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1.
Triplicate porewater lead concentration profiles were determined on six occasions in a Canadian Shield lake. Total Pb concentrations were also measured in a dated core obtained at the same site. This information, as well as an extensive dataset comprising ancillary geochemical measurements on porewaters and sediment and the population densities of benthic animals, is used in a one-dimensional transport-reaction diagenetic model to investigate the transport and mobilization of Pb in these sediments. Application of the model consistently indicates the presence of a zone of Pb production to the porewaters that lies above a zone of Pb consumption. The profiles of various porewater constituents and thermodynamic calculations indicate that Pb is mobilized in the zone of production by the reductive dissolution of iron oxyhydroxides, whereas it is removed in the zone of consumption by precipitation as a solid sulfide. Rate constants are estimated for reductive iron dissolution (kdFe(III) = 2.0 ± 0.5 × 10−1 cm3 mol−1 s−1), Pb adsorption on iron oxyhydroxides (kadsPb = 98 ± 55 cm3 mol−1 s−1), and Pb precipitation (kpptPb = 8 × 10−20 mol cm−3 s−1 to 16 ± 13 × 10−22 mol cm−3 s−1, depending on the solubility product assumed for the precipitation of PbS). According to model calculations, diagenetic processes, such as remobilization, molecular diffusion, bioturbation, and bioirrigation have a negligible influence on the solid phase Pb profile. In agreement with this finding, the present-day fluxes of dissolved Pb by diffusion (JDPb = −6.5 × 10−11 mol cm−2 yr−1), bioturbation (JBPb = −1.1 × 10−13 mol cm−2 yr−1), and bioirrigation (JIPb = −1.5 × 10−11 mol cm−2 yr−1) are small compared to the flux of Pb deposited with settling particles (JSPb = 5.3 × 10−9 mol cm−2 yr−1).  相似文献   

2.
The concentrations of Re, as well as those of several other geochemical variables, were measured in dated sediment cores and in porewater samples from four lacustrine basins in Eastern Canada: one, perennially oxic, located 40 km from Québec City and three, seasonally anoxic, located within 25 km of non-ferrous metal smelters. The drainage basins of these lakes are uninhabited and have not been affected by human activity or wildfires. All of the depth profiles of dissolved Re indicate: higher Re concentrations in the water overlying the sediment than in the porewater; diffusion of Re across the sediment-water interface; a progressive decrease in porewater Re concentrations to reach minimum values of ∼0.5 pM within a 10-cm sediment depth interval. Modeling of these Re porewater profiles with a one-dimensional transport-reaction equation indicates that Re is removed from porewater within this depth interval. Based on thermodynamic predictions of Re speciation and of saturation states and on comparison of these predictions with sulfide porewater profiles, we infer that Re is removed from porewater by precipitation of rheniite (ReS2(s)). The rate constant for the formation of ReS2(s) in sediments is estimated from the modeling exercise to be 0.51 ± 0.64 × 10−21 mol cm−3 s−1. Accumulation of sedimentary Re shows a strong authigenic component, as in anoxic marine sediments. Sharp increases in solid-phase Re during the last century are attributed to atmospheric deposition of anthropogenic Re deriving from coal burning and nearby smelter emissions.  相似文献   

3.
Self-diffusion coefficients for Si and O in Di58An42 liquid were measured from 1 to 4 GPa and temperatures from 1510 to 1764°C. Glass starting powders enriched in 18O and 28Si were mated to isotopically normal glass powders to form simple diffusion couples, and self-diffusion experiments were conducted in the piston cylinder device (1 and 2 GPa) and in the multianvil apparatus (3.5 and 4 GPa). Profiles of 18O/16O and 29,30Si/28Si were measured using secondary ion mass spectrometry. Self-diffusion coefficients for O (D(O)) are slightly greater than self-diffusion coefficients for Si (D(Si)) and are often the same within error. For example, D(O) = 4.20 ± 0.42 × 10−11 m2/s and D(Si) = 3.65 ± 0.37 × 10−11 m2/s at 1 GPa and 1662°C. Activation energies for self-diffusion are 215 ± 13 kJ/mol for O and 227 ± 13 kJ/mol for Si. Activation volumes for self-diffusion are −2.1 ± 0.4 cm3/mol and −2.3 ± 0.4 cm3/mol for O and Si, respectively. The similar self-diffusion coefficients for Si and O, similar activation energies, and small, negative activation volumes are consistent with Si and O transport by a cooperative diffusion mechanism, most likely involving the formation and disassociation of a high-coordinated intermediate species. The small absolute magnitudes of the activation volumes imply that Di58An42 liquid is close to a transition from negative to positive activation volume, and Adam-Gibbs theory suggests that this transition is linked to the existence of a critical fraction (∼0.6) of bridging oxygen.  相似文献   

4.
We investigate the sensitivity of U/Ca, Mg/Ca, and Sr/Ca to changes in seawater [CO32−] and temperature in calcite produced by the two planktonic foraminifera species, Orbulina universa and Globigerina bulloides, in laboratory culture experiments. Our results demonstrate that at constant temperature, U/Ca in O. universa decreases by 25 ± 7% per 100 μmol [CO32−] kg−1, as seawater [CO32−] increases from 110 to 470 μmol kg−1. Results from G. bulloides suggest a similar relationship, but U/Ca is consistently offset by ∼+40% at the same environmental [CO32−]. In O. universa, U/Ca is insensitive to temperature between 15°C and 25°C. Applying the O. universa relationship to three U/Ca records from a related species, Globigerinoides sacculifer, we estimate that Caribbean and tropical Atlantic [CO32−] was 110 ± 70 μmol kg−1 and 80 ± 40 μmol kg−1 higher, respectively, during the last glacial period relative to the Holocene. This result is consistent with estimates of the glacial-interglacial change in surface water [CO32−] based on both modeling and on boron isotope pH estimates. In settings where the addition of U by diagenetic processes is not a factor, down-core records of foraminiferal U/Ca have potential to provide information about changes in the ocean’s carbonate concentration.Below ambient pH (pH < 8.2), Mg/Ca decreased by 7 ± 5% (O. universa) to 16 ± 6% (G. bulloides) per 0.1 unit increase in pH. Above ambient pH, the change in Mg/Ca was not significant for either species. This result suggests that Mg/Ca-based paleotemperature estimates for the Quaternary, during which surface-ocean pH has been at or above modern levels, have not been biased by variations in surface-water pH. Sr/Ca increased linearly by 1.6 ± 0.4% per 0.1 unit increase in pH. Shell Mg/Ca increased exponentially with temperature in O. universa, where Mg/Ca = 0.85 exp (0.096*T), whereas the change in Sr/Ca with temperature was within the reproducibility of replicate measurements.  相似文献   

5.
The diffusion coefficients of Fe2+ and Mg in aluminous spinel at ∼20 kb, 950 to 1325°C, and at 30 kb, 1125°C have been determined via diffusion couple experiments and numerical modeling of the induced diffusion profiles. The oxygen fugacity, fO2, was constrained by graphite encapsulating materials. The retrieved self-diffusion coefficients of Fe2+ and Mg at ∼20 kb, 950 to 1325°C, fit well the Arrhenian relation, D = D0exp(−Q/RT), where Q is the activation energy, with D0(Fe) = 1.8 (±2.8) × 10−5, D0(Mg) = 1.9 (±1.4) × 10−5 cm2/s, Q(Fe) = 198 ± 19, and Q(Mg) = 202 ± 8 kJ/mol. Comparison with the data at 30 kb suggests an activation volume of ∼5 cm3/mol. From analysis of compositional zoning in natural olivine-spinel assemblages in ultramafic rocks, previous reports concluded that D(Fe-Mg) in spinel with Cr/(Cr + Al) ≤0.5 is ∼10 times that in olivine. The diffusion data in spinel and olivine have been applied to the problems of preservation of Mg isotopic inhomogeneity in spinel within the plagioclase-olivine inclusions in Allende meteorite and cooling rates of terrestrial ultramafic rocks.  相似文献   

6.
Weathering rind thicknesses were measured on ∼ 200 basaltic clasts collected from three regionally extensive alluvial fill terraces (Qt 1, Qt 2, and Qt 3) preserved along the Pacific coast of Costa Rica. Mass balance calculations suggest that conversion of unweathered basaltic core minerals (plagioclase and augite) to authigenic minerals in the porous rind (kaolinite, allophane, gibbsite, Fe oxyhydroxides) is iso-volumetric and Ti and Zr are relatively immobile. The hierarchy of cation mobility (Ca ≈ Na > K ≈ Mg > Si > Al > Fe ≈ P) is similar to other tropical weathering profiles and is indicative of differential rates of mineral weathering (anorthite > albite ≈ hypersthene > orthoclase ? apatite). Alteration profiles across the cm-thick rinds document dissolution of plagioclase and augite and the growth of kaolinite, with subsequent dissolution of kaolinite and precipitation of gibbsite as weathering rinds age. The rate of weathering rind advance is evaluated using a diffusion-limited model which predicts a parabolic rate law for weathering rind thickness, rr, as a function of time, t(rr =), and an interface-limited model which predicts a linear rate law for weathering rind thickness as a function of time (rr = kappt). In these rate laws, κ is a diffusion parameter and kapp is an apparent rate constant. The rate of advance is best fit by the interface model.Terrace exposures are confined to the lower reaches of streams draining the Pacific slope near the coast where the stream gradient is less than ∼3 m/km, and terrace deposition is influenced by eustatic sea level fluctuations. Geomorphological evidence is consistent with terrace deposition coincident with sea level maxima when the stream gradient would be lowest. Assigning the most weathered regionally extensive terrace Qt 1 (mean rind thickness 6.9 ± 0. 6cm) to oxygen isotope stage (OIS) 7 (ca. 240 ka), and assuming that at time = 0 rind thickness = 0, it is inferred that terrace Qt 2 (rr = 2.9 ± 0.1 cm) is coincident with stage 5e (ca. 125 ka) and that Qt 3 (rr = 0.9 ± 0.1 cm) is consistent with OIS 3 (ca. 37 ka). These assignments yield a value of kapp of 8.6 × 10−13 cm s−1 (R2 = 0.99). Only this value satisfies both the existing age controls and yields ages coincident with sea level maxima. Using this value, elemental weathering release fluxes across a weathering rind from Qt 2 range from 6.0 × 10−9 mol Si m−2 s−1 to 2.5 × 10−11 mol K m−2 s−1. The rate of rind advance for the Costa Rican terraces is 2.8 × 10−7 m yr−1. Basalt rind formation rates in lower temperature settings described in the literature are also consistent with interface-controlled weathering with an apparent activation energy of about 50 kJ mol−1. Rates of rind formation in Costa Rica are an order of magnitude slower than reported for global averages of soil formation rates.  相似文献   

7.
We employed the thin source technique to investigate tracer diffusion of Mg, Ca, Sr, and Ba in glasses and supercooled melts of albite (NaAlSi3O8) and jadeite (NaAlSi2O6) compositions. The experiments were conducted at 1 bar and at temperatures between 645 and 1025°C. Typical run durations ranged between 30 min and 35 days. The analysis of the diffusion profiles was performed with the electron microprobe. Diffusivities of Ca, Sr, and Ba were found to be independent of either duration t of the experiment or tracer concentration M, initially introduced into the sample. Mg exhibits a diffusivity depending on run time and concentration and tracer diffusivity is derived by extrapolation to M/√t = 0. Temperature dependence of the diffusivity D can be represented by an Arrhenius equation D = Do exp(−Ea/RT), yielding the following least-squares fit parameters (with D in m2/s and Ea in kJ/mol): DMg = 1.8 · 10−5 exp(−234 ± 20/RT), DCa = 3.5 · 10−6 exp(−159 ± 6/RT), DSr = 3.6 · 10−6 exp(−160 ± 6/RT), and DBa = 6.0 · 10−6 exp(−188 ± 12/RT) for albite; and DMg = 8.3 · 10−6 exp(−207 ± 18/RT), DCa = 3.8 · 10−6 exp(−153 ± 4/RT), DSr = 2.3 · 10−6 exp(−150 ± 4/RT), and DBa = 3.7 · 10−5 exp(−198 ± 4/RT) for jadeite composition. Ca and Sr diffusivities agree within error in both compositions and exhibit the fastest diffusivities, whereas Mg reveals the lowest diffusivity. The relationship between activation energy and radius shows a minimum at Ca and Sr for albite and jadeite compositions extending the relationship already observed elsewhere for alkalies. With increasing substitution of Si by (Na + Al), diffusivities increase, whereas activation energies decrease. Furthermore, a simple model modified from that of Anderson and Stuart (Anderson O. L. and Stuart D. A., “Calculation of activation energy of ionic conductivity in silica glasses by classical methods,” J. Am. Ceram. Soc.37, 573-580, 1954) is discussed for calculating the activation energies.  相似文献   

8.
We assess the role of fracturing and seismicity on fluid-driven mass transport of helium using groundwaters from the eastern Morongo Basin (EMB), California, USA. The EMB, located ∼200 km east of Los Angeles, lies within a tectonically active region known as the Eastern California Shear Zone that exhibits both strike-slip and extensional deformation. Helium concentrations from 27 groundwaters range from 0.97 to 253.7 × 10−7 cm3 STP g−1H2O, with corresponding 3He/4He ratios falling between 1.0 and 0.26 RA (where RA is the 3He/4He ratio of air). All groundwaters had helium isotope ratios significantly higher than the crustal production value of ∼0.02 RA. Dissolved helium concentrations were resolved into components associated with solubility equilibration, air entrainment, in situ production within the aquifer, and extraneous fluxes (both crustal and mantle derived). All samples contained a mantle helium-3 (3Hem) flux in the range of 4.5 to 1351 × 10−14 cm3 STP 3He cm−2 yr−1 and a crustal flux (J0) between 0.03 and 300 × 10−7 cm3 STP 4He cm−2 yr−1. Groundwaters from the eastern part of the basin contained significantly higher 3Hem and deep crustal helium-4 (4Hedc) concentrations than other areas, suggesting a localized source for these components. 4Hedc and 3Hem are strongly correlated, and are associated with faults in the basin. A shallow thermal anomaly in a >3,000 m deep graben in the eastern basin suggests upflow of fluids through active faults associated with extensional tectonics. Regional tectonics appears to drive large scale crustal fluid transport, whereas episodic hydrofracturing provides an effective mechanism for mantle-crust volatile transport identified by variability in the magnitude of degassing fluxes (3Hem and J0) across the basin.  相似文献   

9.
Experiments have been carried out to determine the temperature, oxygen fugacity (fO2) and compositional dependence of the tracer diffusion coefficient (D) of calcium in olivine. These data constrain the diffusion coefficient over the temperature range 900 to 1500°C for the three principal crystallographic axes. Well constrained linear relationships between the reciprocal of the absolute temperature and log(D) exist at any given oxygen fugacity. There is a strong dependence of the diffusion coefficient on oxygen fugacity with D ∝ fO2(1/3). This makes a knowledge of the T-fO2 path followed by geological samples a prerequisite for modelling Ca diffusion in olivine. The best fitting preexponential factor (Do) and activation energy (E) to the Arrhenius equation log (D) = log [Do exp(−E/RT)] + 0.31Δ log fO2 for Ca diffusion in olivine at a given oxygen fugacity (fO2*) are given by:diffusion along [100]: log [Do (m2/s)] = −10.78 ± 0.43; E = 193 ± 11 kJ/moldiffusion along [010]: log [Do (m2/s)] = −10.46 ± 0.37; E = 201 ± 10 kJ/moldiffusion along [001]: log [Do (m2/s)] = −10.02 ± 0.29; E = 207 ± 8 kJ/molwhere Δ log fO2 = log[fO2*] − log[10−12] with fO2* in units of bars. There is no measurable compositional dependence of the diffusion coefficient between Fo83 and Fo92. Diffusion in Fo100 has a much higher activation energy than in Fe-bearing olivine and has a weaker fO2 dependence.  相似文献   

10.
Sediment macropores (with effective diameters larger than 100 μm) comprise 11% of the bulk sediment volume in a tidal freshwater wetland vegetated withPeltandra virginica. In order to determine effects of macroporous sediment structure on solute transport, we conducted a solute tracer experiment in the sediment. The effective transport volume (θeff, the volume of sediment through which solute was transported normalized to sediment bulk volume) was 0.15 cm3 cm?3, which is considerably smaller than the total pore space that is potentially available for transport (porosity of sediment is 0.63 cm3 cm?3). A mean transport time of 13 d was required to flush preferential flow paths inPeltandra hummocks; hydrologic turnover of the volumetrically dominant matrix pores (0.53 cm3 cm?3) was apparently much slower. Based on porewater sampler design and hydrological principles, we suggest that N2-purged tension solution samplers and diffusion equilibrators preferentially sample porewater from macropore and matrix domains, respectively. Dissolved ammonium and orthophosphate concentrations were three-fold higher in matrix pores compared to macropores, which is consistent with our finding that more rapid hydrological flushing occurred in macropores compared to matrix pores. Further evaluation of porewater sampler designs in macroporous sediment is needed to improve studies of hydrologic transport and biogeochemical cycling in wetlands.  相似文献   

11.
The thermochemistry of anhydrous sulfates (anglesite, anhydrite, arcanite, barite, celestine) was investigated by high-temperature oxide melt calorimetry and differential scanning calorimetry. Complete retention and uniform speciation of sulfur in the solvent was documented by (a) chemical analyses of the solvent (3Na2O · 4MoO3) with dissolved sulfates, (b) Fourier transform infrared spectroscopy confirming the absence of sulfur species in the gases above the solvent, and (c) consistency of experimental determination of the enthalpy of drop solution of SO3 in the solvent. Thus, the principal conclusion of this study is that high-temperature oxide melt calorimetry with 3Na2O · 4MoO3 solvent is a valid technique for measurement of enthalpies of formation of anhydrous sulfates. Enthalpies of formation (in kJ/mol) from the elements (ΔHfo) were determined for synthetic anhydrite (CaSO4) (−1433.8 ± 3.2), celestine (SrSO4) (−1452.1 ± 3.3), anglesite (PbSO4) (−909.9 ± 3.4), and two natural barite (BaSO4) samples (−1464.2 ± 3.7, −1464.9 ± 3.7). The heat capacity of anhydrite, barite, and celestine was measured between 245 and 1100 K, with low- and high-temperature Netzsch (DSC-404) differential scanning calorimeters. The results for each sample were fitted to a Haas-Fisher polynomial of the form Cp(245 K < T < 1100 K) = a + bT + cT−2 + dT−0.5 + eT2. The coefficients of the equation are as follows: for anhydrite a = 409.7, b = −1.764 × 10−1, c = 2.672 × 106, d = −5.130 × 103, e = 8.460 × 10−5; for barite, a = 230.5, b = −0.7395 × 10−1, c = −1.170 × 106, d = −1.587 × 103, e = 4.784 × 10−5; and for celestine, a = 82.1, b = 0.8831 × 10−1, c = −1.213 × 106, d = 0.1890 × 103, e = −1.449 × 10−5. The 95% confidence interval of the measured Cp varies from 1 to 2% of the measured value at low temperature up to 2 to 5% at high temperature. The measured thermochemical data improve or augment the thermodynamic database for anhydrous sulfates and highlight the remaining discrepancies.  相似文献   

12.
Bulk Cd adsorption isotherm experiments, thermodynamic equilibrium modeling, and Cd K edge EXAFS were used to constrain the mechanisms of proton and Cd adsorption to bacterial cells of the commonly occurring Gram-positive and Gram-negative bacteria, Bacillus subtilis and Shewanella oneidensis, respectively. Potentiometric titrations were used to characterize the functional group reactivity of the S. oneidensis cells, and we model the titration data using the same type of non-electrostatic surface complexation approach as was applied to titrations of B. subtilis suspensions by Fein et al. (2005). Similar to the results for B. subtilis, the S. oneidensis cells exhibit buffering behavior from approximately pH 3-9 that requires the presence of four distinct sites, with pKa values of 3.3 ± 0.2, 4.8 ± 0.2, 6.7 ± 0.4, and 9.4 ± 0.5, and site concentrations of 8.9(±2.6) × 10−5, 1.3(±0.2) × 10−4, 5.9(±3.3) × 10−5, and 1.1(±0.6) × 10−4 moles/g bacteria (wet mass), respectively. The bulk Cd isotherm adsorption data for both species, conducted at pH 5.9 as a function of Cd concentration at a fixed biomass concentration, were best modeled by reactions with a Cd:site stoichiometry of 1:1. EXAFS data were collected for both bacterial species as a function of Cd concentration at pH 5.9 and 10 g/L bacteria. The EXAFS results show that the same types of binding sites are responsible for Cd sorption to both bacterial species at all Cd loadings tested (1-200 ppm). Carboxyl sites are responsible for the binding at intermediate Cd loadings. Phosphoryl ligands are more important than carboxyl ligands for Cd binding at high Cd loadings. For the lowest Cd loadings studied here, a sulfhydryl site was found to dominate the bound Cd budgets for both species, in addition to the carboxyl and phosphoryl sites that dominate the higher loadings. The EXAFS results suggest that both Gram-positive and Gram-negative bacterial cell walls have a low concentration of very high-affinity sulfhydryl sites which become masked by the more abundant carboxyl and phosphoryl sites at higher metal:bacteria ratios. This study demonstrates that metal loading plays a vital role in determining the important metal-binding reactions that occur on bacterial cell walls, and that high affinity, low-density sites can be revealed by spectroscopy of biomass samples. Such sites may control the fate and transport of metals in realistic geologic settings, where metal concentrations are low.  相似文献   

13.
The distribution and speciation of mercury (Hg) in the water column, the inputs (wet deposition and tributaries) and the outputs (atmospheric evasion and outlet) of an artificial partially anoxic tropical lake (Petit-Saut reservoir, French Guiana) were investigated on a seasonal basis in order to appraise the cycling and transformations of this metal. The total mercury (HgT) concentrations in the oxygenated epilimnetic waters averaged 5 ± 3 pmol L−1 in the unfiltered samples (HgTUNF) and 4 ± 2 pmol L−1 in the dissolved (HgTD) phase (<0.45 μm). On average, the monomethylmercury (MMHg) constituted 8%, 40% and 18% of the HgT in the dissolved phase, the particulate suspended matter and in the unfiltered samples, respectively. Covariant elevated concentrations of particulate MMHg and chlorophyll a in the epilimnion suggest that phytoplankton is an active component for the MMHg transfer in the lake. In the anoxic hypolimnion the HgTUNF averages 13 ± 6 pmol L−1 and the HgTD 8 ± 4 pmol L−1. The averages of MMHgP and MMHgD in hypolimnetic waters were two and three times the corresponding values of the epilimnion, 170 ± 90 pmol g−1 and 0.9 ± 0.5 pmol L−1, respectively. In the long dry and wet seasons, at the flooded forest and upstream dam sampling stations, the vertical profiles of MMHgD concentrations accounted for two distinct maxima: one just below the oxycline and the other near the benthic interface. Direct wet atmospheric deposition accounted for 14 moles yr−1 HgTUNF, with 0.7 moles yr−1 as MMHgUNF, while circa 76 moles yr−1 of HgTUNF, with 4.7 moles yr−1 as MMHgUNF, coming from tributaries. Circa 78 moles (∼17% as MMHg) are annually exported through the dam, while 23 moles yr−1 of Hg0 evolve in the atmosphere. A mass balance calculation suggests that the endogenic production of MMHgUNF attained 8.1 moles yr−1, corresponding to a methylation rate of 0.06% d−1. As a result, the Petit-Saut reservoir is a large man-made reactor that has extensively altered mercury speciation in favor of methylated species.  相似文献   

14.
Aqueous cadmium uptake by calcite: a stirred flow-through reactor study   总被引：1，自引：0，他引：1  
Uptake of cadmium ions from solution by a natural Mg-containing calcite was investigated in stirred flow-through reactor experiments. Input NaCl solutions were pre-equilibrated with calcite (pH 8.0) or not (pH 6.0), prior to being spiked with CdCl2. For water residence times in the reactor less than 0.5 h, irreversible uptake of Cd by diffusion into the bulk crystal had a minor effect on the measured cadmium breakthrough curves, hence allowing us to quantify “fast” Cd2+ adsorption. At equal aqueous activities of Cd2+, adsorption was systematically lower for the pre-equilibrated input solutions. The effect of variable solution composition on Cd2+ adsorption was reproduced by a Ca2+-Cd2+ cation exchange model and by a surface complexation model for the calcite-aqueous solution interface. For the range of experimental conditions tested, the latter model predicted binding of aqueous Ca2+ and Cd2+ to the same population of carbonate surface sites. Under these circumstances, both adsorption models were equivalent. Desorption released 80 to 100% of sorbed cadmium, confirming that fast uptake of Cd2+ was mainly due to binding at surface sites. Slow, irreversible cadmium uptake by the solid phase was measured in flow-through reactor experiments with water residence times exceeding 0.7 h. The process exhibited first-order kinetics with respect to the concentration of adsorbed Cd2+, with a linear rate constant at 25°C of 0.03 h−1. Assuming that diffusion into the calcite lattice was the mechanism of slow uptake, a Cd2+ solid-state diffusion coefficient of 8.5×10−21 cm2 s−1 was calculated. Adsorbed Cd2+ had a pronounced effect on the dissolution kinetics of calcite. At maximum Cd2+ surface coverage (∼10−5 mol m−2), the calcite dissolution rate was 75% slower than measured under initially cadmium-free conditions. Upon desorption of cadmium, the dissolution rate increased again but remained below its initial value. Thus, the calcite surface structure and reactivity retained a memory of the adsorbed Cd2+ cations after their removal.  相似文献   

15.
The solubility of gold has been measured in aqueous solutions at temperatures between 300 and 600°C and pressures from 500 to 1500 bar to determine the stability and stoichiometry of the hydroxy complexes of gold(I) in hydrothermal solutions. The experiments were carried out using a flow-through autoclave system. The solubilities, measured as total dissolved gold, were in the range 1.2 × 10−8 to 2.0 × 10−6 mol kg−1 (0.002 to 0.40 mg kg−1), in solutions of total dissolved sodium between 0.0 and 0.5 mol kg−1, and total dissolved hydrogen between 4.0 × 10−6 and 4.0 × 10−4 mol kg−1. At constant hydrogen molality, the solubility of gold increases with increasing temperature and decreases with increasing pressure. The solubilities were found to be independent of pH but increased with decreasing hydrogen molality at constant temperature and pressure. Consequently, gold dissolves in aqueous solutions of acidic to alkaline pH according to the reactionAu(s)+H2O(l)=AuOH(aq)+0.5H2(g) Ks,1The solubility constant, logKs,1, increases with increasing temperature from a minimum of −8.76 (±0.18) at 300°C and 500 bar to a maximum of −7.50 (±0.11) at 500°C and 1500 bar and decreases to −7.61 (±0.08) at 600°C and 1500 bar. From the equilibrium solubility constant and the redox potential of gold, the formation constant to form AuOH(aq) was calculated. At 25°C the complex formation is characterised by an exothermic enthalpy and a positive entropy. With increasing temperature and decreasing pressure, the formation reaction becomes endothermic and is accompanied by a large positive entropy, indicating a greater electrostatic interaction between Au+ and OH−.  相似文献   

16.
Studies of hydrothermal circulation within partly buried basement on the eastern flank of the Juan de Fuca Ridge (JFR) have shown that ridge-flank geochemical fluxes are potentially important for the global budgets of some elements. There are major uncertainties in these flux calculations, however, because the composition of these basement fluids is strongly dependent on temperature and because they may be modified by interaction with the overlying terrigenous sediments, either by diffusive exchange with basement or during upwelling to the seafloor. To better understand the nature and temperature control of basalt-fluid and sediment-fluid reactions at the JFR flank, we have conducted laboratory experiments between 51 and 350°C and at 400 bars pressure. K, Rb, and Si are leached from basalt between 150 and 351°C, and Sr and U are taken up. The direction of exchange of Li and Ca with basalt varies with temperature. Li and Sr are removed from fluid at 150°C, but isotope studies show that there is simultaneous release of both elements from basalt, indicating that uptake is controlled by the formation of secondary minerals. Moreover, our experiments confirm that Sr isotope exchange with oceanic crust occurs at moderate temperature and is not confined to high-temperature axial hydrothermal systems. Our data and field data from the JDR flank indicate that uptake of U into basalt at moderate temperature could remove between 9.9 and 15 × 106 mol U yr−1 from the oceans. This is higher than a recent estimate based on measurements of U in altered ocean crust (5.7 ± 3.3 × 106 mol yr−1), which concords with arguments that the Δelement/heat ratios of JDR flank fluids are too large to be representative of average global flank fluids. K, Ca, Sr, Ba, Li, Si, and B are leached from terrigenous sediments between 51 and 350°C, and U is taken up. Cs and Rb are removed from the fluid below 100°C and leached from the sediment at higher temperature. Sr isotope data show that Sr is preferentially mobilised from volcanic components within terrigenous sediments, which may lead to an overestimation of the ridge-flank Sr isotope flux at the JDR if there is exchange of sediment pore fluids with basement.  相似文献   

17.
A mass balance has been calculated for the elements Li, B, and Sr in the Gulf of Papua from sampling undertaken during 1993 to 1999. Parameters measured included Fly, Kikori, and Purari River inputs of dissolved and particulate phases, removal flux to sediment traps at the base of the continental shelf slope, and century-scale accumulation rates in shelf and slope sediments (derived from excess 210Pb profiles in sediment cores). About 91% of river input Li was in particulate form, and there was conservative behavior of dissolved Li in the salinity gradient of the estuaries. Li accumulation rate in inner-shelf sediments was slightly less than river inputs, suggesting that more than 90% of Li river inputs were trapped in rapid aluminosilicate mud accumulation zones of the inner shelf (<50-m depth). Li removal rate to sediment traps at the base of the slope at ∼1000-m water depth was an order of magnitude smaller than the inner-shelf sedimentation. Export of Li to deep water Coral Sea was estimated to be 1.2 × 108 mol yr−1, and this amount is equivalent to the riverine dissolved Li annual supply rate. About 66% of river input of B was in the particulate phase, and low dissolved B concentrations in freshwater were conservatively mixed with higher concentrations of B in seawater across the salinity gradient. Removal of B to inner-shelf sediments was about 83% of the total river input, indicating a small export of B (1.2 × 108 mol yr−1) to the Coral Sea. About half of the dissolved B input from rivers is sorbed to particles and trapped in inner-shelf sediments. Only 24% of river input of Sr was in particulate form, and low freshwater concentrations of dissolved Sr were conservatively mixed with higher concentrations of Sr in seawater across the salinity gradient. Only 20% of total river inputs of Sr were buried in shelf sediments, and there was a large export (7.3 × 108 mol yr−1) of Sr off the shelf to the Coral Sea. A sediment core from a rapidly accumulating mud deposition zone of the inner shelf shows twofold sympathetic variations in Li, B, and Sr/Ca supply rates over 200- to 1000-yr time intervals.  相似文献   

18.
Mineralization of organic matter and the subsequent dissolution of calcite were simulated for surface sediments of the upper continental slope off Gabon by using microsensors to measure O2, pH, pCO2 and Ca2+ (in situ), pore-water concentration profiles of NO3−, NH4+, Fe2+, and Mn2+ and SO42− (ex situ), as well as sulfate reduction rates derived from incubation experiments. The transport and reaction model CoTReM was used to simulate the degradation of organic matter by O2, NO3−, Fe(OH)3 and SO42−, reoxidation reactions involving Fe2+ and Mn2+, and precipitation of FeS. Model application revealed an overall rate of organic matter mineralization amounting to 50 μmol C cm−2 yr−1, of which 77% were due to O2, 17% to NO3− and 3% to Fe(OH)3 and 3% to SO42−. The best fit for the pH profile was achieved by adapting three different dissolution rate constants of calcite ranging between 0.01 and 0.5% d−1 and accounting for different calcite phases in the sediment. A reaction order of 4.5 was assumed in the kinetic rate law. A CaCO3 flux to the sediment was estimated to occur at a rate of 42 g m−2 yr−1 in the area of equatorial upwelling. The model predicts a redissolution flux of calcite amounting to 36 g m−2 yr−1, thus indicating that ∼90% of the calcite flux to the sediment is redissolved.  相似文献   

19.
Sediment and groundwater profiles were compared in two villages of Bangladesh to understand the geochemical and hydrogeological factors that regulate dissolved As concentrations in groundwater. In both villages, fine-grained sediment layers separate shallow aquifers (< 28 m) high in As from deeper aquifers (40-90 m) containing < 10 μg/L As. In one village (Dari), radiocarbon dating indicates deposition of the deeper aquifer sediments > 50 ka ago and a groundwater age of thousands of years. In the other village (Bay), the sediment is < 20 ka old down to 90 m and the deeper aquifer groundwater is younger, on the order of hundreds of years. The shallow aquifers in both villages that are high in As contain bomb-3H and bomb-14C, indicating recent recharge. The major and minor ion compositions of the shallow and deeper aquifers also differ significantly. Deeper aquifer water is of the Na+-HCO3- type, with relatively little dissolved NH4+ (76 ± 192 μmol/L), Fe (27 ± 43 μmol/L) and Mn (3 ± 2 μmol/L). In contrast, shallow aquifer water is of the Ca2+-Mg2+-HCO3- type, with elevated concentrations of dissolved NH4+ (306 ± 355 μmol/L), Fe (191 ± 73 μmol/L), and Mn (27 ± 43 μmol/L). In both villages, the quantity of As extractable from deeper aquifer sands with a 1 mol/L phosphate solution (0.2 ± 0.3 mg/kg, n = 12; 0.1 ± 0.1 mg/kg, n = 5) is 1 order of magnitude lower than P-extractable As from shallow deposits (1.7 ± 1.2 mg/kg, n = 9; 1.4 ± 2.0 mg/kg, n = 11). The differences suggest that the concentration of P-extractable As in the sediment is a factor controlling the concentration of As in groundwater. Low P-extractable As levels are observed in both deeper aquifers that are low in As, even though there is a large difference in the time of deposition of these aquifers in the two villages. The geochemical data and hydrographs presented in this study suggest that both Holocene and Pleistocene deeper aquifers that are low in As should be a viable source of drinking water as long as withdrawals do not exceed recharge rates of ∼1 cm/yr.  相似文献   

20.
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   

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