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1.
Kinetics of arsenopyrite oxidative dissolution by oxygen   总被引：1，自引：0，他引：1  
We used a mixed flow reactor system to determine the rate and infer a mechanism for arsenopyrite (FeAsS) oxidation by dissolved oxygen (DO) at 25 °C and circumneutral pH. Results indicate that under circumneutral pH (6.3-6.7), the rate of arsenopyrite oxidation, 10−10.14±0.03 mol m−2 s−1, is essentially independent of DO over the geologically significant range of 0.3-17 mg L−1. Arsenic and sulfur are released from arsenopyrite in an approximate 1:1 molar ratio, suggesting that oxidative dissolution by oxygen under circumneutral pH is congruent. Slower rates of iron release from the reactor indicate that some of the iron is lost from the effluent by oxidation to Fe(III) which subsequently hydrolyzes and precipitates. Using the electrochemical cell model for understanding sulfide oxidation, our results suggest that the rate-determining step in arsenopyrite oxidation is the reduction of water at the anodic site rather than the transfer of electrons from the cathodic site to oxygen as has been suggested for other sulfide minerals such as pyrite.  相似文献   

2.
Passive treatment systems for mine drainage use no energy other than gravity, but they require greater area than active treatment systems. Researchers are considering “hybrid” systems that have passive and active components for increased efficiency, especially where space limitations render passive-only technology ineffective. Flow-through reactor field experiments were conducted at two large net-alkaline anthracite mine discharges in central Pennsylvania. Assuming an Fe removal rate of 20 g m−2 day−1 and Fe loading from field data, 3.6 × 103 and 3.0 × 104 m2 oxidation ponds would be required for the passive treatment of Site 21 and Packer 5 discharges, respectively. However, only a small area is available at each site. This paper demonstrates aeration to drive off CO2, increase pH, and increase Fe(II) oxidation rates, enabling treatment within a small area compared to passive treatment methods, and introduces a geochemical model to accurately predict these rates as well as semi-passive treatment system sizing parameters. Both net-alkaline discharges were suboxic with a pH of ≈5.7, Fe(II) concentration of ≈16 mg L−1, and low Mn and Al concentrations. Flow rates were ≈4000 L min−1 at Site 21 and 15,000 L min−1 at Packer 5. Three-h aeration experiments with flow rates scaled to a 14-L reactor resulted in pH increases from 5.7 to greater than 7, temperature increases from 12 to 22 °C, dissolved O2 increases to saturation with respect to the atmosphere, and Fe(II) concentration decreases from 16 to <0.05 mg L−1. A 17,000-L pilot-scale reactor at Site 21 produced similar results although aeration was not as complete as in the smaller reactor. Two non-aerated experiments at Site 21 with 13 and 25-h run times resulted in pH changes of ?0.2 and Fe(II) concentration decreases of less than 3 mg L−1.  相似文献   

3.
The oxygen isotope fractionation factor of dissolved oxygen gas has been measured during inorganic reduction by aqueous FeSO4 at 10−54 °C under neutral (pH 7) and acidic (pH 2) conditions, with Fe(II) concentrations ranging up to 0.67 mol L−1, in order to better understand the geochemical behavior of oxygen in ferrous iron-rich groundwater and acidic mine pit lakes. The rate of oxygen reduction increased with increasing temperature and increasing Fe(II) concentration, with the pseudo-first-order rate constant k ranging from 2.3 to 82.9 × 10−6 s−1 under neutral conditions and 2.1 to 37.4 × 10−7 s−1 under acidic conditions. The activation energy of oxygen reduction was 30.9 ± 6.6 kJ mol−1 and 49.7 ± 13.0 kJ mol−1 under neutral and acidic conditions, respectively. Oxygen isotope enrichment factors (ε) become smaller with increasing temperature, increasing ferrous iron concentration, and increasing reaction rate under acidic conditions, with ε values ranging from −4.5‰ to −11.6‰. Under neutral conditions, ε does not show any systematic trends vs. temperature or ferrous iron concentration, with ε values ranging from −7.3 to −10.3‰. Characterization of the oxygen isotope fractionation factor associated with O2 reduction by Fe(II) will have application to elucidating the process or processes responsible for oxygen consumption in environments such as groundwater and acidic mine pit lakes, where a number of possible processes (e.g. biological respiration, reduction by reduced species) may have taken place.  相似文献   

4.
Redox transformations of iron in the surface waters of the Gulf of Aqaba, Red Sea, were studied on recurrent cruises from September 2006 to May 2007. Fe(II) concentrations and oxidation kinetics were measured in situ using luminol chemiluminescence. High Fe(II) concentrations of 200-400 pM were recorded in the autumn, followed by low concentrations of 20-130 pM in the winter-spring. A distinct diurnal pattern in Fe(II) concentrations was observed in the autumn with maximum values coinciding with maximum solar irradiance. In situ and in vitro Fe(II) oxidation rates showed temporal and spatial variability that was accounted for by changes in water temperature and pH. Dissolved oxygen was found to be the dominant oxidant in all but one cruise. In situ photoreduction rates (deduced from oxidation rates) were linearly correlated with solar irradiance during the autumn, suggesting that the reducible iron pool was not exhausted even at the strongest irradiances and that it was kept constant throughout the season. Phytoplankton had no discernible influence on Fe(II) production, consumption, or oxidation kinetics. Given the fast oxidation and photoreduction rates of up to 180 pM min−1, the turn-over rates of iron were estimated at 10-30 per day. Such a dynamic Fe redox cycle probably influences the chemical reactivity and bioavailability of iron and may enhance the solubility of the abundant aerosol dust.  相似文献   

5.
The oxygenation kinetics of nanomolar concentrations of Fe(II) in aqueous solution have been studied in the absence and presence of millimolar concentrations of phosphate over the pH range 6.0-7.8. At each phosphate concentration investigated, the overall oxidation rate constant varied linearly with pH, and increased with increasing phosphate concentration. A model based on equilibrium speciation of Fe(II) was found to satisfactorily explain the results obtained. From this model, the rate constants for oxygenation of the Fe(II)-phosphate species FeH2PO4+, FeHPO4 and FePO4− have been determined for the first time. FePO4− was found to be the most kinetically reactive species at circumneutral pH with an estimated oxygenation rate constant of (2.2 ± 0.2) × 10 M−1 s−1. FeH2PO4+ and FeHPO4 were found to be less reactive with oxygen, with rate constants of (3.2 ± 2) × 10−2 M−1 s−1 and (1.2 ± 0.8) × 10−1 M−1 s−1, respectively.  相似文献   

6.
Methylmercury can accumulate in fish to concentrations unhealthy for humans and other predatory mammals. Most sources of mercury (Hg) emit inorganic species to the environment. Therefore, ecological harm occurs when inorganic Hg is converted to methylmercury. Sulfate- and iron-reducing bacteria (SRB and FeRB) methylate Hg, but the effects of processes involving oxidized and reduced forms of sulfur and iron on the reactivity of Hg, including the propensity of inorganic Hg to be methylated, are poorly understood. Under abiotic conditions, using a laboratory flow reactor, bisulfide (HS−) was added at 40 to 250 μM h−1 to 5 g L−1 goethite (α-FeOOH) suspensions to which Hg(II) was adsorbed (30-100 nmol m−2) at pH 7.5. Dissolved Hg initially decreased from 103 or 104 nM (depending on initial conditions) to 10−1 nM, during which the concentration of Hg(II) adsorbed to goethite decreased by 80% and metacinnabar (β-HgS(s)) formed, based on identification using Hg LIII-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The apparent coordination of oxygens surrounding Hg(II), measured with EXAFS spectroscopy, increased during one flow experiment, suggesting desorption of monodentate-bound Hg(II) while bidentate-bound Hg(II) persisted on the goethite surface. Further sulfidation increased dissolved Hg concentrations by one to two orders of magnitude (0.5 to 10 nM or 30 nM), suggesting that byproducts of bisulfide oxidation and Fe(III) reduction, primarily polysulfide and potentially Fe(II), enhanced the dissolution of β-HgS(s) and/or desorption of Hg(II). Rapid accumulation of Fe(II) in the solid phase (up to 40 μmol g−1) coincided with faster elevation of dissolved Hg concentrations. Fe(II) served as a proxy for elemental sulfur [S(0)], as S(0) was the dominant bisulfide oxidation product coupled to Fe(III) reduction, based on sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. In one experiment, dissolved Hg concentrations tracked those of all sulfide species [S(-II)]. These results suggest that S(-II) reacted with S(0) to form polysulfide, which then caused the dissolution of β-HgS(s). A secondary Fe-bearing phase resembling poorly formed green rust was observed in sulfidized solids with scanning electron microscopy, although there was no clear evidence that either surface-bound or mineralized Fe(II) strongly affected Hg speciation. Examination of interrelated processes involving S(-II) and Fe(III) revealed new modes of Hg solubilization previously not considered in Hg reactivity models.  相似文献   

7.
The pool of iron oxides, available in sediments for reductive dissolution, is usually estimated by wet chemical extraction methods. Such methods are basically empirically defined and calibrated against various synthetic iron oxides. However, in natural sediments, iron oxides are present as part of a complex mixture of iron oxides with variable crystallinity, clays and organics etc. Such a mixture is more accurately described by a reactive continuum covering a range from highly reactive iron oxides to non-reactive iron oxide. The reactivity of the pool of iron oxides in sediment can be determined by reductive dissolution in 10 mM ascorbic acid at pH 3. Parallel dissolution experiments in HCl at pH 3 reveal the release of Fe(II) by proton assisted dissolution. The difference in Fe(II)-release between the two experiments is attributed to reductive dissolution of iron oxides and can be quantified using the rate equation J/m0 = k′(m/m0)γ, where J is the overall rate of dissolution (mol s−1), m0 the initial amount of iron oxide, k′ a rate constant (s−1), m/m0 the proportion of undissolved mineral and γ a parameter describing the change in reaction rate over time. In the Rømø aquifer, Denmark, the reduction of iron oxides is an important electron accepting process for organic matter degradation and is reflected by the steep increase in aqueous Fe2+ over depth. Sediment from the Rømø aquifer was used for reductive dissolution experiments with ascorbic acid. The rate parameters describing the reactivity of iron oxides in the sediment are in the range k′ = 7·10−6 to 1·10−3 s−1 and γ = 1 to 2.4. These values are intermediate between a synthetic 2-line ferrihydrite and a goethite. The rate constant increases by two orders of magnitude over depth suggesting an increase in iron oxide reactivity with depth. This increase was not captured by traditional oxalate and dithionite extractions.  相似文献   

8.
In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers (∼2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive ΔV of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction.Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 Å, forming “altered biotite”. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 × 10−14 mol biotite m−2 s−1. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 μm resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone.Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 × 10−13 mol hornblende m−2 s−1: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O2 at the bedrock-saprolite interface.  相似文献   

9.
The subsurface behaviour of 99Tc, a contaminant resulting from nuclear fuels reprocessing, is dependent on its valence (e.g., IV or VII). Abiotic reduction of soluble Tc(VII) by Fe(II)(aq) in pH 6-8 solutions was investigated under strictly anoxic conditions using an oxygen trap (<7.5 × 10−9 atm O2). The reduction kinetics were strongly pH dependent. Complete and rapid reduction of Tc(VII) to a precipitated Fe/Tc(IV) form was observed when 11 μmol/L of Tc(VII) was reacted with 0.4 mmol/L Fe(II) at pH 7.0 and 8.0, while no significant reduction was observed over 1 month at pH 6.0. Experiments conducted at pH 7.0 with Fe(II)(aq) = 0.05-0.8 mmol/L further revealed that Tc(VII) reduction was a combination of homogeneous and heterogeneous reaction. Heterogeneous reduction predominated after approximately 0.01 mmol/L of Fe(II) was oxidized. The heterogeneous reaction was more rapid, and was catalyzed by Fe(II) that adsorbed to the Fe/Tc(IV) redox product. Wet chemical and Fe-X-ray absorption near edge spectroscopy measurements (XANES) showed that Fe(II) and Fe(III) were present in the Fe/Tc(IV) redox products after reaction termination. 57Fe-Mössbauer, extended X-ray adsorption fine structure (EXAFS), and transmission electron microscopy (TEM) measurements revealed that the Fe/Tc(IV) solid phase was poorly ordered and dominated by Fe(II)-containing ferrihydrite with minor magnetite. Tc(IV) exhibited homogeneous spatial distribution within the precipitates. According to Tc-EXAFS measurements and structural modeling, its molecular environment was consistent with an octahedral Tc(IV) dimer bound in bidentate edge-sharing mode to octahedral Fe(III) associated with surface or vacancy sites in ferrihydrite. The precipitate maintained Tc(IV)aq concentrations that were slightly below those in equilibrium with amorphous Tc(IV)O2·nH2O(s). The oxidation rate of sorbed Tc(IV) in the Fe/Tc precipitate was considerably slower than Tc(IV)O2·nH2O(s) as a result of its intraparticle/intragrain residence. Precipitates of this nature may form in anoxic sediments or groundwaters, and the intraparticle residence of sorbed/precipitated Tc(IV) may limit 99Tc remobilization upon the return of oxidizing conditions.  相似文献   

10.
The kinetics of iodide (I−) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (δ-MnO2) was investigated over the pH range 4.5-6.25. I− oxidation to iodate proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I− from solution was first order with respect to I− concentration, pH, and birnessite concentration, such that −d[I−]/dt = k[I−][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ± 0.06 × 107 M−2 h−1. The data are consistent with the formation of an inner sphere I− surface complex as the first step of the reaction, and the adsorption of I− exhibited significant pH dependence. Both I2, and to a lesser extent, sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and , as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.  相似文献   

11.
Published solubility data for amorphous ferric arsenate and scorodite have been reevaluated using the geochemical code PHREEQC with a modified thermodynamic database for the arsenic species. Solubility product calculations have emphasized measurements obtained under conditions of congruent dissolution of ferric arsenate (pH < 3), and have taken into account ion activity coefficients, and ferric hydroxide, ferric sulfate, and ferric arsenate complexes which have association constants of 104.04 (FeH2AsO42+), 109.86 (FeHAsO4+), and 1018.9 (FeAsO4). Derived solubility products of amorphous ferric arsenate and crystalline scorodite (as log Ksp) are −23.0 ± 0.3 and −25.83 ± 0.07, respectively, at 25 °C and 1 bar pressure. In an application of the solubility results, acid raffinate solutions (molar Fe/As = 3.6) from the JEB uranium mill at McClean Lake in northern Saskatchewan were neutralized with lime to pH 2-8. Poorly crystalline scorodite precipitated below pH 3, removing perhaps 98% of the As(V) from solution, with ferric oxyhydroxide (FO) phases precipitated starting between pH 2 and 3. Between pH 2.18 and 7.37, the apparent log Ksp of ferric arsenate decreased from −22.80 to −24.67, while that of FO (as Fe(OH)3) increased from −39.49 to −33.5. Adsorption of As(V) by FO can also explain the decrease in the small amounts of As(V)(aq) that remain in solution above pH 2-3. The same general As(V) behavior is observed in the pore waters of neutralized tailings buried for 5 yr at depths of up to 32 m in the JEB tailings management facility (TMF), where arsenic in the pore water decreases to 1-2 mg/L with increasing age and depth. In the TMF, average apparent log Ksp values for ferric arsenate and ferric hydroxide are −25.74 ± 0.88 and −37.03 ± 0.58, respectively. In the laboratory tests and in the TMF, the increasing crystallinity of scorodite and the amorphous character of the coexisting FO phase increases the stability field of scorodite relative to that of the FO to near-neutral pH values. The kinetic inability of amorphous FO to crystallize probably results from the presence of high concentrations of sulfate and arsenate.  相似文献   

12.
The mechanism of pyrite oxidation in carbonate-containing alkaline solutions at 80 °C was investigated with the help of rate experiments, thermodynamic modeling and diffuse reflectance infrared spectroscopy (DRIFTS). Pyrite oxidation rate increased with pH and was enhanced by addition of bicarbonate/carbonate ions. The carbonate effect was found to be limited to moderately alkaline conditions (pH 8-11). Metastable Eh-pH diagrams, at 25 °C, indicate that soluble iron-carbonate complexes (FeHCO3−, FeCO30, Fe(CO3)(OH)− and FeCO32−) may coexist with pyrite in the pH range of 6-12.5. Above pH 11 and 13, the Fe(II) and Fe(III) hydroxocomplexes, respectively, become stable, even in the presence of carbonate/bicarbonate ions. Surface-bound carbonate complexes on iron were also identified with DRIFTS as products of pyrite oxidation in addition to iron oxyhydroxides and soluble sulfate species. The conditions under which thermodynamic and DRIFTS analyses indicate the presence of carbonate compounds also correspond to those in which the fastest rate of pyrite oxidation in carbonate solutions was observed. Following the Singer-Stumm model for pyrite oxidation in acidic solutions, it is assumed that Fe(III) is the preferred pyrite oxidant under alkaline conditions. We propose that carbonate ions facilitate the electron transfer from soluble iron(II)-carbonate to O2, increase the iron solubility, and provide buffered, favorable alkaline conditions at the reaction front, which in turn favors the overall kinetics of pyrite oxidation. Therefore, the electron transfer from sulfur atoms to O2 is facilitated by the formation of the cycle of Fe(II)-pyrite/Fe(III)-carbonate redox couple at the pyrite surface.  相似文献   

13.
In laboratory experiments, we investigated the effect of five individual Fe-binding ligands: phaeophytin, ferrichrome, desferrioxamine B (DFOB), inositol hexaphosphate (phytic acid), and protoporphyrin IX (PPIX) on the Fe(II) photoproduction using seawater of the open Southern Ocean. Addition of 10-100 nM Fe(III) to open Southern Ocean seawater without the model ligands and containing; 1.1 nM dissolved Fe(III), 1.75 ± 0.28 equivalents of nM Fe of natural ligands with a conditional stability constant (log K′) of 21.75 ± 0.34 and a concentration DOC of 86.8 ± 1.13 μM C leads to the formation of amorphous Fe(III) hydroxides. These amorphous Fe(III) hydroxides are the major source for the photoproduction of Fe(II). The addition of the model ligands changed the Fe(II) photoproduction considerably and in various ways. Phaeophytin showed higher Fe(II) photoproduction than ferrichrome and the control, i.e., amorphous Fe(III) hydroxides. Additions of phytic acid between 65 and 105 nM increased the concentration of photoproduced Fe(II) with 0.16 nM Fe(II) per nM phytic acid, presumably due to the co-aggregation of Fe(III) and phytic acid leading via an increasing colloidal surface to an increasing photoreducible Fe(III) fraction. DFOB and PPIX strongly decreased the photoproduced Fe(II) concentration. The low Fe(II) photoproduction with DFOB confirmed reported observations that Fe(III) complexed to DFOB is photo-stable. The PPIX hardly binds Fe(III) in the open Southern Ocean seawater but decreased the photoproduced Fe(II) concentration by complexing the Fe(II) with a binding rate constant of kFe(II)PPIX = 1.04 × 10−4 ± 1.53 × 10−5 s−1 nM−1 PPIX. Subsequently, PPIX is suggested to act as a photosensitizing producer of superoxide, thus increasing the dark reduction of Fe(III) to Fe(II). Our research shows that the photochemistry of Fe(III) and the resulting photoproduced Fe(II) concentration is strongly depending on the identity of the Fe-binding organic ligands and that a translation to natural conditions is not possible without further characterization of the natural occurring ligands.  相似文献   

14.
Microbial Mn(II) oxidation kinetics in response to oxygen concentration were assessed in suboxic zone water at six sites throughout the Black Sea. Mn(II) oxidation rates increased asymptotically with increasing oxygen concentration, consistent with Michaelis-Menten enzyme kinetics. The environmental half-saturation constant, KE, of Mn(II) removal (oxidation) varied from 0.30 to 10.5 μM dissolved oxygen while the maximal environmental rate, VE−max, ranged from 4 to 50 nM h−1. These parameters varied spatially and temporally, consistent with a diverse population of enzymes catalyzing Mn oxide production in the Black Sea. Coastally-influenced sites produced lower KE and higher VE−max constants relative to the Western and Eastern Gyre sites. In the Bosporus Region, the Mn(II) residence time calculated using our KE and VE−max values with 0.1 μM oxygen was 4 days, 25-fold less than previous estimates. Our results (i) indicate that rapid Mn(II) oxidation to solid phase Mn oxides in the Black Sea’s suboxic zone is stimulated by oxygen concentrations well below the 3-5 μM concentration reliably detected by current oceanographic methods, (ii) suggest the existence of multiple, diverse Mn(II)-oxidizing enzymes, (iii) are consistent with shorter residence times than previously calculated for Mn(II) in the suboxic zone and (iv) cast further doubt on the existence of proposed reactions coupling solid phase Mn oxide production to electron acceptors other than oxygen.  相似文献   

15.
The objective of this research is to assess critically the experimental rate data for O2 oxidation of dissolved Mn(II) species at 25°C and to interpret the rates in terms of the solution species of Mn(II) in natural waters. A species kinetic rate expression for parallel paths expresses the total rate of Mn(II) oxidation as Σki aij, where ki is the rate constant of species i and aij is the species concentration fraction in solution j. Among the species considered in the rate expression are Mn(II) hydrolysis products, carbonate complexes, ammonia complexes, and halide and sulfate complexes, in addition to the free aqueous ion. Experiments in three different laboratory buffers and in seawater yield an apparent rate constant for Mn(II) disappearance, kapp,j ranging from 8.6 × 10−5 to 2.5 × 10−2 (M−1s−1), between pH 8.03 and 9.30, respectively. Observed values of kapp exceed predictions based on Marcus outer-sphere electron transfer theory by more than four orders of magnitude, lending strong support to the proposal that Mn(II) + O2 electron transfer follows an inner-sphere path. A multiple linear regression analysis fit of the observed rates to the species kinetic rate expression yields the following oxidation rate constants (M−1s−1) for the most reactive species: MnOH+, 1.66 × 10−2; Mn(OH)2, 2.09 × 101; and Mn(CO3)22−, 8.13 × 10−2. The species kinetic rate expression accounts for the influence of pH and carbonate on oxidation rates of Mn(II), through complex formation and acid-base equilibria of both reactive and unreactive species. At pH ∼8, the greater fraction of the total rate is carried by MnOH+. At pH greater than ∼8.4, the species Mn(OH)2 and Mn(CO3)22− make the greater contributions to the total rate.  相似文献   

16.
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   

17.
The range in 56Fe/54Fe isotopic compositions measured in naturally occurring iron-bearing species is greater than 5‰. Both theoretical modeling and experimental studies of equilibrium isotopic fractionation among iron-bearing species have shown that significant fractionations can be caused by differences in oxidation state (i.e., redox effects in the environment) as well as by bond partner and coordination number (i.e., nonredox effects due to speciation).To test the relative effects of redox vs. nonredox attributes on total Fe equilibrium isotopic fractionation, we measured changes, both experimentally and theoretically, in the isotopic composition of an Fe2+-Fe3+-Cl-H2O solution as the chlorinity was varied. We made use of the unique solubility of FeCl4− in immiscible diethyl ether to create a separate spectator phase against which changes in the aqueous phase could be quantified. Our experiments showed a reduction in the redox isotopic fractionation between Fe2+- and Fe3+-bearing species from 3.4‰ at [Cl−] = 1.5 M to 2.4‰ at [Cl−] = 5.0 M, due to changes in speciation in the Fe-Cl solution. This experimental design was also used to demonstrate the attainment of isotopic equilibrium between the two phases, using a 54Fe spike.To better understand speciation effects on redox fractionation, we created four new sets of ab initio models of the ferrous chloride complexes used in the experiments. These were combined with corresponding ab initio models for the ferric chloride complexes from previous work. At 20 °C, 1000 ln β (β = 56Fe/54Fe reduced partition function ratio relative to a dissociated Fe atom) values range from 6.39‰ to 5.42‰ for Fe(H2O)62+, 5.98‰ to 5.34‰ for FeCl(H2O)5+, and 5.91‰ to 4.86‰ for FeCl2(H2O)4, depending on the model. The theoretical models predict ferric-ferrous fractionation about half as large (depending on model) as the experimental results.Our results show (1) oxidation state is likely to be the dominant factor controlling equilibrium Fe isotope fractionation in solution and (2) nonredox attributes (such as ligands present in the aqueous solution, speciation and relative abundances, and ionic strength of the solution) can also have significant effects. Changes in the isotopic composition of an Fe-bearing solution will influence the resultant Fe isotopic signature of any precipitates.  相似文献   

18.
《Applied Geochemistry》1999,14(4):511-530
The oxidation of Fe(II) is apparently the rate-limiting step in passive treatment of coal mine drainage. Little work has been done to determine the kinetics of oxidation in such field systems, and no models of passive treatment systems explicitly consider iron oxidation kinetics. A Stella II™ model using Fe(II)init concentration, pH, temperature, Thiobacillus ferrooxidans and O2 concentration, flow rate, and pond volume is used to predict Fe(II) oxidation rates and concentrations in seventeen ponds under a wide range of conditions (pH 2.8 to 6.8 with Fe(II) concentrations of less than 240 mg L−1) from 6 passive treatment facilities. The oxidation rate is modeled based on the combination of published abiotic and biological laboratory rate laws. Although many other variables have been observed to influence Fe(II) oxidation rates, the 7 variables above allow field systems to be modeled reasonably accurately for conditions in this study.Measured T. ferrooxidans concentrations were approximately 107 times lower than concentrations required in the model to accurately predict field Fe(II) concentrations. This result suggests that either 1) the most probable number enumeration method underestimated the bacterial concentrations, or 2) the biological rate law employed underestimated the influence of bacteria, or both. Due to this discrepancy, bacterial concentrations used in the model for pH values of less than 5 are treated as fit parameters rather than empirically measured values.Predicted Fe(II) concentrations in ponds agree well with measured Fe(II) concentrations, and predicted oxidation rates also agree well with field-measured rates. From pH 2.8 to approximately pH 5, Fe(II) oxidation rates are negatively correlated with pH and catalyzed by T. ferrooxidans. From pH 5 to 6.4, Fe(II) oxidation appears to be primarily abiotic and is positively correlated with pH. Above pH 6.4, oxidation appears to be independent of pH. Above pH 5, treatment efficiency is affected most by changing design parameters in the following order: pH>temperature≈influent Fe(II)>pond volume≈O2. Little to no increase in Fe(II) oxidation rate occurs due to pH increases above pH 6.4. Failure to consider Fe(II) oxidation rates in treatment system design may result in insufficient Fe removal.  相似文献   

19.
Rates of anaerobic respiration are of central importance for the long-term burial of carbon (C) in peatlands, which are a relevant sink in the global C cycle. To identify constraints on anaerobic peat decomposition, we determined detailed concentration depth profiles of decomposition end-products, i.e. methane (CH4) and dissolved inorganic carbon (DIC), along with concentrations of relevant decomposition intermediates at an ombrotrophic Canadian peat bog. The magnitude of in situ net production rates of DIC and CH4 was estimated by inverse pore-water modeling. Vertical transport in the peat was slow and dominated by diffusion leading to the buildup of DIC and CH4 with depth (5500 μmol L−1 DIC, 500 μmol L−1 CH4). Highest DIC and CH4 production rates occurred close to the water table (decomposition constant kd ∼ 10−3-10−4 a−1) or in some distinct zones at depth (kd ∼ 10−4 a−1). Deeper into the peat, decomposition proceeded very slowly at about kd = 10−7 a−1. This pattern could be related to thermodynamic and transport constraints. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (−20 to −25 kJ mol−1 CH4). The methanogenic precursor acetate also accumulated (150 μmol L−1). In line with these findings, CH4 was formed by hydrogenotrophic methanogenesis at Gibbs free energies of −35 to −40 kJ mol−1 CH4. This was indicated by an isotopic fractionation αCO2-CH4 of 1.069-1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol−1 substrate. Although methanogenesis was apparently limited by some other factor in some peat layers, transport and thermodynamic constraints likely impeded respiratory processes in the deeper peat. Constraints on the removal of DIC and CH4 may thus slow decomposition and contribute to the sustained burial of C in northern peatlands.  相似文献   

20.
Forward dissolution rates of Na-Montmorillonite (Wyoming) SWy-2 smectite (Ca0.06Na0.56)[Al3.08Fe(III)0.38Mg0.54] [Si7.93 Al0.07]O20(OH)4 were measured at 25 °C in a mixed-flow reactor equipped with interior dialysis compartment (6-8 kDa membrane) as a function of pH (1-12), dissolved carbonate (0.5-10 mM), phosphate (10−5 to 0.03 M), and nine organic ligands (acetate, oxalate, citrate, EDTA, alginate, glucuronic acid, 3,4-dihydroxybenzoic acid, gluconate, and glucosamine) in the concentration range from 10−5 to 0.03 M. In organic-free solutions, the Si-based rates decrease with increasing pH at 1 ? pH ? 8 with a slope close to −0.2. At 9 ? pH ? 12, the Si-based rates increase with a slope of ∼0.3. In contrast, non-stoichiometric Mg release weakly depends on pH at 1 ? pH ? 12 and decreases with increasing pH. The empirical expression describing Si-release rates [R, mol/cm2/s] obtained in the present study at 25 °C, I = 0.01 M is given by
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