processes fail to predict the bone Sr/Ca values. Therefore, the metabolism of Ca as a function of temperature still needs to be fully understood. However, the biogenic Sr thermometer is used to calculate an average seawater temperature of 30.6 °C using the Sr/Ca compositions of fossil shark teeth at the Cretaceous/Tertiary boundary, and a typical seawater Sr/Ca ratio of 0.02. Finally, while the present work should be completed with data obtained in natural contexts, it is clear that Sr/Ca and Ba/Ca ratios in fossil biogenic apatite already constitute attractive thermometers for marine paleoenvironments.  相似文献   

2.
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   

3.
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   

4.
As paleoceanographic archives, deep sea coral skeletons offer the potential for high temporal resolution and precise absolute dating, but have not been fully investigated for geochemical reconstructions of past ocean conditions. Here we assess the utility of skeletal P/Ca, Ba/Ca and U/Ca in the deep sea coral D. dianthus as proxies of dissolved phosphate (remineralized at shallow depths), dissolved barium (trace element with silicate-type distribution) and carbonate ion concentrations, respectively. Measurements of these proxies in globally distributed D. dianthus specimens show clear dependence on corresponding seawater properties. Linear regression fits of mean coral Element/Ca ratios against seawater properties yield the equations: P/Cacoral (μmol/mol) = (0.6 ± 0.1) P/Casw(μmol/mol) - (23 ± 18), R2 = 0.6, n = 16 and Ba/Cacoral(μmol/mol) = (1.4 ± 0.3) Ba/Casw(μmol/mol) + (0 ± 2), R2 = 0.6, n = 17; no significant relationship is observed between the residuals of each regression and seawater temperature, salinity, pressure, pH or carbonate ion concentrations, suggesting that these variables were not significant secondary dependencies of these proxies. Four D. dianthus specimens growing at locations with Ωarag ? 0.6 displayed markedly depleted P/Ca compared to the regression based on the remaining samples, a behavior attributed to an undersaturation effect. These corals were excluded from the calibration. Coral U/Ca correlates with seawater carbonate ion: U/Cacoral(μmol/mol) = (−0.016 ± 0.003) (μmol/kg) + (3.2 ± 0.3), R2 = 0.6, n = 17. The residuals of the U/Ca calibration are not significantly related to temperature, salinity, or pressure. Scatter about the linear calibration lines is attributed to imperfect spatial-temporal matches between the selected globally distributed specimens and available water column chemical data, and potentially to unresolved additional effects. The uncertainties of these initial proxy calibration regressions predict that dissolved phosphate could be reconstructed to ±0.4 μmol/kg (for 1.3-1.9 μmol/kg phosphate), and dissolved Ba to ±19 nmol/kg (for 41-82 nmol/kg Basw). Carbonate ion concentration derived from U/Ca has an uncertainty of ±31μmol/kg (for ). The effect of microskeletal variability on P/Ca, Ba/Ca, and U/Ca was also assessed, with emphasis on centers of calcification, Fe-Mn phases, and external contaminants. Overall, the results show strong potential for reconstructing aspects of water mass mixing and biogeochemical processes in intermediate and deep waters using fossil deep-sea corals.  相似文献   

5.
The Yucatan Peninsula consists of a karstic terrain that allows the aquifer to directly recharge from rainfall. Due to the various dissolution/precipitation reactions occurring during groundwater flow, the groundwater discharge in the coastal zone becomes a source of trace elements including Ba. The aim of this study was to use the coralline Ba/Ca record as a proxy of precipitation under the consideration that rainfall rates vary at inter-annual time scales. Annual Ba/Ca ratios, both the total content (Ba/CaTC) and the Ca-substitutive fraction (Ba/CaCaF), were quantified in a 52-a old coral colony of Montastraea annularis from the Punta Nizuc Reef, Mexican Caribbean. Average Ba/CaTC (5.90 ± 0.56 μmol/mol) was ∼20% higher than Ba/CaCaF (4.85 ± 0.33 μmol/mol) indicating that Ba is also incorporated in other fractions. Correlation between annual precipitation and Ba/CaTC time-series is significant (r = 0.77, p < 0.05), allowing the use of the Ba/CaTC ratio as a proxy of precipitation, and hence, enabling the reconstruction of precipitation patterns through time. Likewise, the Ba/CaCaF ratio can be used for the reconstruction of dissolved Ba in coastal seawater.  相似文献   

6.
Trace/minor element signatures (DCd, DBa, DMg, and DSr) were measured in the tests (shells) of benthic foraminifera cultured in a trace-metal-concentration-controlled system. The culture system was constructed of inert materials and designed to limit microhabitat effects. This system ensured that variation observed in cultured foraminiferal element:calcium (TE/Ca) signatures was due to biologically mediated (vital) effects only. Two species, Bulimina aculeata and Rosalina vilardeboana, reproduced prolifically during two 4-to-8-month culture periods. In every case (i.e., for both species and each element), the inter-individual variability was larger than the analytical precision. Mean (±1 standard deviation) DE signatures for B. aculeata were: DCd: 1.5 ± 0.4, DBa × 10: 2.1 ± 0.7, DMg × 1000: 0.62 ± 0.15, and DSr × 10: 1.5 ± 0.1. Cultured B. aculeata DMg, calibrated from culture and core-top (live) field specimens, predicted temperatures within ±2.0 °C. The observed inter-individual variability from culture specimens was as large or larger than comparable results from core-top investigations. R. vilardeboana DCd signatures were significantly lower, while DBa, DMg, and DSr signatures were significantly higher than B. aculeata values. Since our culture system minimizes microhabitat variability, the variation in measured TE/Ca ratios suggests that biological processes are a significant factor in inter-individual and inter-species variability. Comparison of cultured and field-collected foraminiferal DBa signatures supports previous findings that pore-water chemistry is a major environmental influence on foraminiferal test chemistry.  相似文献   

7.
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   

8.
A series of confirmed and suspected dammed palaeo‐lake sedimentary successions is scattered within the middle Yarlung Tsangpo valley in Tibet. However, the chronology, the genesis of the dam and its location, the water level of the dammed lake, the process of dam failure and the spatiotemporal relationships between the sedimentary successions remain controversial. Here, we focus on one sedimentary succession of the suspected dammed palaeo‐lake at Xigazê. We measured the grain‐size distribution, magnetic susceptibility, organic and inorganic carbon content, and δ13Corg and δ15Ntotal ratios of the sediments. In addition, we measured the δ18Oshell and δ13Cshell values of modern and fossil Radix sp. shells, and the δ18Owater and δ13CDIC values of the ambient water with different hydrological regimes. The results indicate that the δ18Oshell values of modern Radix sp. and the δ18Owater of the ambient water body significantly depend on its hydrological status. In addition, a strong positive relationship was observed between δ18Oshell values of modern Radix sp. shells and the δ18Owater of the ambient water on the Tibetan Plateau. According to this correlation, the δ18Owater values of the palaeo‐water body are reconstructed using the δ18Oshell values of Radix sp. fossil shells in the Xigazê section. Further, based on the δ18Oshell values of fossil Radix sp., the reconstructed δ18Owater of the palaeo‐water body and the specific habitats of Radix sp., we infer that the sedimentary succession in the Xigazê broad valley was mainly formed within the backwater terminal zone of a dammed palaeo‐lake and that the elevation of the water level of the lake was approximately 3811 m a.s.l. AMS 14C dating indicates that the deposits of the dammed palaeo‐lake were formed at about 33–22 cal. ka BP. Finally, the presence of Radix sp. fossil shells within the Xigazê section suggests that Radix sp. survived the late Last Glacial Period on the Tibetan Plateau.  相似文献   

9.
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   

10.
The trace elemental composition of calcified larval hard parts may serve as useful tags of natal origin for invertebrate population studies. We examine whether the trace metal barium (Ba) deposits into the calcium carbonate matrix of molluscan larval statolith and protoconch in proportion to seawater Ba concentration at two temperatures (11.5 and 17°C). We also examine strontium (Sr) uptake as a function of temperature. Using encapsulated larvae of the marine gastropod, Kelletia kelletii, reared in the laboratory under controlled conditions, we demonstrate a significant inverse effect of temperature and a positive effect of seawater Ba/Ca ratio on Ba incorporation into larval carbonates. Ba/Ca partition coefficients (DBa) in protoconch were 1.13 at 11.4°C and 0.88 at 17.1°C, while DBa in larval statolith measured 1.58 at 11.4°C and 1.29 at 17.1°C. Strontium incorporation into statoliths is also inversely affected by temperature, but there was a significant positive effect of temperature on Sr incorporation into protoconch. These data suggest larval statoliths and protoconchs can meaningfully record variation in seawater physical and chemical properties, and, hence, have potential as natural tags of natal origin.  相似文献   

11.
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   

12.
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   

13.
The Mg/Ca ratio of seawater has varied significantly throughout the Phanerozoic Eon, primarily as a function of the rate of ocean crust production. Specimens of the crustose coralline alga Neogoniolithon sp. were grown in artificial seawaters encompassing the range of Mg/Ca ratios shown to have existed throughout the Phanerozoic. Significantly, the coralline algae’s skeletal Mg/Ca ratio varied in lockstep with the Mg/Ca ratio of the artificial seawater. Specimens grown in seawater treatments formulated with identical Mg/Ca ratios but differing absolute concentrations of Mg and Ca exhibited no significant differences in skeletal Mg/Ca ratios, thereby emphasizing the importance of the ambient Mg/Ca ratio, and not the absolute concentration of Mg, in determining the Mg/Ca ratio of coralline algal calcite. Specimens grown in seawater of the lowest molar Mg/Ca ratio (mMg/Ca = 1.0) actually changed their skeletal mineralogy from high-Mg (skeletal mMg/Ca > 0.04) to low-Mg calcite (skeletal mMg/Ca < 0.04), suggesting that ancient calcitic red algae, which exhibit morphologies and modes of calcification comparable to Neogoniolithon sp., would have produced low-Mg calcite from the middle Cambrian to middle Mississippian and during the middle to Late Cretaceous, when oceanic mMg/Ca approached unity. By influencing the original Mg content of carbonate facies in which these algae have been ubiquitous, this condition has significant implications for the geochemistry and diagenesis of algal limestones throughout most of the Phanerozoic. The crustose coralline algae’s precipitation of high-Mg calcite from seawater that favors the abiotic precipitation of aragonite indicates that these algae dictate the precipitation of the calcitic polymorph of CaCO3. However, the algae’s nearly abiotic pattern of Mg fractionation in their skeletal calcite suggests that their biomineralogical control is limited to polymorph specification and is generally ineffectual in the regulation of skeletal Mg incorporation. Therefore, the Mg/Ca ratio of well-preserved fossils of crustose coralline algae, when corrected for the effect of seawater temperature, may be an archive of oceanic Mg/Ca throughout the Phanerozoic. Magnesium fractionation algorithms that model algal skeletal Mg/Ca as a function of seawater Mg/Ca and temperature are presented herein. The results of this study support the empirical fossil evidence that secular variation of oceanic Mg/Ca has caused the mineralogy and skeletal chemistry of many calcifying marine organisms to change significantly over geologic time.  相似文献   

14.
Sorption and catalytic oxidation of Fe(II) at the surface of calcite   总被引：1，自引：0，他引：1  
The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds-minutes) was followed by (b) a slower incorporation (hours-weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA57 (1993), 3505; Pokrovsky et al., Langmuir16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO3Fe+ and >CO3FeCO3H0. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system (t1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite (t1/2 = 41 ± 1 min and t1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO3FeCO3H0, for which the species specific rate constant was estimated.  相似文献   

15.
Calcium isotope fractionation in calcite and aragonite   总被引：1，自引：0，他引：1  
Calcium isotope fractionation was measured on skeletal aragonite and calcite from different marine biota and on inorganic calcite. Precipitation temperatures ranged from 0 to 28°C. Calcium isotope fractionation shows a temperature dependence in accordance with previous observations: 1000 · ln(αcc) = −1.4 + 0.021 · T (°C) for calcite and 1000 · ln(αar) = −1.9 + 0.017 · T (°C) for aragonite. Within uncertainty the temperature slopes are identical for the two polymorphs. However, at all temperatures calcium isotopes are more fractionated in aragonite than in calcite. The offset in δ44/40Ca is about 0.6‰. The underlying mechanism for this offset may be related to the different coordination numbers and bond strengths of the calcium ions in calcite and aragonite crystals, or to different Ca reaction behavior at the solid-liquid interface. Recently, the observed temperature dependence of the Ca isotope fractionation was explained quantitatively by the temperature control on precipitation rates of calcium carbonates in an experimental setting (Lemarchand et al., 2004). We show that this mechanism can in principle also be applied to CaCO3 precipitation in natural environments in normal marine settings. Following this model, Ca isotope fractionation in marine Ca carbonates is primarily controlled by precipitation rates. On the other hand the larger Ca isotope fractionation of aragonite compared to calcite can not be explained by different precipitation rates. The rate control model of Ca isotope fractionation predicts a strong dependence of the Ca isotopic composition of carbonates on ambient CO32− concentration. While this model is in general accordance with our observations in marine carbonates, cultured specimens of the planktic foraminifer Orbulina universa show no dependence of Ca-isotope fractionation on the ambient CO32− concentration. The latter observation implies that the carbonate chemistry in the calcifying vesicles of the foraminifer is independent from the ambient carbonate ion concentration of the surrounding water.  相似文献   

16.
226Ra, 228Ra and Ba distributions as well as 228Ra/226Ra and 226Ra/Ba ratios were measured in seawater, suspended and sinking particles at the DYFAMED station in the Western Mediterranean Sea at different seasons of year 2003 in order to track the build-up and fate of barite through time. The study of the 228Raex/226Raex ratios (Raex = Ra activities corrected for the lithogenic Ra) of suspended particles suggests that Baex (Baex = Ba concentrations corrected for the lithogenic Ba, mostly barite) formation takes place not only in the upper 500 m of the water column but also deeper (i.e. throughout the mesopelagic layer). Temporal changes in the 228Raex/226Raex ratios of sinking particles collected at 1000 m depth likely reflect changes in the relative proportion of barite originating from the upper water column (with a high 228Ra/226Ra ratio) and formed in the mesopelagic layer (with a low 228Ra/226Ra ratio). 228Raex/226Raex ratios measured in sinking particles collected in the 1000 m-trap in April and May suggest that barite predominantly formed in the upper water column during that period, while barite found outside the phytoplankton bloom period (February and June) appears to form deeper in the water column. Combining ratios of both the suspended and sinking particles provides information on aggregation/disaggregation processes. High 226Raex/Baex ratios were also found in suspended particles collected in the upper 500 m of the water column. Because celestite is expected to be enriched in Ra [Bernstein R. E., Byrne R. H. and Schijf J. (1998) Acantharians: a missing link in the oceanic biogeochemistry of barium. Deep-Sea Res. II45, 491-505], acantharian skeletons may contribute to these high ratios in shallow waters. The formation of both acantharian skeletons and barite enriched in 226Ra may thus contribute to the decrease in the dissolved 226Ra activity and 226Ra/Ba ratios of surface waters observed between February and June 2003 at the DYFAMED station.  相似文献   

17.
Specimens of two species of planktic foraminifera, Globigerinoides ruber and Globigerinella siphonifera, were grown under controlled laboratory conditions at a range of temperatures (18-31 °C), salinities (32-44 psu) and pH levels (7.9-8.4). The shells were examined for their calcium isotope compositions (δ44/40Ca) and strontium to calcium ratios (Sr/Ca) using Thermal Ionization Mass Spectrometry and Inductively Coupled Plasma Mass Spectrometry. Although the total variation in δ44/40Ca (∼0.3‰) in the studied species is on the same order as the external reproducibility, the data set reveals some apparent trends that are controlled by more than one environmental parameter. There is a well-defined inverse linear relationship between δ44/40Ca and Sr/Ca in all experiments, suggesting similar controls on these proxies in foraminiferal calcite independent of species. Analogous to recent results from inorganically precipitated calcite, we suggest that Ca isotope fractionation and Sr partitioning in planktic foraminifera are mainly controlled by precipitation kinetics. This postulation provides us with a unique tool to calculate precipitation rates and draws support from the observation that Sr/Ca ratios are positively correlated with average growth rates. At 25 °C water temperature, precipitation rates in G. siphonifera and G. ruber are calculated to be on the order of 2000 and 3000 μmol/m2/h, respectively. The lower δ44/40Ca observed at ?29 °C in both species is consistent with increased precipitation rates at high water temperatures. Salinity response of δ44/40Ca (and Sr/Ca) in G. siphonifera implies that this species has the highest precipitation rates at the salinity of its natural habitat, whereas increasing salinities appear to trigger higher precipitation rates in G. ruber. Isotope effects that cannot be explained by precipitation rate in planktic foraminifera can be explained by a biological control, related to a vacuolar pathway for supply of ions during biomineralization and a pH regulation mechanism in these vacuoles. In case of an additional pathway via cross-membrane transport, supplying light Ca for calcification, the δ44/40Ca of the reservoir is constrained as −0.2‰ relative to seawater. Using a Rayleigh distillation model, we calculate that calcification occurs in a semi-open system, where less than half of the Ca supplied by vacuolization is utilized for calcite precipitation. Our findings are relevant for interpreting paleo-proxy data on δ44/40Ca and Sr/Ca in foraminifera as well as understanding their biomineralization processes.  相似文献   

18.
Batch uptake experiments and X-ray element mapping and spectroscopic techniques were used to investigate As(V) (arsenate) uptake mechanisms by calcite, including adsorption and coprecipitation. Batch sorption experiments in calcite-equilibrated suspensions (pH 8.3; PCO2 = 10−3.5 atm) reveal rapid initial sorption to calcite, with sorption rate gradually decreasing with time as available sorption sites decrease. An As(V)-calcite sorption isotherm determined after 24 h equilibration exhibits Langmuir-like behavior up to As concentrations of 300 μM. Maximum distribution coefficient values (Kd), derived from a best fit to a Langmuir model, are ∼190 L kg−1.Calcite single crystals grown in the presence of As(V) show well-developed rhombohedral morphology with characteristic growth hillocks on surfaces at low As(V) concentrations (?5 μM), but habit modification is evident at As(V) concentrations ?30 μM in the form of macrostep development preferentially on the − vicinal surfaces of growth hillocks. Micro-X-ray fluorescence element mapping of surfaces shows preferential incorporation of As in the − vicinal faces relative to + vicinals. EXAFS fit results for both adsorption and coprecipitation samples confirm that As occurs in the 5+ oxidation state in tetrahedral coordination with oxygen, i.e., as arsenate. For adsorption samples, As(V) forms inner-sphere surface complexes via corner-sharing with Ca octahedra. As(V) coprecipitated with calcite substitutes in carbonate sites but with As off-centered, as indicated by two Ca shells, and with likely disruption of local structure. The results indicate that As(V) interacts strongly with the calcite surface, similar to often-cited analog phosphate, and uptake can occur via both adsorption and coprecipitation reactions. Therefore, calcite may be effective for partial removal of dissolved arsenate from aquatic and soil systems.  相似文献   

19.
Land snails provide a unique opportunity to study terrestrial paleoenvironments because their shells, which are generally highly abundant and well-preserved in the fossil record, contain a temporal record of environmental change in the form of isotope codes. To evaluate the utility of this approach for a low-latitude oceanic setting, 207 modern shells of 18 species of land snail were analyzed for their oxygen and carbon isotope composition along a north and south facing altitudinal gradient (10-2160 m a.s.l.) in Tenerife Island (∼28°N) of the Canary Archipelago.Shells collected at each locality showed a relatively large range in isotope composition which was greater along the south facing transect (drier and hotter), suggesting that the variance in shell isotope values may be related to water-stress. Although pooled isotope values did not generally show strong relationships with environmental variables (i.e., altitude, temperature and precipitation), mean isotope values were strongly associated with some climatic factors when grouped by site. The mean δ18O value of the shell (δ18Oshell) by site displayed a negative correlation with elevation, which is consistent with the positive relationship observed between temperature and the δ18O value of rain (δ18Orain). Calculated δ18O values of the snail body water (δ18Obody) derived from observed temperatures and δ18Oshell values (using the equation of Grossman and Ku [Grossman E. L. and Ku T. L. (1986) Oxygen and carbon isotope fractionation in biogenic aragonite. Chem. Geol. (Isotope Geosci. Sec.)59, 59-74]) displayed a trend with respect to altitude that was similar to measured and hypothetical δ18O values for local rain water. The calculated δ18Obody values from the shell declined 0.17‰ (VSMOW) per 100 m, which is consistent with the “altitude effect” observed for tropical rains in Western Africa, and it correlated negatively with rainfall amount. Accordingly, lower δ18Oshell values indicate lower temperatures, lower δ18Orain values and possibly, higher rainfall totals. A positive correlation between the mean δ13C values of shells (δ13Cshell) and plants by site suggests that shells potentially record information about the surrounding vegetation. The δ13Cshell values varied between −15.7 and −0.6‰ (VPDB), indicating that snails consumed C3 and C4/CAM plants, where more negative δ13Cshell values probably reflects the preferential consumption of C3 plants which are favored under wetter conditions. Individuals with more positive δ13Cshell values consumed a larger percentage of C4 plants (other potential factors such as carbonate ingestion or atmospheric CO2 contribution were unlikely) that were more common at lower elevations of the hotter and drier south facing transect. The relatively wide range of shell isotope values within a single site requires the analysis of numerous shells for meaningful paleoclimatic studies. Although small differences were observed in isotope composition among snail species collected at a single sampling site, they were not significant, suggesting that isotope signatures extracted from multi-taxa snail data sets may be used to infer environmental conditions over a broad range of habitats.  相似文献   

20.
Magnesium/calcium, Sr/Ca, and Na/Ca atom ratios were determined in the calcite and aragonite regions of Mytilus edulis shells which were grown in semi-artificial ‘seawater’ solutions having varying Mg/Ca, Sr/Ca, and Na/Ca ratios. These ratios were measured by instrumental neutron activation, atomic absorption, and electron microprobe analytical techniques. Strontium/calcium ratios in both calcite and aragonite were linearly proportional to solution Sr/Ca ratios. Magnesium/calcium ratios in calcite increased exponentially when solution Mg/Ca ratios were raised above the normal seawater ratio; whereas in aragonite, Mg/Ca ratios increased linearly with increases in solution Mg/Ca ratios. Sodium/calcium and sulfur/calcium ratios in calcite covaried with Mg/Ga solution ratios. Conversely, in aragonite, Na/Ca ratios varied linearly with solution Na/Ca ratios.Magnesium is known to inhibit calcite precipitation at its normal seawater concentration. We infer from the results of the work reported here that Mytilus edulis controls the Mg activity of the outer extrapallial fluid, thus facilitating the precipitation of calcitic shell. Increases in sulfur content suggest that changes in shell organic matrix content occur as a result of environmental stress. Certain increases in Mg content may also be correlated to stress. Sodium/calcium variations, and their absolute amounts in calcite and aragonite, are best explained by assuming that a substantial amount of Na is adsorbed on the calcium carbonate crystal surface. Strontium/calcium ratios show more promise than either Mg/Ca or Na/Ca ratios as seawater paleochemistry indicators, because the Sr/Ca distribution coefficients for both aragonite and calcite are independent of seawater Ca and Sr concentrations.  相似文献   

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