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1.
Citrate released by plants, bacteria, and fungi into soils is subject to abiotic oxidation by MnO2(birnessite), yielding 3-ketoglutarate, acetoacetate, and MnII. Citrate loss and generation of products as a function of time all yield S-shaped curves, indicating autocatalysis. Increasing the citrate concentration decreases the induction period. The maximum rate (rmax) along the reaction coordinate follows a Langmuir-Hinshelwood dependence on citrate concentration. Increases in pH decrease rmax and increase the induction time. Adding MnII, ZnII, orthophosphate, or pyrophosphate at the onset of reaction decreases rmax. MnII addition eliminates the induction period, while orthophosphate and pyrophosphate addition increase the induction period. These findings indicate that two parallel processes are responsible. The first, relatively slow process involves the oxidation of free citrate by surface-bound MnIII,IV, yielding MnII and citrate oxidation products. The second process, which is subject to strong positive feedback, involves electron transfer from MnII-citrate complexes to surface-bound MnIII,IV, generating MnIII-citrate and MnII. Subsequent intramolecular electron transfer converts MnIII-citrate into MnII and citrate oxidation products.  相似文献   

2.
Chromium (Cr) is a heavy metal that exists in soils in two stable oxidation states, +III and +VI. The trivalent species is an essential nutrient, whereas the hexavalent species is highly toxic. This study investigated the environmental impact of CrIII potentially released into soil from wastes and various materials by determining the risk of oxidation of initially soluble inorganic CrIII into hazardous CrVI. The principal aim was to describe the pH-dependent mechanisms that regulate 1) the formation of CrVI from the easily soluble CrIII and 2) the potential bioavailability of CrIII and that of CrVI species produced in the oxidation of CrIII in agricultural soil (fine sand, organic carbon 3.2%). The amount of CrVI formed in oxic soil conditions was regulated by two counteracting reactions: 1) oxidation of CrIII into CrVI by manganese oxide (MnIVO2) and 2) the subsequent reduction of CrVI by organic matter back to CrIII. The effect of pH on this net-oxidation of CrIII and on the chemical availability of both CrIII and CrVI species was investigated in soil samples incubated with or without excessive amounts of synthetic MnO2, over the chemically adjusted pH range of 3.9–6.3 (+22 °C, 47 d). In soil subsamples without added MnO2, the net-oxidation of CrIII into CrVI (1 mM CrCl3 in soil suspensions, 1:10 w/V) was negligible. As for the MnO2-treated soils, at maximum only 4.7% of added CrIII was oxidized – regardless of the high oxidation potential of these subsamples. The lowest production of CrVI was observed under acidic soil conditions at pH ∼4. At low pH, the net-oxidation diminished as result of enhanced reduction of CrVI back to CrIII. At higher pHs, the oxidation was limited by enhanced precipitation (or adsorption) of CrIII, which lowered the overall amount of CrIII susceptible for oxidation. Moreover, the oxidation reactions by MnO2 were inhibited by formation of Cr(OH)3 coverage on its surface. The pH-dependent chemical bioavailability of added CrIII differed from that of the CrVI formed. At elevated pHs the chemical availability of CrIII decreased, whereas that of CrVI produced increased. However, the risk of CrVI formation through oxidation of the easily soluble inorganic CrIII was considered to be low in agricultural soils high in organic matter and low in innate MnO2.  相似文献   

3.
The complex interaction between CrIIIaq and manganite (γ-MnOOH) was systematically studied at room temperature over a pH range of 3 to 6, and within a concentration range of 10−4 to 10−2 M CrOH2+aq. Solution compositional changes during batch reactions were characterized by inductively coupled plasma spectroscopy and ultraviolet-visible spectrophotometry. The manganites were characterized before and after reaction with X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), high-resolution field-emission SEM, and energy-dispersive spectroscopy analysis. Fluid-cell atomic force microscopy was used to follow these metal-mineral interactions in situ. The reactions are characterized by (1) sorption of CrIII and the surface-catalyzed microprecipitation of CrIII-hydroxy hydrate on manganite surfaces, (2) the acidic dissolution of the manganite, and (3) the simultaneous reductive dissolution of manganite coupled with the oxidation of CrIIIaq to highly toxic CrVIaq. CrIII-hydroxy hydrate was shown to precipitate on the manganite surface while still undersaturated in bulk solution. The rate of manganite dissolution increased with decreasing pH due both to acid-promoted and Mn-reduction-promoted dissolution. Cr oxidation also increased in the lower pH range, this as a result of its direct redox coupling with Mn reduction. Neither MnII nor CrVI were ever detected on manganite surfaces, even at the maximum rate of their generation. At the highest pHs of this study, CrIIIaq was effectively removed from solution to form CrIII-hydroxy hydrate on manganite surfaces and in the bulk solution, and manganite dissolution and CrVIaq generation were minimized. All interface reactions described above were heterogeneous across the manganite surfaces. This heterogeneity is a direct result of the heterogeneous semiconducting nature of natural manganite crystals and is also an expression of the proximity effect, whereby redox processes on semiconducting surfaces are not limited to next nearest neighbor sites.  相似文献   

4.
To examine the pathways that form Mn(III) and Mn(IV) in the Mn(II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn(IV)O2 formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn(III) complex or insoluble Mn(IV)O2 minerals - but not both simultaneously. PVD-Mn(III) was present, and MnO2 precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn(III) arose by predominantly ligand-mediated air oxidation of Mn(II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn(III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn(III), a process linked to the production of both MnO2 and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn(III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO2 to appear. These results suggest that P. putida cultures produce soluble Mn(III) or MnO2 by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO2 under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn(III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn(III) versus MnO2) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn.  相似文献   

5.
The initial solid phase oxidation products formed during the oxidation of aqueous Mn(II) at 25°C were studied as a function of time. The analyses included morphology (TEM), mineralogy (x-ray diffraction), OMn ratio (iodometric method), oxidation state of manganese (XPS), and dissolved manganese. The initial solid formed under our conditions was Mn3O4 (hausmannite) which converted completely to γMnOOH (manganite) after eight months. βMnOOH (feitknechtite) appeared to be an intermediate in this transformation. The OMn ratio was initially 1.37 and increased to 1.49 over the same time span. Throughout the course of this study the XPS analyses showed that the surface of the solids (<50 Å) was dominated by Mn(III). The solution pH and dissolved manganese concentrations were consistent with disproportionation and oxidation reactions that favor the transformation of Mn3O4 to γMnOOH but not to γMnO2.  相似文献   

6.
Manganese oxides precipitated by bubbling air through 0.01 molar solutions of MnCl2, Mn(NO3)2, MnSO4, or Mn(ClO4)2 at a constantly maintained pH of 8.5 to 9.5 at temperatures of 25°C or higher consisted mainly of hausmannite, Mn3O4. At temperatures near 0°C, but with other conditions the same, the product is feitknechtite, βMnOOH, except that if the initial solution is MnSO4 and the temperature is near 0°C the product is a mixture of manganite, γMnOOH and groutite, αMnOOH.All these oxides are metastable in aerated solution and alter by irreversible processes to more highly oxidized species during aging. A two-step nonequilibrium thermodynamic model predicts that the least stable species, βMnOOH, should be most readily converted to MnO2. Some preparations of βMnOOH aged in their native solution at 5°C attained a manganese oxidation state of +3.3 or more after 7 months. Hausmannite aged at 25°C altered to γMnOOH. The latter is more stable than a or βMnOOH, and manganese oxidation states above 3.0 were not reached in hausmannite precipitates during 4 months of aging. Initial precipitation of MnCO3 rather than a form of oxide is likely only where oxygen availability is very low.Composition of solutions and oxidation state and morphology of solids were determined during the aging process by chemical analyses, X-ray and electron diffraction and transmission electron micrographs.  相似文献   

7.
The rate of crystal growth of Mn3O4 (hausmannite) and βMnOOH (feitknechtite) in aerated aqueous manganous perchlorate systems, near 0.01 M in total manganese, was determined at pH levels ranging from 7.00 to 9.00 and at temperatures from 0.5 to 37.4°C. The process is autocatalytic, but becomes psuedo first-order in dissolved Mn2+ activity when the amount of precipitate surface is large compared to the amount of unreacted manganese. Reaction rates determined by titrations using an automated pH-stat were fitted to an equation for precipitate growth. The rates are proportional to surface area of oxide and degree of supersaturation with respect to Mn2+. The oxide obtained at the higher temperature was Mn3O4, but at 0.5° C only βMnOOH was formed. At intermediate temperatures, mixtures of these solids were formed. The rate of precipitation of hausmannite is strongly influenced by temperature, and that of feitknechtite much less so. The difference in activation energy may be related to differences in crystal structure of the oxides and the geometry of polymeric hydroxy ion precursors.  相似文献   

8.
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   

9.
The competitive binding of rare earth elements (REE) to purified humic acid (HA) and MnO2 was studied experimentally using various HA/MnO2 ratios over a range of pH (3 to 8). MnO2, humic acid and REE solutions were simultaneously mixed to investigate the kinetics of the competitive reactions. Aqueous REE–HA complex is the dominant species whatever the experiment time, pH and HA/MnO2 ratio. The value of the distribution coefficients between MnO2 and solution (log KdRee/Mno2) increases with the HA/MnO2 ratio, indicating that part of the REE–HA complexes are adsorbed onto MnO2. The development of a Ce anomaly appears strongly limited in comparison with inorganic experimental conditions. Throughout the experimental run time, for HA/MnO2 ratios of less than 0.4, MnO2 acts as a competitor leading to a partial dissociation of the REE–HA complex. The majority of the dissociated REE is readsorbed onto the MnO2 surface. The readsorption of REE is expressed by an increased Ce anomaly on the log KdRee/Mno2 pattern as well as a change in shape of the coefficient distribution of REE between soluble HA and solution pattern (log KdRee/HA decrease for the heavy rare earth elements — HREE). Thus, REE are not only bound to MnO2 as a REE–HA complex, but also as REE(III). Moreover, the competition between HA and MnO2 for REE binding is shown to be higher at low pH (< 6) and low DOC/Mn ratio. This study partially confirms previous work that demonstrated the control of REE adsorption by organic matter, while shedding more light on the impact of pH as well as complexation reaction competition on long-term REE partitioning between solid surface and organic solutions. The latter point is important as regards to REE speciation under conditions typical of rock and/or mineral alteration.  相似文献   

10.
Study on the kinetics of iron oxide leaching by oxalic acid   总被引：2，自引：0，他引：2  
The presence of iron oxides in clay or silica raw materials is detrimental to the manufacturing of high quality ceramics. Although iron has been traditionally removed by physical mineral processing, acid washing has been tested as it is more effective, especially for extremely low iron (of less than 0.1% w/w). However, inorganic acids such as sulphuric or hydrochloric acids easily contaminate the clay products with SO42− and Cl−, and therefore should be avoided as much as possible. On the other hand, if oxalic acid is used, any acid left behind will be destroyed during the firing of the ceramic products. The characteristics of dissolution of iron oxides were therefore investigated in this study.The dissolution of iron oxides in oxalic acid was found to be very slow at temperatures within the range 25–60 °C, but its rate increases rapidly above 90 °C. The dissolution rate also increases with increasing oxalate concentration at the constant pH values set within the optimum range of pH2.5–3.0. At this optimum pH, the dissolution of fine pure hematite (Fe2O3) (105–140 μm) follows a diffusion-controlled shrinking core model. The rate expression expressed as 1 − (2 / 3)x − (1 − x)2 / 3 where x is a fraction of iron dissolution was found to be proportional to [oxalate]1.5.The addition of magnetite to the leach liquor at 10% w/w hematite was found to enhance the dissolution rate dramatically. Such addition of magnetite allows coarser hematite in the range 0.5–1.4 mm to be leached at a reasonable rate.  相似文献   

11.
The Pinal creek drainage basin in Arizona is a good example of the principal non-coal source of mining-related acid drainage in the U.S.A., namely copper mining. Infiltration of drainage waters from mining and ore refining has created an acid groundwater plume that has reacted with calcite during passage through the alluvium, thereby becoming less acid. Where O2 is present and the water is partially neutralized, iron oxides have precipitated and, farther downstream where the pH of the stream water is near neutral, high-Mn crusts have developed.Trace metal composition of several phases in the Pinal Creek drainage basin illustrates the changes caused by mining activities and the significant control Mn-crusts and iron oxide deposits exert on the distribution and concentration of trace metals. The phases and locales considered are the dissolved phase of Webster Lake, a former acid waste disposal pond; selected sections of cores drilled in the alluvium within the intermittent reach of Pinal Creek; and the dissolved phase, suspended sediments, and streambed deposits at specified locales along the perennial reach of Pinal creek.In the perennial reach of Pinal Creek, manganese oxides precipitate from the streamflow as non-cemented particulates and coatings of streambed material and as cemented black crusts. Chemical and X-ray diffraction analyses indicate that the non-cemented manganese oxides precipitate in the reaction sequence observed in previous laboratory experiments using simpler solution composition, Mn3O4 to MnOOH to an oxide of higher oxidation number usually <4.0, i.e. Na-birnessite, and that the black cemented crusts contain (Ca,Mn,Mg)CO3 and a 7-Åphyllomanganate mixture of rancieite ((Ca,Mn)Mn4O9 · (3H2O)) and takanelite ((Mn,Ca)Mn4O9 · (3H2O)). In the laboratory, aerating and increasing the pH of Pinal Creek water to 9.00 precipitated (Ca,Mn,Mg)CO3 from an anoxic groundwater that contained CO2 HCO3, and precipitated Mn3O4 and subsequently MnOOH from an oxic surface water from which most of the dissolved CO2 had been removed.It is suggested that the black cemented crusts form by precipitation of Fe on the Mn-enriched carbonates, creating a site for the MnFe oxidation cycle and thus encouraging the conversion of the carbonates to 7-Åphysllomanganates. The non-magnetic <63-μm size-fractions of the black cemented crusts consisted mostly of the manganese-calcium oxides but also contained about 20% (Ca,Mn,Mg)CO3, 5% Fe (calculated as FeOOH), 2–4% exchangeable cations, and trace amounts of several silicates.  相似文献   

12.
We have examined the effects of aqueous complexation on rates of dissimilatory reductive precipitation of uranium by Shewanella putrefaciens. Uranium(VI) was supplied as sole terminal electron acceptor to Shewanella putrefaciens (strain 200R) in defined laboratory media under strictly anaerobic conditions. Media were amended with different multidentate organic acids, and experiments were performed at different U(VI) and ligand concentrations. Organic acids used as complexing agents were oxalic, malonic, succinic, glutaric, adipic, pimelic, maleic, citric, and nitrilotriacetic acids, tiron, EDTA, and Aldrich humic acid. Reductive precipitation of U(VI), resulting in removal of insoluble amorphous UO2 from solution, was measured as a function of time by determination of total dissolved U. Reductive precipitation was measured, rather than net U(VI) reduction to U(IV), to assess overall U removal rates from solution, which may be used to gauge the influence of chelation on microbial U mineralization. Initial linear rates of U reductive precipitation were found to correlate with stability constants of 1:1 aqueous U(VI):ligand and U(IV):ligand complexes. In the presence of strongly complexing ligands (e.g., NTA, Tiron, EDTA), UO2 precipitation did not occur. Our results are consistent with ligand-retarded precipitation of UO2, which is analogous to ligand-assisted solid phase dissolution but in reverse: ligand exchange with the U4+ aquo cation acts as a rate-limiting reaction moderating coordination of water molecules with U4+, which is a necessary step in UO2 precipitation. Ligand exchange kinetics governing dissociation rates of ligands from U(VI)-organic complexes may also influence overall UO2 production rates, although the magnitude of this effect is unclear relative to the effects of U(IV)-organic complexation. Our results indicate that natural microbial-aqueous systems containing abundant organic matter can inhibit the formation of biogenic amorphous UO2.  相似文献   

13.
Strong enrichments of cobalt occur in marine manganese nodules, soils, wads, and natural and synthetic minerals such as hollandite, cryptomelane, psilomelane, lithiophorite, birnessite, and δ-MnO2. Previously, it was suggested that Co3+ ions in these minerals replace either Mn3+ or substitute for Fe3+ in incipient goethite epitaxially intergrown with δ-MnO2. Neither of these interpretations is now considered to be satisfactory on account of the large discrepancy of ionic radius between octahedrally coordinated low-spin Co3+ and high-spin Mn3+ or Fe3+ in oxide structures. The close agreement between the ionic radii of Co3+ and Mn4+ suggests that some cobalt substitutes for Mn4+ ions in edge-shared [MnO6] octahedra in many manganese(IV) oxide mineral structures. It is proposed that hydrated cations, including Co2+ ions, are initially adsorbed on to the surfaces of certain Mn(IV) oxides in the vicinity of essential vacancies found in the chains or sheets of edge-shared [MnO6] octahedra. Subsequently, fixation of cobalt takes place as a result of oxidation of adsorbed Co2+ ions by Mn4+ and replacement of the displaced manganese by low-spin Co3+ ions in the [MnO6] octahedra or vacancies.  相似文献   

14.
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   

15.
Pore water profiles of total-CO2, pH, PO3?4, NO?3 plus NO?2, SO2?4, S2?, Fe2+ and Mn2+ have been obtained in cores from pelagic sediments of the eastern equatorial Atlantic under waters of moderate to high productivity. These profiles reveal that oxidants are consumed in order of decreasing energy production per mole of organic carbon oxidized (O2 > manganese oxides ~ nitrate > iron oxides > sulfate). Total CO2 concentrations reflect organic regeneration and calcite dissolution. Phosphate profiles are consistent with organic regeneration and with the effects of release and uptake during inorganic reactions. Nitrate profiles reflect organic regeneration and nitrate reduction, while dissolved iron and manganese profiles suggest reduction of the solid oxide phases, upward fluxes of dissolved metals and subsequent entrapment in the sediment column. Sulfate values are constant and sulfide is absent, reflecting the absence of strongly anoxic conditions.  相似文献   

16.
Pyrite (FeS2) and iron monosulfide (FeS) play a central role in the sulfur and iron cycles of marine sediments. They may be buried in the sediment or oxidized by O2 after transport by bioturbation to the sediment surface. FeS2 and FeS may also be oxidized within the anoxic sediment in which NO3−, Fe(III) oxides, or MnO2 are available as potential electron acceptors. In chemical experiments, FeS2 and FeS were oxidized by MnO2 but not with NO3− or amorphous Fe(III) oxide (Schippers and Jørgensen, 2001). Here we also show that in experiments with anoxic sediment slurries, a dissolution of tracer-marked 55FeS2 occurred with MnO2 but not with NO3− or amorphous Fe(III) oxide as electron acceptor. To study a thermodynamically possible anaerobic microbial FeS2 and FeS oxidation with NO3− or amorphous Fe(III) oxide as electron acceptor, more than 300 assays were inoculated with material from several marine sediments and incubated at different temperatures for > 1 yr. Bacteria could not be enriched with FeS2 as substrate or with FeS and amorphous Fe(III) oxide. With FeS and NO3−, 14 enrichments were obtained. One of these enrichments was further cultivated anaerobically with Fe2+ and S0 as substrates and NO3− as electron acceptor, in the presence of 55FeS2, to test for co-oxidation of FeS2, but an anaerobic microbial dissolution of 55FeS2 could not been detected. FeS2 and FeS were not oxidized by amorphous Fe(III) oxide in the presence of Fe-complexing organic compounds in a carbonate-buffered solution at pH 8. Despite many different experiments, an anaerobic microbial dissolution of FeS2 could not be detected; thus, we conclude that this process does not have a significant role in marine sediments. FeS can be oxidized microbially with NO3− as electron acceptor. O2 and MnO2, but not NO3− or amorphous Fe(III) oxide, are chemical oxidants for both FeS2 and FeS.  相似文献   

17.
Geochemical modeling of coal mine drainage, Summit County, Ohio   总被引：4，自引：1，他引：4  
A. Foos 《Environmental Geology》1997,31(3-4):205-210
 Geochemical modeling was used to investigate downstream changes in coal mine drainage at Silver Creek Metro-park, Summit County, Ohio. A simple mixing model identified the components that are undergoing conservative transport (Cl–, PO4 3–, Ca2+, K+, Mg2+ and Na+) and those undergoing reactive transport (DO, HCO3 –, SO4 2–, Fe2+, Mn2+ and Si). Fe2+ is removed by precipitation of amorphous iron-hydroxide. Mn2+ are removed along with Fe2+ by adsorption onto surfaces of iron-hydroxides. DO increases downstream due to absorption from the atmosphere. The HCO3 – concentration increases downstream as a result of oxidation of organic material. The rate of Fe2+ removal from the mine drainage was estimated from the linear relationship between Fe+2 concentration and downstream distance to be 0.126 mg/s. Results of this study can be used to improve the design of aerobic wetlands used to treat acid mine drainage. Received: 4 June 1996 · Accepted: 17 September 1996  相似文献   

18.
Speciation and colloid transport of arsenic from mine tailings   总被引：2，自引：0，他引：2  
In addition to affecting biogeochemical transformations, the speciation of As also influences its transport from tailings at inoperative mines. The speciation of As in tailings from the Sulfur Bank Mercury Mine site in Clear Lake, California (USA) (a hot-spring Hg deposit) and particles mobilized from these tailings have been examined during laboratory-column experiments. Solutions containing two common, plant-derived organic acids (oxalic and citric acid) were pumped at 13 pore volumes d−1 through 25 by 500 mm columns of calcined Hg ore, analogous to the pedogenesis of tailings. Chemical analysis of column effluent indicated that all of the As mobilized was particulate (1.5 mg, or 6% of the total As in the column through 255 pore volumes of leaching). Arsenic speciation was evaluated using X-ray absorption spectroscopy (XAS), indicating the dominance of arsenate [As(V)] sorbed to poorly crystalline Fe(III)-(hydr)oxides and coprecipitated with jarosite [KFe3(SO4, AsO4)2(OH)6] with no detectable primary or secondary minerals in the tailings and mobilized particles. Sequential chemical extractions (SCE) of <45 μm mine tailings fractions also suggest that As occurs adsorbed to Fe (hydr)oxides (35%) and coprecipitated within poorly crystalline phases (45%). In addition, SCEs suggest that As is associated with 1 N acid-soluble phases such as carbonate minerals (20%) and within crystalline Fe-(hydr)oxides (10%). The finding that As is transported from these mine tailings dominantly as As(V) adsorbed to Fe (hydr)oxides or coprecipitated within hydroxysulfates such as jarosite suggests that As release from soils and sediments contaminated with tailings will be controlled by either organic acid-promoted dissolution or reductive dissolution of host phases.  相似文献   

19.
We used fine-scale porewater profiles and rate measurements together with a multiple component transport–reaction model to investigate carbon degradation pathways and the coupling between electron and proton transfer reactions in Lake Champlain sediments. We measured porewater profiles of O2, Mn2+, Fe2+, HS−, pH and pCO2 at mm resolution by microelectrodes, and profiles of NO3 −, SO4 2−, NH4 +, total inorganic carbon (DIC) and total alkalinity (TA) at cm resolution using standard wet chemical techniques. In addition, sediment–water fluxes of oxygen, DIC, nitrate, ammonium and N2 were measured. Rates of gross and net sulfate reduction were also measured in the sediments. It is shown that organic matter (OM) decomposes via six pathways: oxic respiration (35.2%), denitrification (10.4%), MnO2 reduction (3.6%), FeOOH reduction (9.6%), sulfate reduction (14.9%), and methanogenesis (26.4%). In the lake sediments, about half of the benthic O2 flux is used for aerobic respiration, and the rest is used for the regeneration of other electron acceptors produced during the above diagenetic reactions. There is a strong coupling between O2 usage and Mn2+ oxidation. MnO2 is also an important player in Fe and S cycles and in pH and TA balance. Although nitrate concentrations in the overlying water were low, denitrification becomes a quantitatively important pathway for OM decomposition due to the oxidation of NH4 + to NO3 −. Finally, despite its low concentration in freshwater, sulfate is an important electron acceptor due to its high efficiency of internal cycling. This paper also discusses quantitatively the relationship between redox reactions and the porewater pH values. It is demonstrated here that pH and pCO2 are sensitive variables that reflect various oxidation and precipitation reactions in porewater, while DIC and TA profiles provide effective constraints on the rates of various diagenetic reactions.  相似文献   

20.
Acid mine drainage is a major source of water pollution in the Sarcheshmeh porphyry copper mine area. The concentrations of heavy metals and rare earth elements (REEs) in the host rocks, natural waters and acid mine drainage (AMD) associated with mining and tailing impoundments are determined. Contrary to the solid samples, AMDs and impacted stream waters are enriched in middle rare earth elements (MREEs) and heavy rare earth elements (HREEs) relative to light rare earth elements (LREEs). This behavior suggests that REE probably fractionate during sulfide oxidation and acid generation and subsequent transport, so that MREE and HREE are preferentially enriched. Speciation modeling predict that the dominant dissolved REE inorganic species are Ln3+, Ln(SO4)2−, LnSO4+, LnHCO32+, Ln(CO3)2− and LnCO3+. Compared to natural waters, Sarcheshmeh AMD is enriched in REEs and SO42−. High concentrations of SO42− lead to the formation of stable LnSO4+, thereby resulting in higher concentrations of REEs in AMD samples. The model indicates that LnSO4+ is the dissolved form of REE in acid waters, while carbonate and dicarbonate complexes are the most abundant dissolved REE species in alkaline waters. The speciation calculations indicate that other factors besides complexation of the REE's, such as release of MREE from dissolution and/or desorption processes in soluble salts and poorly crystalline iron oxyhydroxy sulfates as well as dissolution of host rock MREE-bearing minerals control the dissolved REE concentrations and, hence, the MREE-enriched patterns of acid mine waters.  相似文献   

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