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1.
Comparative concentrations of carbonate and hydroxide complexes in natural solutions can be expressed in terms of reactions with bicarbonate that have no explicit pH dependence (). Stability constants for this reaction with n = 1 were determined using conventional formation constant data expressed in terms of hydroxide and carbonate. Available data indicate that stability constants appropriate to seawater at 25 °C expressed in the form are on the order of 104.2 for a wide range of cations (Mz+) with z = +1, +2 and +3. Φ1 is sufficiently large that species appear to substantially dominate MOHz−1 species in seawater. Evaluations of comparative stepwise carbonate and hydroxide stability constant behavior leading to the formation of n = 2 and n = 3 complexes suggest that carbonate complexes generally dominate hydroxide complexes in seawater, even for cations whose inorganic speciation schemes in seawater are currently presumed to be strongly dominated by hydrolyzed forms (). Calculated stability constants, and , indicate that the importance of carbonate complexation is sufficiently large that carbonate and hydroxide complexes would be generally comparable even if calculated Φ2 and Φ3 values are overestimated by two or more orders of magnitude. Inclusion of mixed ligand species in carbonate-hydroxide speciation models allows cation complexation intensities (MT/[Mz+]) to be expressed in the following form:
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2.
In a recent study, sulphate-bearing green rust (GRSO4) was shown to incorporate Na+ in its structure (NaFeII6FeIII3(OH)18(SO4)2(s); GRNa,SO4). The compound was synthesised by aerial oxidation of Fe(OH)2(s) in the presence of NaOH. This paper reports on its free energy of formation .Freshly synthesised GRNa,SO4 was titrated with 0.5 M H2SO4 in an inert atmosphere at 25 °C, producing dissolved Fe2+ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions:
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3.
Several studies have shown that there is a strong relationship between the distribution of crenarchaeotal isoprenoid glycerol dibiphytanyl glycerol tetraethers (GDGTs) and sea surface temperature (SST). Based on this, a ratio of certain GDGTs, called TEX86 (TetraEther indeX of tetraethers consisting of 86 carbon atoms), was developed as a SST proxy. In this study, we determined the distribution of crenarchaeotal isoprenoid GDGTs in 116 core-top sediments mostly from (sub)polar oceans and combined these data with previously published core-top data. Using this extended global core-top dataset (n = 426), we re-assessed the relationship of crenarchaeal isoprenoid GDGTs with SST. We excluded data from the Red Sea from the global core-top dataset to define new indices and calibration models, as the Red Sea with its elevated salinity appeared to behave differently compared to other parts of the oceans. We tested our new indices and calibration models on three different paleo datasets, representing different temperature ranges. Our results indicate that the crenarchaeol regio-isomer plays a more important role for temperature adaptation in (sub)tropical oceans than in (sub)polar oceans, suggesting that there may be differences in membrane adaptation of the resident crenarchaeotal communities at different temperatures. We, therefore, suggest to apply two different calibration models. For the whole calibration temperature range (−3 to 30 °C), a modified version of TEX86 with a logarithmic function which does not include the crenarchaeol regio-isomer, called , is shown to correlate best with SST: (r2 = 0.86, n=396, p <0.0001). Application of on sediments from the subpolar Southern Ocean results in realistic absolute SST estimates and a similar SST trend compared to a diatom SST record from the same core. , which is defined as the logarithmic function of TEX86, yields the best correlation with SST, when the data from the (sub)polar oceans are removed: (r2 = 00.87, n = 255, p < 0.0001). Furthermore, gives the best correlation for mescosm data with temperatures ranging between 10 and 46 °C. For Quaternary sediments from the tropical Arabian Sea, both and yield similar trends and SST estimates. However, the extrapolation of calibration on a sediment record from a greenhouse world ocean predicts more reliable absolute SST estimates and relative SST changes in agreement with estimates based on the δ18O of planktonic foraminifera. Based on the comparison of and derived SSTs using the core top data, we recommend applying above 15 °C and below 15 °C. In cases where paleorecords encompass temperatures both below and above 15 °C, we suggest to use .  相似文献   

4.
Although the stable oxygen isotope fractionation between dissolved sulfate ion and H2O (hereafter ) is of physico-chemical and biogeochemical significance, no experimental value has been established until present. The primary reason being that uncatalyzed oxygen exchange between and H2O is extremely slow, taking ∼105 years at room temperature. For lack of a better approach, values of 16‰ and 31‰ at 25 °C have been assumed in the past, based on theoretical ‘gas-phase’ calculations and extrapolation of laboratory results obtained at temperatures >75 °C that actually pertain to the bisulfate system. Here I use novel quantum-chemistry calculations, which take into account detailed solute-water interactions to establish a new value for of 23‰ at 25 °C. The results of the corresponding calculations for the bisulfate ion are in agreement with observations. The new theoretical values show that sediment -data, which reflect oxygen isotope equilibration between sulfate and ambient water during microbial sulfate reduction, are consistent with the abiotic equilibrium between and water.  相似文献   

5.
We performed a series of synthesis experiments at 1 atm pressure to investigate the substitution mechanisms of 1+ and 3+ ions into olivine. Forsterite crystals were grown from bulk compositions that contained the element of interest (e.g. Li) and different amounts of additional single trace elements. By working at constant (major element) liquid composition and temperature we eliminated all compositional effects other than those due to the trace elements. Mineral-melt pairs were then analysed to determine the compositional-dependence of the partition coefficient (D), which corresponds to , and where [element] refers to weight concentration of the element in the respective phase.We find that Li forms a stable coupled substitution with Sc and, at above ∼500 ppm Sc in the crystal, Li+ and Sc3+ ions form an ordered neutral complex ([LiSc]). This complex dissociates at lower trace element concentrations and a second, concentration-independent, mechanism begins to dominate. This second solution mechanism is most likely 2Li+ ⇔ Mg2+ where one of the Li atoms is in an interstitial position in the crystal lattice. Natural olivines show Li contents slightly greater than Sc (on an atomic basis), indicating that both substitution mechanisms are significant. Unlike Sc, Al does not appear to form a stable complex with Li in the olivine structure.Sodium is highly incompatible in olivine with of ∼0.00015-0.03. Olivine-liquid partitioning of Na+ is independent of Sc3+ or Al3+ concentration. This indicates that the coupled substitution of Na+ with any 3+ ions is unlikely. Instead, the relevant substitution mechanism appears to be 2Na+ ⇔ Mg2+. Although independent of 3+ ion concentration, is inversely correlated with the Li concentration of both melts and crystals, implying that Na competes (unsuccessfully) with Li to replace Mg in the olivine structure.Aluminium is highly incompatible in forsterite . Values of are similar for all phase pairs synthesised from starting materials containing between 10 and 100,000 ppm Al. This suggests that Al is principally incorporated in forsterite by replacing one Mg and one Si atom , where the Al atoms on octahedral (Mg) and tetrahedral (Si) sites are dissociated from one another.The incorporation of gallium into forsterite is influenced by the presence of Li. Where Li concentration in the crystal is much greater than that of Ga (on an atomic basis) we find an excellent correlation between and melt Li content. This relationship indicates that Ga3+ and Li+ replace 2Mg2+ on octahedral sites and that the Ga and Li atoms are, like Sc and Li, strongly associated in the crystal structure.The mechanism by which scandium is incorporated into forsterite is strongly governed by the presence Li. As discussed above, ordered complexes form readily in forsterite in Li-rich experiments. Under Li-absent but Sc-rich conditions (Sc in the crystal >∼500 ppm), is proportional to the concentration of Sc in the melt. This indicates that Sc incorporation is charge-balanced by the formation of magnesium vacancies , and that both species are associated . At lower Sc concentrations (<500 ppm in the crystal), the concentration-dependence of partitioning indicates that the complexes dissociate.Our results demonstrate that partitioning of 1+ and 3+ ions into olivine is complex and involves a range of point defects which yield strongly composition-dependent crystal-melt partition coefficients. Since physical and chemical properties of natural olivine, such as diffusion of 6Li and 7Li and H2O solubility, depend on the concentrations of the defects identified in this study, our results provide an important insight into how determining substitution mechanisms can improve our understanding of large-scale mantle processes and properties.  相似文献   

6.
As a contribution to the systematic study of iron oxide thermodynamics, this work reports enthalpies of formation of green rust, a double layered (FeII, FeIII) hydroxide with the ideal stoichiometry , with sulfate as the anion in the interlayer. Samples were characterized by X-ray powder diffraction, thermogravimetric analysis, infrared spectroscopy, and Mössbauer spectroscopy. Full chemical analysis was performed. Contents of FeII, FeIII, water, and sulfate were obtained. We report standard enthalpies of formation for green rust with different FeII/FeIII ratios. Enthalpies of formation from single cation compounds, namely, Fe(OH)2, Fe(OH)3, FeSO4 and H2O show reasonable agreement with Gibbs free energies of formation from single cation compounds recalculated from the reported literature values. These values show that green rust has little stabilization over a mechanical mixture of these single cation compounds and there is no thermodynamic preference for any particular FeII/FeIII ratio.  相似文献   

7.
Sedimentary S cycling is usually conceptualized and interpreted within the context of steadily accreting (1-D) transport-reaction regimes. Unsteady processes, however, are common in many sedimentary systems and can result in dramatically different S reaction balances and diagenetic products than steady conditions. Globally important common examples include tropical deltaic topset and inner shelf muds such as those extending from the Amazon River ∼1600 km along the Guianas coast of South America. These deposits are characterized by episodic reworking of the surface seabed over vertical depths of ∼0.1-3 m. Reworked surface sediments act as unsteady, suboxic batch reactors, unconformably overlying relict anoxic, often methanic deposits, and have diagenetic properties largely decoupled from net accumulation of sediment. Despite well-oxygenated water and an abundant reactive organic matter supply, physical disturbance inhibits macrofauna, and benthic communities are dominated by microbial biomass across immense areas. In the surficial suboxic layer, molecular biological analyses, tracer experiments, sediment C/S/Fe compositions, and δ34S, δ18O of pore water indicate close coupling of anaerobic C, S, and Fe cycles. δ18O- can increase by 2-3‰ during anaerobic recycling without net change in δ34S-, demonstrating reduction coupled to complete anaerobic reoxidation to and a δ18O- reduction + reoxidation fractionation factor?12‰ (summed magnitudes). S reoxidation must be coupled to Fe-oxide reduction, contributing to high dissolved Fe2+ (∼1 mM) and Fe mobilization-export. The reworking of Amazon-Guianas shelf muds alone may isotopically alter δ18O- equivalent in mass to?25% of the annual riverine delivery of to the global ocean. Unsteady conditions result in preservation of unusually heavy δ34S isotopic compositions of residual Cr reducible S, ranging from 0‰ to >30‰ in physically reworked deposits. In contrast, bioturbated facies adjacent to physically reworked regions accumulate isotopically light S (δ34S to −20‰) in otherwise similar decomposition regimes. The isotopic patterns of both physically and biologically reworked regions can be simulated with simple diagenetic models. Heavy S isotopic signatures are largely a consequence of unsteady diffusion and progressive anaerobic burndown into underlying deposits, whereas isotopically depleted bioturbated deposits predominantly reflect biogenic diffusive scaling and isotopic distillation/diffusive pumping associated with reoxidation in burrow walls immediately adjacent to reduced zones. The S isotopic transition from unsteady physically controlled regions of the Amazon delta moving laterally into bioturbated facies mimics the transition of S isotopic patterns temporally in the geologic record during the rise of bioturbation. No special role for S disproportionation is required to explain these differences. The potential role of unsteady, suboxic diagenesis and dynamic reworking of sediments has been largely ignored in models of the evolution of surficial elemental cycling and interpretations of the geologic record.  相似文献   

8.
Four or five sets of ab initio models, including Unrestricted Hartree Fock (UHF) and hybrid Density Functional Theory (DFT) are calculated for each species in a series of aqueous ferric aquo-chloro complexes: , , , FeCl3(H2O)3, FeCl3(H2O)2, , FeCl5H2O2−, , ) in order to determine the relative isotopic fractionation among the complexes, to compare the results of different models for the same complexes, to examine factors that influence the magnitude of the isotopic fractionation, and to compare bond-partner-driven fractionation with redox-driven fractionation.Relative to , all models show a nearly linear decrease in 56Fe/54Fe as the number of Cl− ions per Fe3+ ion increases, with slopes of −0.8‰ to −1.0‰ per Cl− at 20 °C. At 20 °C, 1000 ln β (β = 56Fe/54Fe reduced partition function ratio relative to a dissociated Fe atom) values range from 8.93‰ to 9.73‰ for , 8.04-9.12‰ for , 7.61-8.73‰ for , 7.14-8.25‰ for , and 3.09-4.41‰ for . The fractionation between and ranges from 1.5‰ to 2.6‰, depending on the model; this is comparable in magnitude to fractionation effects due to Fe3+/Fe2+ redox reactions. β values from the UHF models are consistently higher than those from the hybrid DFT models.Isotopic fractionation is shown to be sensitive to differences in ligand bond stiffness (above), coordination number, bond length, and the frequency of the asymmetric Fe-X stretching vibrational mode, as predicted by previous theoretical studies. Complexes with smaller coordination numbers have higher 1000 ln β (7.46‰, 5.25‰, and 3.48‰ for , ,, respectively, from the B3LYP/6-31G(d) model). Species with the same number of chlorides but fewer waters also show the effect of coordination number on 1000 ln β: (7.46‰ vs. 7.05‰ for FeCl3(H2O)2 vs. FeCl3(H2O)3 and 5.25‰ vs. 4.94‰ for vs. FeCl5H2O2− with the B3LYP/6-31G(d) model). As more Fe-Cl bonds substitute for Fe-OH2 bonds (with a resulting decrease in β), the lengths of the Fe-Cl bonds and the Fe-O bonds increase.Preliminary modeling of shows an Fe3+/Fe2+ fractionation of 3.2‰ for the B3LYP/6-31G(d) model, in agreement with previous studies. The addition of an explicit outer hydration sphere of 12 H2O molecules to models of improves agreement with measured vibrational frequencies and bond lengths; 1000 ln β increases by 0.8-1.0‰. An additional hydration sphere around increases 1000 ln β by only 0.1‰.Isotopic fractionations predicted for this simple system imply that ligands present in an aqueous iron environment are potentially important drivers of fractionation, and suggest that significant fractionation effects are likely in other aqueous systems containing sulfides or organic ligands. Fractionation effects due to both speciation and redox must be considered when interpreting iron isotope fractionations in the geological record.  相似文献   

9.
The effect of sulfur dissolved as sulfide (S2−) in silicate melts on the activity coefficients of NiO and some other oxides of divalent cations (Ca, Cr, Mn, Fe and Co) has been determined from olivine/melt partitioning experiments at 1400 °C in six melt compositions in the system CaO-MgO-Al2O3-SiO2 (CMAS), and in derivatives of these compositions at 1370 °C, obtained from the six CMAS compositions by substituting Fe for Mg (FeCMAS). Amounts of S2− were varied from zero to sulfide saturation, reaching 4100 μg g−1 S in the most sulfur-rich silicate melt. The sulfide solubilities compare reasonably well with those predicted from the parameterization of the sulfide capacity of silicate melts at 1400 °C of O’Neill and Mavrogenes (2002), although in detail systematic deviations indicate that a more sophisticated model may improve the prediction of sulfide capacities.The results show a barely discernible effect of S2− in the silicate melt on Fe, Co and Ni partition coefficients, and also surprisingly, a tiny but resolvable effect on Ca partitioning, but no detectable effect on Cr, Mn or some other lithophile incompatible elements (Sc, Ti, V, Y, Zr and Hf). Decreasing Mg# of olivine (reflecting increasing FeO in the system) has a significant influence on the partitioning of several of the divalent cations, particularly Ca and Ni. We find a remarkably systematic correlation between and the ionic radius of M2+, where M = Ca, Cr, Mn, Fe, Co or Ni, which is attributable to a simple relationship between size mismatch and excess free energies of mixing in Mg-rich olivine solid solutions.Neither the effect of S2− nor of Mg#ol is large enough by an order of magnitude to account for the reported variations of obtained from electron microprobe analyses of olivine/glass pairs from mid-ocean ridge basalts (MORBs). Comparing these MORB glass analyses with the Ni-MgO systematics of MORB from other studies in the literature, which were obtained using a variety of analytical techniques, shows that these electron microprobe analyses are anomalous. We suggest that the reported variation of with S content in MORB is an analytical artifact.Mass balance of melt and olivine compositions with the starting compositions shows that dissolved S2− depresses the olivine liquidus of haplobasaltic silicate melts by 5.8 × 10−3 (±1.3 × 10−3) K per μg g−1 of S2−, which is negligible in most contexts. We also present data for the partitioning of some incompatible trace elements (Sc, Ti, Y, Zr and Hf) between olivine and melt. The data for Sc and Y confirm previous results showing that and decrease with increasing SiO2 content of the melt. Values of average 0.01 with most falling in the range 0.005-0.015. Zr and Hf are considerably more incompatible than Ti in olivine, with and about 10−3. The ratio / is well constrained at 0.611 ± 0.016.  相似文献   

10.
A two-dimensional (2D) reactive transport model is used to investigate the controls on nutrient (, , PO4) dynamics in a coastal aquifer. The model couples density-dependent flow to a reaction network which includes oxic degradation of organic matter, denitrification, iron oxide reduction, nitrification, Fe2+ oxidation and sorption of PO4 onto iron oxides. Porewater measurements from a well transect at Waquoit Bay, MA, USA indicate the presence of a reducing plume with high Fe2+, , DOC (dissolved organic carbon) and PO4 concentrations overlying a more oxidizing -rich plume. These two plumes travel nearly conservatively until they start to overlap in the intertidal coastal sediments prior to discharge into the bay. In this zone, the aeration of the surface beach sediments drives nitrification and allows the precipitation of iron oxide, which leads to the removal of PO4 through sorption. Model simulations suggest that removal of through denitrification is inhibited by the limited overlap between the two freshwater plumes, as well as by the refractory nature of terrestrial DOC. Submarine groundwater discharge is a significant source of to the bay.  相似文献   

11.
We present major and trace element and Sr-Nd-Pb and U-Th-Pa-Ra isotope data for a small sample suite of primarily post-glacial, mildly alkalic volcanic rocks from the Snaefellsjökull central volcano situated off the main rift systems in western Iceland. The volcanic rocks are crystal-poor and range from olivine alkali basalt to trachyte and show tight correlations of major and trace elements that are explained by fractional crystallization involving removal of olivine, plagioclase, clinopyroxene, Fe-Ti oxide and apatite. Sr-Nd-Pb isotopes are practically invariant, consistent with derivation from the same source region. During fractionation from primitive basalt to evolved trachyte, (230Th/232Th), (230Th/238U) and (231Pa/235U) decrease progressively at broadly constant (238U/232Th). A continuous closed-system fractionation model that assumes constant initial (230Th/232Th) in the basaltic precursor melt indicates that hawaiite was derived from olivine basalt by ∼50% fractional crystallization within and trachyte by ∼80% fractionation within . An overrepresentation of evolved basalts and hawaiites with young inferred magma ages in the dataset is consistent with the parental precursor to these magmas intruded into the sub-volcanic magma plumbing system as a consequence of lithospheric rebound caused by deglaciation. Lavas affected by apatite removal have higher (231Pa/235U) than predicted for simple radioactive decay, suggesting apatite significantly fractionates U from Pa. The proposed fractionation model consistently explains our U-series data assuming and and . If applicable, these D values would indicate that the effect of apatite fractionation must be adequately considered when assessing differentiation time scales using (231Pa/235U) disequilibria data.  相似文献   

12.
Elemental and isotopic abundances of lithium in chondrule constituents in the Allende CV3 meteorite were determined using secondary ion mass spectrometry. Olivines and mesostasis dominated by a feldspathic phase are depleted in Li ( and , respectively). In contrast, low-Ca pyroxenes and mesostasis dominated by a Na-rich phase are enriched in Li ( and , respectively) and the interchondrule matrix is generally enriched in Li ( on average). The Li isotopic abundance of olivine ranges from to 21. The spatial distributions of elemental and isotopic abundances of Li in olivines within individual chondrules exhibit no systematic pattern. This suggests that the distribution of Li in olivine was not disturbed during aqueous alteration or thermal metamorphism on the Allende meteorite parent body. Although mesostasis is the last crystallizing phase from a chondrule melt and is expected to be enriched in Li, in the Allende meteorite it is generally depleted in Li. We suggest that during aqueous alteration on the CV asteroid, Li in mesostasis was leached out by aqueous fluids. The Li-enriched Na-rich mesostasis was probably produced later by infiltration of Na-rich fluids. It seems likely that aqueous fluids sequestered alkali elements from the Allende-chondrite region in the CV parent asteroid, although significant amounts of Li are preserved in ferrous olivine in the interchondrule matrix.  相似文献   

13.
The influence of solution complexation on the sorption of yttrium and the rare earth elements (YREEs) by amorphous ferric hydroxide was investigated at 25 °C over a range of pH (4.0-7.1) and carbonate concentrations . Distribution coefficients, defined as , where [MSi]T is the total concentration of sorbed YREE, MT is the total YREE concentration in solution, and [Si] is the concentration of amorphous ferric hydroxide, initially increased in magnitude with increasing carbonate concentration, and then decreased. The initial increase of is due to sorption of YREE carbonate complexes , in addition to sorption of free YREE ions (M3+). The subsequent decrease of , which is more extensive for the heavy REEs, is due to the increasing intensity of YREE solution complexation by carbonate ions. The competition for YREEs between solution complexation and surface complexation was modeled via the equation:
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14.
Arsenic, iron and sulfur co-diagenesis in lake sediments   总被引：3，自引：0，他引：3  
Profiles of porewater pH and dissolved As, Fe, Mn, sulfate, total sulfide (ΣS−II), total zero-valent sulfur (ΣS0), organic carbon and major ion concentrations, as well as those of solid As, acid-volatile sulfide (AVS), total S, Fe, Mn, Al, organic C, 210Pb and 137Cs were determined in the sediment of four lakes spanning a range of redox and geochemical conditions. An inverse modeling approach, based on a one-dimensional transport-reaction equation assuming steady-state, was applied to the porewater As profiles and used to constrain the net rates of reactions involving As (). The model defines depth intervals where As is either released to (positive ) or removed from (negative ) the porewaters.At two of the sites, whose bottom water were oxygenated at sampling time, a production zone ( = 12 × 10−18 mol cm−3 s−1-71 × 10−18 mol cm−3 s−1) is inferred a few cm below the sediment-water interface, coincident with sharp porewater As and Fe peaks that indicate an intense coupled recycling of As and Fe. This process is confirmed by solid As and Fe maxima just below the sediment surface. In these two lakes a zone of As consumption ( = −5 × 10−18 mol cm−3 s−1 to −53 × 10−18 mol cm−3 s−1), attributed to the slow adsorption of As to authigenic Fe oxyhydroxides, occurs just above the production zone. A second-order rate constant of 0.12 ± 0.03 cm3 mol−1 s−1 is estimated for this adsorption reaction.Such features in the porewater and solid profiles were absent from the two other lakes that develop a seasonally anoxic hypolimnion. Thermodynamic calculations indicate that the porewaters of the four lakes, when sulfidic (i.e., ΣS−II ? 0.1 μM), were undersaturated with respect to all known solid As sulfides; the calculation also predicts the presence of AsV oxythioanions in the sulfidic waters, as suggested by a recent study. In the sulfidic waters, the removal of As ( = −1 × 10−18 mol cm−3 s−1 to −23 × 10−18 mol cm−3 s−1) consistently occurred when saturation, with respect to FeS(s), was reached and when AsV oxythioanions were predicted to be significant components of total dissolved As. This finding has potential implications for As transport in other anoxic waters and should be tested in a wider variety of natural environments.  相似文献   

15.
We report high-precision analyses of internally-normalised Ni isotope ratios in 12 bulk iron meteorites. Our measurements of 60Ni/61Ni, 62Ni/61Ni and 64Ni/61Ni normalised to 58Ni/61Ni and expressed in parts per ten thousand (?) relative to NIST SRM 986 as and , vary by 0.146, 0.228 and 0.687, respectively. The precision on a typical analysis is 0.03?, 0.05? and 0.08? for , and , respectively, which is comparable to our sample reproducibility. We show that this ‘mass-independent’ Ni isotope variability cannot be ascribed to interferences, inaccurate correction of instrumental or natural mass-dependent fractionation, fractionation controlled by nuclear field shift effects, nor the influence of cosmic ray spallation. These results thus document the presence of mass-independent Ni isotopic heterogeneity in bulk meteoritic samples, as previously proposed by Regelous et al. (2008) (EPSL 272, 330-338), but our new analyses are more precise and include determination of 64Ni. Intriguingly, we find that terrestrial materials do not yield homogenous internally-normalised Ni isotope compositions, which, as pointed out by Young et al. (2002) (GCA 66, 1095-1104), may be the expected result of using the exponential (kinetic) law and atomic masses to normalise all fractionation processes. The certified Ni isotope reference material NIST SRM 986 defines zero in this study, while appropriate ratios for the bulk silicate Earth are given by the peridotites JP-1 and DTS-2 and, relative to NIST SRM 986, yield deviations in , and of −0.006?, 0.036? and 0.119?, respectively. There is a strong positive correlation between and in iron meteorites analyses, with a slope of 3.03 ± 0.71. The variations of Ni isotope anomalies in iron meteorites are consistent with heterogeneous distribution of a nucleosynthetic component from a type Ia supernova into the proto-solar nebula.  相似文献   

16.
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17.
Lead speciation in many aqueous geochemical systems is dominated by carbonate complexation. However, direct observations of Pb2+ complexation by carbonate ions are few in number. This work represents the first investigation of the equilibrium over a range of ionic strength. Through spectrophotometric observations of formation at 25 °C in NaHCO3-NaClO4 solutions, formation constants of the form were determined between 0.001 and 5.0 molal ionic strength. Formation constant results were well represented by the equation:
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18.
The concentration and distribution of Pt and Au in a fluid-melt system has been investigated by reacting the metals with S-free, single-phase aqueous brines (20, 50, 70 wt% eq. NaCl) ± peraluminous melt at a confining pressure of 1.5 kbar and temperatures of 600 to 800 °C, trapping the fluid in synthetic fluid inclusions (quartz-hosted) and vesicles (silicate melt-hosted), and quantifying the metal content of the trapped fluid and glass by laser ablation ICP-MS. HCl concentration was buffered using the assemblage albite-andalusite-quartz and fO2 was buffered using the assemblage Ni-NiO. Over the range of experimental conditions, measured concentrations of Pt and Au in the brines (, ) are on on the order of 1-103 ppm. Concentrations of Pt and Au in the melt (, ) are ∼35-100 ppb and ∼400-1200 ppb, respectively. Nernst partition coefficients (, ) are on the order of 102-103 and vary as a function of (non-Henry’s Law behavior). Trapped fluids show a significant range of metal concentrations within populations of inclusions from single experiments (∼ 1 log unit variability for Au; ∼2-3 log unit variability for Pt). Variability in metal concentration within single inclusion groups is attributed to premature brine entrapment (prior to metal-fluid-melt equilibrium being reached); this allows us to make only minimum estimates of metal solubility using metal concentrations from primary inclusions. The data show two trends: (i) maximum and average values of and in inclusions decrease ∼2 orders of magnitude as fluid salinity () increases from ∼4 to 40 molal (20 to 70 wt % eq. NaCl) at a constant temperature; (ii) maximum and average values of increase approximately 1 order of magnitude for every 100°C increase temperature at a fixed . The observed behavior may be described by the general expression:
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19.
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20.
Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1-10), temperature, and high concentrations of fluoride (up to 50 mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50 °C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006-2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H+ and Al3+ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3-30% for more than 90% of samples at or above 10−6 molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F−, and major complexes (, AlF2+, and ) account for more than 95% of total fluoride. Occasionally, some complex species like , FeF2+, , MgF+ and may comprise 1-10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al.  相似文献   

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