首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 265 毫秒
1.
Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)aq and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in 56Fe/54Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ56FeFe(OH)3-Fe(II)aq fractionation factor of +3.0‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)aq and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)aq by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)aq oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)aq and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of biological and abiological Fe(II) oxidation.  相似文献   

2.
We use a reactive diffusion model to investigate what happens to CO2 injected into a subsurface sandstone reservoir capped by a chlorite- and illite-containing shale seal. The calculations simulate reaction and transport of supercritical (SC) CO2 at 348.15 K and 30 MPa up to 20,000 a. Given the low shale porosity (5%), chemical reactions mostly occurred in the sandstone for the first 2000 a with some precipitation at the ss/sh interface. From 2000 to 4000 a, ankerite, dolomite and illite began replacing Mg–Fe chlorite at the sandstone/shale interface. Transformation of chlorite to ankerite is the dominant reaction occluding the shale porosity in most simulations: from 4000 to 7500 a, this carbonation seals the reservoir and terminates reaction. Overall, the carbonates (calcite, ankerite, dolomite), chlorite and goethite all remain close to local chemical equilibrium with brine. Quartz is almost inert from the point of its dissolution/precipitation. However, the rate of quartz reaction controls the long-term decline in aqueous silica activity and its evolution toward equilibrium. The reactions of feldspars and clays depend strongly on their reaction rate constants (microcline is closer to local equilibrium than albite). The timing of porosity occlusion mostly therefore depends on the kinetic constants of kaolinite and illite. For example, an increase in the kaolinite kinetic constant by 0.25 logarithmic units hastened porosity closure by 4300 a. The earliest simulated closure of porosity occurred at approximately 108 a for simulations designed as sensitivity tests for the rate constants.These simulations also emphasize that the rate of CO2 immobilization as aqueous bicarbonate (solubility trapping) or as carbonate minerals (mineral trapping) in sandstone reservoirs depends upon reaction kinetics – but the relative fraction of each trapped CO2 species only depends upon the initial chemical composition of the host sandstone. For example, at the point of porosity occlusion the fraction of bicarbonate remaining in solution depends upon the initial Na and K content in the host rock but the fraction of carbonate mineralization depends only on the Ca, Mg, Fe content. Since ankerite is the dominant mineral that occludes porosity, the dissolved concentration of ferrous iron is also an important parameter. Future efforts should focus on cross-comparisons and ground-truthing of simulations made for standard case studies as well as laboratory measurements of the reactivities of clay minerals.  相似文献   

3.
Iron transformations in a calcium carbonate rich fresh-water sediment were studied by analyzing the relevant constituents of both interstitial water and solid matter. Analysis of interstitial water shows that the observed redox sequence NO−3/NH+4, MnO2/Mn(II), FeOOH/Fe(II), SO2−4/S(−II) is roughly in agreement with that predicted by the Gibbs Free Energy for the corresponding reactions. In contrast to marine sediments, these redox transitions occur in the uppermost sediments, i.e., at depths of 0–4 cm.

Deeper in the sedimentary sequence, the depth profile for dissolved iron exhibits a steady non-linear increase up to 400 μmol dm−3. In this anoxic zone, according to thermodynamic predictions, iron (II)-minerals such as iron sulfide, siderite, and vivianite should precipitate while Fe(III) oxides should be completely dissolved. However, microscopic analysis showed that Fe(III) oxides were present throughout the studied sediment. Furthermore, scanning electron microscope/energy dispersive spectroscopy analysis suggests the presence of iron sulfide could be verified but not that of siderite or vivianite. These observations indicate kinetic control of iron transformations.

We have investigated the importance of kinetic control of iron distribution in anoxic sediments using a diagenetic model for dissolved iron(II). A rough estimate of time scales for dissolution and precipitation rates was made by imposing limiting boundary conditions. Using the calculated rate constant, we established that more than 1000 years would be required for the complete dissolution of Fe(III) oxides, which is agreement with our observations and experimental data from the literature. Calculated precipitation rates of Fe(II) for a given mineral phase such as siderite yield a maximum value of 3 μg(FeCO3) g−1(dry sediment) yr−1. Such low rates would explain the absence of siderite and vivianite.

Finally, it can be inferred from the MnT/FeT ratio in the sediments that this ratio depends on the redox conditions of the sediment-water interface at the time of deposition. Thus, this ratio can be used as “paleo-redox indicator” in lacustrine sediments.  相似文献   


4.
In order to evaluate the complex interplay between dissolution and precipitation reaction kinetics, we examined the hypothesis of partial equilibria between secondary mineral products and aqueous solutions in feldspar-water systems. Speciation and solubility geochemical modeling was used to compute the saturation indices (SI) for product minerals in batch feldspar dissolution experiments at elevated temperatures and pressures and to trace the reaction paths on activity-activity diagrams. The modeling results demonstrated: (1) the experimental aqueous solutions were supersaturated with respect to product minerals for almost the entire duration of the experiments; (2) the aqueous solution chemistry did not evolve along the phase boundaries but crossed the phase boundaries at oblique angles; and (3) the earlier precipitated product minerals did not dissolve but continued to precipitate even after the solution chemistry had evolved into the stability fields of minerals lower in the paragenesis sequence. These three lines of evidence signify that product mineral precipitation is a slow kinetic process and partial equilibria between aqueous solution and product minerals were not held. In contrast, the experimental evidences are consistent with the hypothesis of strong coupling of mineral dissolution/precipitation kinetics [e.g., Zhu C., Blum A. E. and Veblen D. R. (2004a) Feldspar dissolution rates and clay precipitation in the Navajo aquifer at Black Mesa, Arizona, USA. In Water-Rock Interaction (eds. R. B. Wanty and R. R. I. Seal). A.A. Balkema, Saratoga Springs, New York. pp. 895-899]. In all batch experiments examined, the time of congruent feldspar dissolution was short and supersaturation with respect to the product minerals was reached within a short period of time. The experimental system progressed from a dissolution driven regime to a precipitation limited regime in a short order. The results of this study suggest a complex feedback between dissolution and precipitation reaction kinetics, which needs to be considered in the interpretation of field based dissolution rates.  相似文献   

5.
Flow injection analysis was used to study the effect of a fulvic acid on the kinetics of iron(II) oxidation and iron colloid formation under conditions approximating fresh natural waters. While iron(II) oxidation in high-carbonate inorganic solutions is predicted well by a recently proposed homogeneous model, it overestimates the oxidation rate in low-carbonate solutions, possibly due to the formation of an intermediate iron(II) colloid or surface species. Results in fulvic acid solutions are consistent with the formation of an iron(II)-fulvic acid complex at both pH 6.0 and 8.0 which accelerates the overall oxidation rate relative to inorganic solutions. However, iron(III) complexation by fulvic acid greatly slows the formation of iron colloids, stabilizing dissolved iron(III). Decreased pH and increased ionic strength slow and decrease iron colloid formation. Evidence of a kinetic control on the distribution of iron(III) between organically complexed and colloidal forms is presented.  相似文献   

6.
Fe(III) complexed by organic ligands (Fe(III)L) is the primary form of dissolved Fe in marine and coastal environments. Superoxide, typically produced in biological and photochemical processes, is one of the reducing agents that contributes to transformation of Fe(III)L to bioavailable, free dissolved Fe(II) (Fe(II)′). In this work, the kinetics of superoxide-mediated Fe(II)′ formation from Fe(III)L in a simulated coastal water system were investigated and a comprehensive kinetic model was developed using citrate and fulvic acid as exemplar Fe-binding ligands. To simulate a coastal environment in laboratory experiments, Fe(III)L samples with various ligand/Fe ratios were incubated for 5 min to 1 week in seawater medium. At each ratio and incubation time, the rate of superoxide-mediated Fe(II)′ formation was determined in the presence of the strong Fe(II) binding ligand ferrozine by spectrophotometrically measuring the ferrous-ferrozine complex generated at a constant concentration of superoxide. The Fe(II)′ formation rate generally decreased with incubation time, as Fe(III)L gradually dissociated to form less reactive Fe(III) oxyhydroxide. However, when the ligand/Fe ratio was sufficiently high, the dissociation of Fe(III)L (and subsequent Fe precipitation) was suppressed and Fe(II)′ was formed at a higher rate. The rate of Fe(II)′ produced during the experiment was explained by the kinetic model. The model confirmed that both the ligand/Fe ratio and incubation time have a significant effect on the pathway via which Fe(II)′ is formed from Fe(III)-fulvic acid complexes.  相似文献   

7.
The kinetics of the formation and precipitation of nanocolloidal silica from geologically relevant aqueous solutions is investigated. Changes in monomeric (SiO2(mono)), nanocolloidal (SiO2(nano)) and precipitated silica (SiO2(ppt)) concentrations in aqueous solutions from pH 3 to 7, ionic strengths (IS) of 0.01 and 0.24 molal, and initial SiO2 concentrations of 20.8, 12.5 and 4.2 mmolal (reported in [Icopini, G.A., Brantley, S.L., Heaney, P.J., 2005. Kinetics of silica oligomerization and nanocolloid formation as a function of pH and ionic strength at 25 °C. Geochim. Cosmochim. Acta69(2), 293-303.]) were fit using two kinetic models. The first model, termed the concentration model, is taken from Icopini et al. (2005) and assumes that the rate of change of SiO2(mono) as a function of time has a fourth-order dependence on the concentration of SiO2(mono) in solution. The second model, termed the supersaturation model, incorporates the equilibrium concentration of amorphous silica and predicts that polymerization will be a function of the degree of silica supersaturation in solution with respect to amorphous silica. While both models generally predicted similar rate constants for a given set of experimental conditions, the supersaturation model described the long-term equilibrium behavior of the SiO2(mono) fraction more accurately, resulting in significantly better fits of the monomeric data. No difference was seen between the model fits of the nanocolloidal silica fraction. At lower pH values (3-4), a metastable equilibrium was observed between SiO2(mono) and SiO2(nano). This equilibrium SiO2(mono) concentration was found to be 6 mmolal, or three times the reported solubility of bulk amorphous silica under the experimental conditions studied and corresponds to the predicted solubility of amorphous silica colloids approximately 3 nm in diameter. Atomic force microscopy was used to determine the average size of the primary nanocolloidal particles to be ∼3 nm, which is in direct agreement with the solubility calculations. Larger aggregates of the primary nanocolloids were also observed to range in size from 30 to 40 nm. This work provides the first kinetic models describing the formation and evolution of nanocolloidal silica in environmentally relevant aqueous solutions. Results indicate that nanocolloidal silica is an important species at low pH and neutral pH at low ionic strengths and may play a more important role in geochemical cycles in natural aqueous systems than previously considered.  相似文献   

8.
The kinetics of Fe(III) precipitation in synthetic buffered waters have been investigated over the pH range 6.0-9.5 using a combination of visible spectrophotometry, 55Fe radiometry combined with ion-pair solvent extraction of chelated iron and numerical modeling. The rate of precipitation, which is first order with respect to both dissolved and total inorganic ferric species, varies by nearly two orders of magnitude with a maximum rate constant of 16 ± 1.5 × 106 M−1 s−1 at a pH of around 8.0. Our results support the existence of the dissolved neutral species, Fe(OH)30, and suggest that it is the dominant precursor in Fe(III) polymerization and subsequent precipitation at circumneutral pH. The intrinsic rate constant of precipitation of Fe(OH)30 was calculated to be allowing us to predict rates of Fe(III) precipitation in the pH range 6.0-9.5. The value of this rate constant, and the variation in the precipitation rate constant over the pH range considered, are consistent with a mechanism in which the kinetics of iron precipitation are controlled by rates of water exchange in dissolved iron hydrolysis species.  相似文献   

9.
We studied the effects of humic substances (HS) on the sorption of Fe(II) onto Al-oxide and clay sorbents at pH 7.5 with a combination of batch kinetic experiments and synchrotron Fe K-edge EXAFS analyses. Fe(II) sorption was monitored over the course of 4 months in anoxic clay and Al-oxide suspensions amended with variable HS types (humic acid, HA; or fulvic acid, FA) and levels (0, 1, and 4 wt%), and with differing Fe(II) and HS addition sequences (co-sorption and pre-coated experiments, where Fe(II) sorbate was added alongside and after HS addition, respectively). In the Al-oxide suspensions, the presence of HS slowed down the kinetics of Fe(II) sorption, but had limited, if any, effect on the equilibrium aqueous Fe(II) concentrations. EXAFS analyses revealed precipitation of Fe(II)–Al(III)-layered double hydroxide (LDH) phases as the main mode of Fe(II) sorption in both the HA-containing and HA-free systems. These results demonstrate that HS slow down Fe(II) precipitation in the Al-oxide suspensions, but do not affect the composition or stability of the secondary Fe(II)–Al(III)-LDH phases formed. Interference of HS with the precipitation of Fe(II)–Al(III)-LDH was attributed to the formation organo-Al complexes HS limiting the availability of Al for incorporation into secondary layered Fe(II)-hydroxides. In the clay systems, the presence of HA caused a change in the main Fe(II) sorption product from Fe(II)–Al(III)-LDH to a Fe(II)-phyllosilicate containing little structural Al. This was attributed to complexation of Al by HA, in combination with the presence of dissolved Si in the clay suspension enabling phyllosilicate precipitation. The change in Fe(II) precipitation mechanism did not affect the rate of Fe(II) sorption at the lower HA level, suggesting that the inhibition of Fe(II)–Al(III)-LDH formation in this system was countered by enhanced Fe(II)-phyllosilicate precipitation. Reduced rates of Fe(II) sorption at the higher HA level were attributed to surface masking or poisoning by HA of secondary Fe(II) mineral growth at or near the clay surface. Our results suggest that HS play an important role in controlling the kinetics and products of Fe(II) precipitation in reducing soils, with effects modulated by soil mineralogy, HS content, and HS properties. Further work is needed to assess the importance of layered Fe(II) hydroxides in natural reducing environments.  相似文献   

10.
The interaction of aqueous As(III) with magnetite during its precipitation from aqueous solution at neutral pH has been studied as a function of initial As/Fe ratio. Arsenite is sequestered via surface adsorption and surface precipitation reactions, which in turn influence the crystal growth of magnetite. Sorption samples were characterized using EXAFS spectroscopy at the As K-edge in combination with HRTEM observations, energy dispersive X-ray analysis at the nanoscale, electron energy loss spectroscopy at the Fe L3-edge, and XRD-Rietveld analyses of reaction products. Our results show that As(III) forms predominantly tridentate hexanuclear As(III)O3 complexes (3C), where the As(III)O3 pyramids occupy vacant tetrahedral sites on {1 1 1} surfaces of magnetite particles. This is the first time such a tridentate surface complex has been observed for arsenic. This complex, with a dominant As-Fe distance of 3.53 ± 0.02 Å, occurs in all samples examined except the one with the highest As/Fe ratio (0.33). In addition, at the two highest As/Fe ratios (0.133 and 0.333) arsenite tends to form mononuclear edge-sharing As(III)O3 species (2E) within a highly soluble amorphous As(III)-Fe(III,II)-containing precipitate. At the two lowest As/Fe ratios (0.007 and 0.033), our results indicate the presence of additional As(III) species with a dominant As-Fe distance of 3.30 ± 0.02 Å, for which a possible structural model is proposed. The tridentate 3C As(III)O3 complexes on the {1 1 1} magnetite surface, together with this additional As(III) species, dramatically lower the solubility of arsenite in the anoxic model systems studied. They may thus play an important role in lowering arsenite solubility in putative magnetite-based water treatment processes, as well as in natural iron-rich anoxic media, especially during the reductive dissolution-precipitation of iron minerals in anoxic environments.  相似文献   

11.
  相似文献   

12.
Siderite (FeCO3) is an important reduced phase iron mineral and end product of bacteria anaerobic respiration. This study addresses its dissolution behavior in the presence of the oxidant chromate, which is a common environmental contaminant. Macroscopic dissolution experiments combined with microscopic observations by atomic force microscopy show that at pH < 4.5 the dissolution rate with chromate is slower than that in control solution without chromate. Isolated deep dissolution pits and clustered shallow pits occur simultaneously with surface precipitation. The implication is that the surface precipitate inhibits further dissolution. For 5 < pH < 9.5, the slowest dissolution and the fastest precipitation rates are observed, both at edge steps and on terraces. For pH > 10, the dissolution rate in the presence of chromate exceeds that of the control, plausibly due to electron transfer facilitated by [Fe3+(OH)4]-. Dissolution and re-precipitation of round hillocks are observed. X-ray photoelectron spectroscopy indicates the presence of Cr(III) as well as reaction products in a hydroxide form. Based on the redox reaction mechanism, macroscopic dissolution behavior, and previous studies on the reaction products of Fe(II) with Cr(VI), we propose the formation of a low solubility nano-sized Cr(III)-Fe(III)-hydroxide as the surface precipitate. Results from this study provide a basis for understanding and quantifying the interactions between reduced-iron minerals and aqueous-phase oxidants.  相似文献   

13.
The first precipitate formed through the reaction between aqueous Fe(II) salts and dissolved sulphide at ambient temperatures and pH < 9, appears to be a highly disordered gel approaching the composition Fe(HS)2 on a water-free basis. After 0.4 s this precipitate loses sulphide and amorphous FeS begins to appear. The mackinawite structure begins to develop after several hours.

The rate of formation of the initial precipitate can be approximated by a pseudo first-order reaction, directly dependent on total sulphide concentration and with an apparent pseudo first-order rate constant of 48 ± 9 s−1. Dissolved Fe concentration does not appear to be rate limiting.

The estimated solubility of the initial phase is variable but consistently one to two orders of magnitude greater than the measured solubilities for amorphous FeS. In natural systems this may lead to variable Fe(II) solubilities in sulphidic environments. This initial material may play a more central role in iron sulphide reaction pathways than either mackinawite or amorphous FeS.  相似文献   


14.
This paper presents a hydrogeochemical modeling code HYDROS, which combines the multi-component transport model with equilibrium speciation module MINTEQA2. The processes of adsorption, aqueous speciation and mineral precipitation/dissolution are represented in the model. The numerical model uses a sequential iterative approach for solving the solute transport and the equilibrium geochemistry modules. Further the transport part is solved using an operator split approach wherein a finite volume method is used for solving the advective equations while a classical finite difference method is employed for solving the dispersive equations. The model performance is evaluated by comparing it with MINTOX for a literature problem. HYDROS is then applied to the case study of the transfer of transition metals with organic colloids in the swamp groundwater system of the experimental Nsimi watershed, representative of the humid tropical ecosystem of the South Cameroon Plateau. Field observations at the site swamp system suggest that the carbon is mainly transferred as organic colloids (i.e., dissolved organic carbon) produced by the slow biodegradation of the swamp organic matter. Using HYDROS, the behaviour of Al(III) and Fe(III) elements in the base flow system is simulated during inter rain events of a short rainy season (May–June 1996). The elemental time-series for Al, Fe, Cl, pH compare well with the simulation results. The colloids are found to have a strong impact on the mobilization and transfer of Al(III) and Fe(III), which are considered to have low mobility in weathering environment.  相似文献   

15.
Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42− and Cl− salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor αFe(III)aq-Fe(II)aq ∼ 1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (∼1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (∼1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9‰ (αFe(III)aq-Fe(II)aq ∼ 1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments revealed that 56Fe/54Fe ratios of Fe(III)aq were generally equal to or greater than those of Fe(III)ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record.  相似文献   

16.
The aqueous geochemistry of Zn, Cu, Cd, Fe, Mn and As is discussed within the context of an anaerobic treatment wetland in Butte, Montana. The water being treated had a circum-neutral pH with high concentrations of trace metals and sulfate. Reducing conditions in the wetland substrate promoted bacterial sulfate reduction (BSR) and precipitation of dissolved metal as sulfide minerals. ZnS was the most common sulfide phase found, and consisted of framboidal clusters of individual spheres with diameters in the submicron range. Some of the ZnS particles passed through the subsurface flow, anaerobic cells in suspended form. The concentration of "dissolved" trace metals (passing through a 0.45 μm filter) was monitored as a function of H2S concentration, and compared to predicted solubilities based on experimental studies of aqueous metal complexation with dissolved sulfide. Whereas the theoretical predictions produce "U-shaped" solubility curves as a function of H2S, the field data show a flat dependence of metal concentration on H2S. Observed metal concentrations for Zn, Cu and Cd were greater than the predicted values, particularly at low H2S concentration, whereas Mn and As were undersaturated with their respective metal sulfides. Results from this study show that water treatment facilities employing BSR have the potential to mobilize arsenic out of mineral substrates at levels that may exceed regulatory criteria. Dissolved iron was close to equilibrium saturation with amorphous FeS at the higher range of sulfide concentrations observed (>0.1 mmol H2S), but was more likely constrained by goethite at lower H2S levels. Inconsistencies between our field results and theoretical predictions may be due to several problems, including: (i) a lack of understanding of the form, valence, and thermodynamic stability of poorly crystalline metal sulfide precipitates; (ii) the possible influence of metal sulfide colloids imparting an erroneously high "dissolved" metal concentration; (iii) inaccurate or incomplete thermodynamic data for aqueous metal complexes at the conditions of the treatment facility; and (iv) difficulties in accurately measuring low concentrations of dissolved sulfide in the field.  相似文献   

17.
Equilibrium-kinetic model of water-rock interaction   总被引：1，自引：0，他引：1  
A computer model was developed for chemical interaction in water-rock systems. The model is based on the concept of partial equilibrium [1] and combines the calculation of chemical equilibria in multicomponent systems with accounting for the kinetics of the congruent dissolution of minerals as a function of pH (zeroth order kinetic reactions). The development of the process in time is simulated as a series of sequential partial equilibria, and the bulk chemical composition of the system is calculated at each time step from the chemical composition of aqueous solution at the beginning of the step and masses of minerals dissolved during time Δt. The dissolution rates of individual minerals are calculated at each time step for the given temperature, current pH value, and the degree of solution saturation with respect to minerals. Variations in the surface area of minerals due to precipitation and dissolution are accounted for. Model application is exemplified by the calculation of chemical equilibria in the water-granite system. The model may be useful for understanding the character of low-temperature interactions in water-rock systems under stagnant conditions, in particular, the multistage development of groundwater chemistry, interaction of liquid radioactive waste injected into underground repositories, etc.  相似文献   

18.
Microbial dissimilatory iron reduction (DIR) has been identified as a mechanism for production of aqueous Fe(II) that has low 56Fe/54Fe ratios in modern and ancient suboxic environments that contain ferric oxides or hydroxides. These studies suggest that DIR could have played an important role in producing distinct Fe isotope compositions in Precambrian banded iron formations or other marine sedimentary rocks. However, the applicability of experimental studies of Fe isotope fractionation produced by DIR in geochemically simple systems to ancient marine environments remains unclear. Here we report Fe isotope fractionations produced during dissimilatory microbial reduction of hematite by Geobacter sulfurreducens in the presence and absence of dissolved Si at neutral and alkaline pH. Hematite reduction was significantly decreased by Si at alkaline (but not neutral) pH, presumably due to Si polymerization at the hematite surface. The presence of Si altered Fe isotope fractionation factors between aqueous Fe(II) or sorbed Fe(II) and reactive Fe(III), reflecting changes in bonding environment of the reactive Fe(III) component at the oxide surface. Despite these changes in isotopic fractionations, our results demonstrate that microbial Fe(III) oxide reduction produces Fe(II) with negative δ56Fe values under conditions of variable pH and dissolved Si, similar to the large inventory of negative δ56Fe in Neoarchean and Paleoproterozoic age marine sedimentary rocks.  相似文献   

19.
碳羟磷灰石（CHap）在含镉溶液和空白溶液中溶解特性的对比实验结果表明：介质pH值是影响CHap溶解的重要因素,强酸务件下,溶解度最大;溶钙量和溶磷量的摩尔比均不是1、67;溶解初期阶段反应速度快,动力学过程复杂,后期阶段符合一级反应动力学特征,说明CHap溶解机理符合氢催化模型、非化学计量比溶解模型、多核模型,在含镉溶液中溶解时,还包括离子交换模型,即溶液中的镉离子与CHap中的钙离子发生交换作用。从溶解特性的角度推测：CHap除镉过程中存在有离子交换作用机理。  相似文献   

20.
We use reactive transport modeling to better understand the kinetics of chemical weathering in the Cretaceous Middendorf aquifer of South Carolina, USA, and the relationship of this process to subsurface microbial activity. We constructed a model accounting for the kinetics of mineral dissolution and precipitation, ion exchange, and the CO2 and bicarbonate produced by iron reducing and sulfate reducing bacteria in the aquifer. We then fit the model to observed trends in the chemical composition of groundwater along the aquifer by adjusting the rate constants for the kinetic reactions considered. The modeling portrays weathering in the Middendorf as a slow process by which groundwater gradually reacts toward equilibrium with minerals in the aquifer. The rate constants predicted are 6 to 7 orders of magnitude smaller than measured in laboratory experiments and 3 to 4 orders of magnitude less than those inferred from weathering rates in soils. The rate constants are smaller even than expected by projecting observed trends with the duration of weathering to the geologic age of the Middendorf. Weathering is driven largely by biological activity: about half the acid consumed is CO2 derived from the recharge area, and about half is supplied by iron reducing bacteria in the aquifer; only about 1% of the acid is of atmospheric origin, from CO2 dissolved in rainwater.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号