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1.
Acid mine drainage (AMD) is a common pollution in mining areas due to the oxidation of pyrite and associated sulfide minerals at mines, tailings and mine dumps. Elevated metals (Fe, Mn, Al) and metalloids (As, Hg) in AMD would deteriorate the local aquatic environment and influence the water supply. A carbonate basin with deposits of high-arsenic coal in Xingren County, southwestern China, was chosen to study the behavior of As and other chemical constituents along a river receiving AMD. Heavy metals (Fe, Mn) and major ions such as (Ca2+, Mg2+, Cl−, SO4 2−) in surface water, and As in sediment and surface water were analyzed. It was found that high concentrations of SO4 2− (1,324–7,560 mg/L) and Fe (369–1,472 mg/L) in surface water were mainly controlled by the interactions between water and rocks such as the oxidation of pyrite in the local coal seams, precipitation and adsorption of iron minerals. Although ubiquitous carbonate minerals in the bedrock and the riverbeds, low pH (<3) water was maintained until 2 km downstream from the AMD source due to the Fe(hydro)oxide minerals coating on the surface of carbonate minerals to restrain the neutralization of acidic water. Moreover, the formation of Fe(hydro)oxide precipitations absorbed As was dominated the attenuation of As from water to sediment. Whereas, the dilution also played an important role in decrease of As in river water.  相似文献   

2.
《Applied Geochemistry》2003,18(11):1705-1721
Armoring of limestone is a common cause of failure in limestone-based acid-mine drainage (AMD) treatment systems. Limestone is the least expensive material available for acid neutralization, but is not typically recommended for highly acidic, Fe-rich waters due to armoring with Fe(III) oxyhydroxide coatings. A new AMD treatment technology that uses CO2 in a pulsed limestone bed reactor minimizes armor formation and enhances limestone reaction with AMD. Limestone was characterized before and after treatment with constant flow and with the new pulsed limestone bed process using AMD from an inactive coal mine in Pennsylvania (pH=2.9, Fe =150 mg/l, acidity =1000 mg/l CaCO3). In constant flow experiments, limestone is completely armored with reddish-colored ochre within 48 h of contact in a fluidized bed reactor. Effluent pH initially increased from the inflow pH of 2.9 to over 7, but then decreased to <4 during the 48 h of contact. Limestone grains developed a rind of gypsum encapsulated by a 10- to 30-μm thick, Fe-Al hydroxysulfate coating. Armoring slowed the reaction and prevented the limestone from generating any additional alkalinity in the system. With the pulsed flow limestone bed process, armor formation is largely suppressed and most limestone grains completely dissolve resulting in an effluent pH of >6 during operation. Limestone removed from a pulsed bed pilot plant is a mixture of unarmored, rounded and etched limestone grains and partially armored limestone and refractory mineral grains (dolomite, pyrite). The ∼30% of the residual grains in the pulsed flow reactor that are armored have thicker (50- to 100-μm), more aluminous coatings and lack the gypsum rind that develops in the constant flow experiment. Aluminium-rich zones developed in the interior parts of armor rims in both the constant flow and pulsed limestone bed experiments in response to pH changes at the solid/solution interface.  相似文献   

3.
《Applied Geochemistry》2006,21(9):1469-1481
The removal of chromate from aqueous solutions, using finely ground pyrite and biotite, was investigated by batch experiments. The kinetics and mechanism of chromate reduction are discussed here. Chromate reduction by pyrite was about 100 times faster than that by biotite, and was also faster at pH 3 than 4. When pyrite was used, more than 90% of the initial chromate was reduced within 4 h at pH 4, and within 40 min. at pH 3. However, with biotite more than 400 h was required for the reduction of 90% of the initial chromate. The results indicate that the rate of chromate reduction was strongly depending on the amount and dissolution rate of the Fe(II) in the minerals. The reduction of chromate at pH 4 resulted in the precipitation of (Cr, Fe)(OH)3(s), which is believed to have limited the concentrations of dissolved Cr(III) and Fe(III) to less than the expected values. When biotite was used, the amounts of decreased Fe(II) and reduced Cr(VI) showed no stoichiometric relationship, which implies that not only was there chromate reduction by Fe(II) ions in the acidic solution, but also heterogeneous reduction of Fe(III) ions by structural Fe(II) in biotite. However, the results from a series of the experiments using pyrite showed that the concentrations of the decreased Fe(II) and the reduced Cr(VI) were close to the stoichiometric ratio of 3:1. This was because the oxidation of pyrite rapidly created Fe(II) ions, even in oxygenated solutions, and the chromate reduction by the Fe(II) ions was significantly faster than the Fe(II) ion oxygenation. When compared with the experimental sets controlled at an initial pH of 3, the pH of the biotite batch, which was not controlled, increased to 3.4. Because of the increase in the pH, Cr(VI) was not completely removed, and 25% (1.2–1.3 mg/L Cr(VI)) of the initial concentration remained for up to 1000 h. The pH increase is, in most cases, caused by the hydrolysis of clay minerals. However, in the pyrite batches, there was no difference in the variations of the chromate reduction in relation to the pH control. There was also no difference in the capacity and rate of Cr(VI) reduction in 0.01 M NaCl or Na2SO4 solutions. In the 0.01 M NaH2PO4 solution pyrite experiment, the Cr(VI) was not completely removed, despite the maintenance of the pH at 3. The dominant Fe species was about 10 mg/L Fe(III) and few Fe(II) ions existed in solution. The Fe phosphate (Fe3(PO4)2 or FePO4) coatings on the surface of pyrite prevented access of O2 or Cr(VI). Therefore, the surface coatings are likely to have caused the deterioration of the Cr(VI) reduction capacity in the NaH2PO4 solution.  相似文献   

4.
Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO4 and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O2) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O2) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO4 and water was observed over a pH range of 0–2 only at 50 °C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 °C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T  25 °C, pH  3) for decades.Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O2 to pyrite surface sites. The sorption of molecular O2 is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO4. The calculated bulk contribution of atmospheric O2 in the dissolved SO4 reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O2 in the early-formed sulfates, chemisorption and electron transfer of molecular O2 on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction of hydroxyls from water with S at the anodic S pyrite surface site. Then, the role of molecular O2 is as proposed in previous studies: acting as electron acceptor only at the cathodic Fe pyrite surface site for oxidation of Fe(II) to Fe(III).  相似文献   

5.
This paper demonstrates the use of dissolution-rate data obtained in the laboratory to indicate the potential quality of effluent from a field-scale oxic limestone drain (OLD) treatment system for neutralization of dilute acidic mine drainage (AMD). Effluent from the Reevesdale Mine South Dip Tunnel, a large source of AMD and base flow to the Wabash Creek and Little Schuylkill River in the Southern Anthracite Coalfield of east-central Pennsylvania, is representative of AMD with low concentrations but high loadings of dissolved Fe, Al and other metals because of a high flow rate. In January 2003, rapid neutralization of the AMD from the Reevesdale Mine was achieved in laboratory tests of its reaction rate with crushed limestone in closed, collapsible containers (Cubitainers). The tests showed that net-alkaline effluent could be achieved with retention times greater than 3 h and that effluent alkalinities and associated dissolution rates were equivalent for Fe(OH)3-coated and uncoated limestone. On the basis of the laboratory results, a flushable OLD containing 1450 metric tons of high-purity calcitic limestone followed by two 0.7-m deep wetlands were constructed at the Reevesdale Mine. During the first year of operation, monthly data at the inflow, outflow and intermediate points within the treatment system were collected (April 2006–2007). The inflow to the treatment system ranged from 6.8 to 27.4 L/s, with median pH of 4.7, net acidity of 9.1 mg/L CaCO3, and concentrations of dissolved Al, Fe and Mn of 1.0, 1.9 and 0.89 mg/L, respectively. The corresponding effluent from the OLD had computed void-volume retention times of 4.5–18 h, with median pH of 6.6, net acidity of −93.2 mg/L CaCO3, and concentrations of dissolved Al, Fe and Mn of <0.1, 0.08 and 0.52 mg/L, respectively. The wetlands below the OLD were effective for retaining metal-rich solids flushed at monthly or more frequent intervals from the OLD, but otherwise had little effect on the effluent quality. During the first year of operation, approximately 43 metric tons of limestone were dissolved and 2 metric tons of Al, Fe and Mn were precipitated within the OLD. However, because of the accumulation of these metals within the OLD and possibly other debris from the mine, the effectiveness of the treatment system declined. Despite the installation of a flush-pipe network at the base of the OLD to remove precipitated solids, the limestone bed clogged near the inflow. Consequently, a large fraction of the AMD bypassed the treatment system. To promote flow through the OLD, the flush pipes were open continuously during the last 4 months of the study; however, this effluent was only partially treated because short-circuiting through the pipes decreased contact between the effluent and limestone. A reconfiguration of the flow path through the limestone bed from horizontal to vertical upward could increase the limestone surface area exposed to the metal-laden influent, increase the cross-sectional area perpendicular to flow, decrease the flow path for solids removal, and, consequently, decrease potential for clogging.  相似文献   

6.
When pyrite oxidizes at near neutral pH in the presence of sufficient alkalinity, Fe oxyhydroxide coatings develop on the surface. As these coatings grow thicker and denser they block oxidant transport from the solution to the pyrite surface and reduce the rate of pyrite oxidation. The authors’ measurements of pyrite oxidation rates in a NaHCO3 solution show that the coating grows in two stages. In the first stage Fe oxyhydroxide colloids form and then attach to the pyrite surface to produce a slight reduction in oxidant transport. In the second stage interstitial precipitation of Fe oxyhydroxide material between the colloidal particles reduces the oxidant’s diffusion coefficient by more than five orders of magnitude. This causes the pyrite oxidation rate to decline as the square root of time. The kinetic predominance diagram, which compares the rates of Fe transformation reactions, shows that when pyrite oxidation releases Fe quickly enough for the total Fe concentration to rise to about 10−8 m, ferrihydrite forms but lower rates of Fe release will not produce coatings. Extrapolation of the results to longer times predicts that pyrite-bearing materials need to be treated with an extra source of alkalinity for several decades to produce coatings that are thick enough to be sustained by alkalinity levels typical of groundwater. However, once the coatings develop no additional treatment is needed and further pyrite oxidation simply causes the coating to grow thicker and denser until the entire pyrite grain is pseudomorphically replaced by goethite.  相似文献   

7.
Limestone drains are often implemented in the treatment of acid mine drainage (AMD), but when the AMD contains high levels of dissolved Fe their lifetime is dependent on the rate of precipitation of Fe hydroxide on the limestone surface. This study used a small-scale laboratory experiment to define the longevity of a limestone drain by determining the thickness of the Fe coating encapsulating the limestone particles when the system lost its maximum neutralising potential. Synthetic AMD (100 mg/L Fe, pH 4–4.8) was pumped through a column containing limestone particles for 1110 h, when the effluent pH had dropped from a maximum of 6.45–4.9. The decline in neutralisation during the experiment was due to the formation of Fe hydroxide coatings on the limestone grains. These coatings are composed of lepidocrocite/goethite in three distinct layers: an initial thick porous orange layer, overlain by a dense dark brown crust, succeeded by a layer of loosely-bound, porous orange globules. After 744 h, a marked increase in the rate of pH decline occurred, and the system was regarded as having effectively failed. At this time the Fe hydroxide crust effectively encapsulated the limestone grains, forming a diffusion barrier that slowed down limestone dissolution. Between the coating and the limestone substrate was a 60 μm wide void, so that agitation of the limestone sample would readily remove the coating from the limestone surface.  相似文献   

8.
Field experiments were conducted over a 460-day period to assess the efficiency of different mixtures of organic substrates to remediate coalmine-generated acid mine drainage (AMD). Five pilot-scale, flow-through bioreactors containing mixtures of herbaceous and woody organic substrates along with one control reactor containing only limestone were constructed at the Tab-Simco site and exposed to AMD in situ. Tab-Simco is an abandoned coal mine near Carbondale, Illinois that produces AMD with pH ∼2.5 and notably high average concentrations of SO4 (5050 mg/L), Fe (950 mg/L), Al (200 mg/L), and Mn (44 mg/L). Results showed that the sequestration of SO4 and metals was achieved in all reactors; however, the presence and type of organic carbon matrix impacted the overall system dynamics and the AMD remediation efficiency. All organic substrate-based reactors established communities of sulfate reducing microorganisms that contributed to enhanced removal of SO4, Fe, and trace metals (i.e., Cu, Cd, Zn, Ni) via microbially-mediated reduction followed by precipitation of insoluble sulfides. Additional mechanisms of contaminant removal were active in all reactors and included Al- and Fe-rich phase precipitation and contaminant surface sorption on available organic and inorganic substrates. The organic substrate-based reactors removed more SO4, Fe, and Al than the limestone-only control reactor, which achieved an average removal of ∼19 mol% SO4, ∼49 mol% Fe, 36 mol% Al, and 2 mol% Mn. In the organic substrate-based reactors, increasing herbaceous content correlated with increased removal efficiency of SO4 (26–35 mol%), Fe (36–62 mol%), Al (78–83 mol%), Mn (2–6 mol%), Ni (64–81 mol%), Zn (88–95 mol%), Cu (72–85 mol%), and Cd (90–92 mol%), while the diversity of the intrinsic microbial community remained relatively unchanged. The extrapolation of these results to the full-scale Tab-Simco treatment system indicated that, over the course of a 460-day period, the predominantly herbaceous bioreactors could remove up to 92,500 kg SO4, 30,000 kg Fe, 8,950 kg Al, and 167 kg Mn, which represents a 18.3 wt%, 36.8 wt%, 4.1 wt% and 82.3 wt% increase in SO4, Fe, Al, and Mn, respectively, removal efficiency compared to the predominantly ligneous bioreactors.The results imply that anaerobic organic substrate bioreactors are promising technologies for remediation of coal-generated AMD and that increasing herbaceous content in the organic substrate matrix can enhance contaminant sequestration. However, in order to improve the remediation capacity, future designs must optimize not only the organic carbon substrate but also include a pretreatment phase in which the bulk of dissolved Fe/Al-species are removed from the influent AMD prior to entering the bioreactor because of 1) seasonal variations in temperature and redox gradients could induce dissolution of the previously formed redox sensitive compounds, and 2) microbially-mediated sulfate reduction activity may be inhibited by the excessive precipitation of Al- and Fe-rich phases.  相似文献   

9.
A series of experiments was conducted to better understand the bacterial influence on the release of trace metals during oxidation of sphalerite mineral and element cycles in acid mine drainage (AMD) systems. Batch experiments were carried out as biotic and abiotic control at pH 3. Acidithiobacillus ferrooxidans, sulfur and Fe(II) oxidizer, was used in the biotic sphalerite experiment. The abiotic control experiment was run without adding the bacteria. The release behavior of six trace metals (As, Cd, Co, Pb, Cu and Mn), Fe and Zn were determined during the period of 54 days. Compared to the abiotic experiments, enhanced oxidation of sphalerite by bacteria produced high sulfate (~2,000 mg/L) and Fetot (139 mg/L) along with the low pH (<2.3). Consistent with this, the concentration of trace metals (As, Cd, Co, Pb, Cu and Mn) was significantly higher in the biotic experiments than those in the abiotic experiments. Results indicate that the distributions of Co and Cd in both biotic and abiotic experiments are directly related to the sphalerite dissolution whereas Pb, Cu distribution shows no strong relation to sphalerite dissolution especially in the abiotic experiments. Pb distribution in the solution appears to be controlled by pH-dependent solubility. Approximately 80% of the trace metals were removed from the solution at the end of the biotic experiments along with biologically induced Fe precipitation. Experimental results showed that bacteria play major role not only in the release of trace metal from sphalerite but also in controlling concentration of the metals in the solution by producing Fe-oxyhydroxides. The study suggest that in order to develop an effective rehabilitation strategy for AMD, it is necessary to understand bio/geochemical processes governing mobilization and deposition of trace metals in the environment.  相似文献   

10.
Passive treatment systems have become one of the most sustainable and feasible ways of remediating acid mine drainage (AMD). However, conventional treatments show early clogging of the porosity or/and coating of the reactive grains when high acidity and metal concentrations are treated. The performance of fine-grained reagents dispersed in a high porosity matrix of wood shavings was tested as an alternative to overcome these durability problems. The system consisted of two tanks of 3 m3 filled with limestone sand and wood shavings, and one tank of 1 m3 with caustic magnesia powder and wood shavings, separated by several oxidation cascades and decantation ponds. The system treated about 1.5 m3/day of AMD containing an average of 360 mg/L Fe, 120 mg/L Al, 390 mg/L Zn, 10 mg/L Cu, 300 μg/L As and 140 μg/L Pb, a mean pH of 3.08 and a net acidity of 2500 mg/L as CaCO3 equivalent. The water reached pH 5 and 6 in the first and second limestone tanks, respectively (suitable to remove trivalent metals); and pH 8–9 in the MgO tank (suitable to remove divalent metals). After 9 months of operation, the system achieved an average removal of 100% Al, Cu, As, Pb, more than 70% Fe, about 25% Zn and 80% acidity. Goethite, schwertmannite, hydrobasaluminite, amorphous Al(OH)3 and gypsum were the main precipitates in the two limestone tanks. Precipitation of divalent metals (Fe (II), Zn, and traces of Cd, Ni and Co) were complete inside the third tank of MgO, but preferential flow along the walls was responsible for its low treatment performance. Goethite, gypsum, Zn-schulenbergite and sauconite are the crystalline solid phases identified in the MgO tank.  相似文献   

11.
The geochemical and mineralogical study of the Quiulacocha tailings impoundment has shown that the hydrological connection of the three studied mine-waste systems at Cerro de Pasco (Pyrite-rich waste-rock dump Excelsior, old tailings impoundment Quiulacocha, and the active tailings impoundment Ocroyoc) is a critical concern for effective acid mine drainage (AMD) control and mine-waste management. The Quiulacocha tailings covered 114 ha, comprising 79 Mt of tailings, which contained  50 wt.% pyrite, and are located at 4340 m altitude in a tropical puna climate with about 1025 mm/a rainfall and 988 mm/a of evaporation. The tailings were partially overlain by the Excelsior waste-rock dump, which contains about 26,400,000 m3 of waste rocks that cover 94 ha and contained  60 wt.% of pyrite, which origin from a massive pyrite-quartz replacement body. Therefore, these two mine-waste deposits had a direct hydrological connection, resulting in the export of AMD produced at Excelsior towards Quiulacocha. In the Quiulacocha impoundment there are two different types of tailings recognized, that interact with the AMD from Excelsior: 1) Zn–Pb-rich tailings and 2) Cu–As-rich tailings. During the sampling, the Zn–Pb-rich part of Quiulacocha was not producing important excesses of AMD from the oxidation zone, since the pH increased to near neutral values at 1 m depth. The underlying tailings were still able to neutralize the acidity produced in the oxidation zone through sulfide oxidation by the carbonates (mainly dolomite and siderite) contained in the Zn–Pb mineral assemblage. The main source of AMD in this mine-waste system is the Excelsior waste-rock dump. Its acid seepage infiltrates into Quiulacocha forming a Fe–Zn–Pb plume with a pH 5.5–6.1 and containing up to 7440 mg/L Fe, 627 mg/L Zn, and 1.22 mg/L Pb. The plume was detected at 10–13 m depth in the stratigraphy of Quiulacocha tailings. Additionally, the AMD seepage outcropping at the base of the Excelsior waste-rock dump was channeled on the tailings surface into the Quiulacocha pond (pH 2.3), which covered the Cu–As-rich tailings. Infiltration of this Fe(III)-rich AMD increased tailings oxidation in the southwestern part of the impoundment, and subsequently liberated arsenic by enargite oxidation. Additionally, the AMD collected in the Quiulacocha pond was pumped into the active Ocroyoc tailings impoundment, where sulfide oxidation was strongly enhanced by the input of dissolved Fe(III). Therefore, the AMD management and a hydrological separation of the different mine-waste systems could be a first step to prevent further extension of the AMD problem in order to prevent increased sulfide oxidation by Fe(III)-rich solutions.  相似文献   

12.
Ag, Pb, Sn and Zn ores have been intensively mined and processed at Cerro Rico de Potosí, Bolivia since 1545. Acid mine drainage (AMD) and mineral processing plant effluent are prime sources of water contamination in the headwaters of the Upper Rio Pilcomayo watershed. Streams receiving AMD drainage from the slopes of Cerro Rico and surrounding landscapes were sampled during the dry (July–August 2006) and wet (March 2007) seasons of one water-year. In-stream waters contained total metal concentrations of up to 16 mg/L As, 4.9 mg/L Cd, 0.97 mg/L Co, 1,100 mg/L Fe, 110 mg/L Mn, 4.1 mg/L Pb, and 1,500 mg/L Zn with pH ranging from 2.8 to 9.5. AMD-impacted streams contained elevated concentrations of the same major ecotoxic constituents present in AMD discharges at concentrations orders of magnitude greater than in those streams unimpacted by AMD. Many of the AMD impacted water bodies are more degraded than class “D” of the Bolivian receiving water body criteria, rendering them unfit for domestic or agricultural use. Natural attenuation is insufficient to render waters safe for use, however, some of these waters are currently being utilized for irrigation and livestock watering. The data indicate that historic and current mining activities have transformed these key natural resources into potential human and environmental health hazards.  相似文献   

13.
《Applied Geochemistry》1998,13(2):235-241
A series of experiments was conducted to study the uptake of Cu by colloidal SiO2 in aqueous solution. Solutions consisting of 2400 mg l−1 monomeric SiO2 were allowed to polymerize for 24 h at pH values from 4 to 9, producing coexisting populations of monomer and polymer in each solution. These solutions were combined with aqueous CuCl2 solutions in final Cu concentrations of 5–30 mg l−1. After the solutions had equilibrated for 24 h, they were filtered through 0.1 μm Millipore filters and analyzed by ICP-AES and gel filtration chromatography (GFC).Experiments conducted at pH 7 with varying Cu concentrations yielded a critical coagulation concentration of 15±1 mg l−1 Cu. GFC analyses of solutions in which coagulation occurred revealed no SiO2 polymer in the filtrates, suggesting that coagulation is due to the coalescence of SiO2 polymers by Cu. Experiments conducted with 20 mg l−1 Cu exhibited a gradual increase in Cu uptake from pH 5 to 7, followed by a sharp decrease in Cu uptake from pH 7.25 to 7.50. The gradual increase in Cu uptake up to pH 7 may reflect the increasingly negative surface charge of SiO2 polymer with increasing pH. The abrupt decrease in the adsorption of Cu to SiO2 polymer at pH values > 7.25 may be attributed to the decrease in dissociated Cu2+ relative to Cu(OH)2° at higher pH. Although it is traditionally held that the formation of Cu silicates, such as chrysocolla, occurs under acid conditions in supergene Cu deposits, this investigation suggests that Cu silicate formation may be favored in near-neutral solutions in nature.  相似文献   

14.
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   

15.
《Geochimica et cosmochimica acta》1999,63(19-20):3171-3182
The oxidation rate of pyrite at pH 7, 25°C and at constant partial pressure of oxygen (0.21 and 0.177 atm) was measured in the presence of the Fe(III)-chelators NTA, oxalate, leucine, EDTA, citrate, IDA and the Fe(III)-reductant ascorbic acid. With the exception of leucine and EDTA, non-reducing Fe(III)-chelators increased the oxidation rate relative to the reference state of formation of the Fe(OH)2+ complex at pH 7. The rate increase was proportional to the logarithm of the conditional stability constant of the ligands for the complexation of Fe3+. No effect on the oxidation rate was observed in the presence of EDTA, which shifted the redox potential of the redox couple Fe2+/Fe3+ to a value below that in the absence of any ligand at pH 7. Ascorbic acid decreased the pyrite oxidation rate by a factor of 5 at ascorbic acid concentrations between 10−4 and 10−2 mol L−1. Comparison of the rate constants for the oxidation of ascorbic acid by surface bound Fe(III) in the absence and presence of pyrite shows that the pyrite surface accelerates this reaction by a factor of 10. The oxidation of both pyrite and ascorbic acid is of fractional order with respect to ascorbic acid (HAsc): rpy=0.55 c(HAsc)−0.35 rHAsc=3.6 c(HAsc)0.59. Both the results from experiments with Fe(III)-chelating ligands and the Fe(III)-reductant, suggest a very efficient interference in the electron cycling between Fe(II) and Fe(III) at the pyrite surface. The interference seems to be mainly related to the reductive side of the iron cycling. It is therefore concluded that the electron transfer between ferric iron and pyritic sulfur limits the pyrite oxidation rate at pH 7.  相似文献   

16.
Acid mine drainage (AMD) from the Zn–Pb(–Ag–Bi–Cu) deposit of Cerro de Pasco (Central Peru) and waste water from a Cu-extraction plant has been discharged since 1981 into Lake Yanamate, a natural lake with carbonate bedrock. The lake has developed a highly acidic pH of ∼1. Mean lake water chemistry was characterized by 16,775 mg/L acidity as CaCO3, 4330 mg/L Fe and 29,250 mg/L SO4. Mean trace element concentrations were 86.8 mg/L Cu, 493 mg/L Zn, 2.9 mg/L Pb and 48 mg/L As, which did not differ greatly from the discharged AMD. Most elements showed increasing concentrations from the surface to the lake bottom at a maximal depth of 41 m (e.g. from 3581 to 5433 mg/L Fe and 25,609 to 35,959 mg/L SO4). The variations in the H and O isotope compositions and the element concentrations within the upper 10 m of the water column suggest mixing with recently discharged AMD, shallow groundwater and precipitation waters. Below 15 m a stagnant zone had developed. Gypsum (saturation index, SI ∼ 0.25) and anglesite (SI ∼ 0.1) were in equilibrium with lake water. Jarosite was oversaturated (SI ∼ 1.7) in the upper part of the water column, resulting in downward settling and re-dissolution in the lower part of the water column (SI ∼ −0.7). Accordingly, jarosite was only found in sediments from less than 7 m water depth. At the lake bottom, a layer of gel-like material (∼90 wt.% water) of pH ∼1 with a total organic C content of up to 4.40 wet wt.% originated from the kerosene discharge of the Cu-extraction plant and had contaminant element concentrations similar to the lake water. Below the organic layer followed a layer of gypsum with pH 1.5, which overlaid the dissolving carbonate sediments of pH 5.3–7. In these two layers the contaminant elements were enriched compared to lake water in the sequence As < Pb ≈ Cu < Cd < Zn = Mn with increasing depth. This sequence of enrichment was explained by the following processes: (i) adsorption of As on Fe-hydroxides coating plant roots at low pH (up to 3326 mg/kg As), (ii) adsorption at increasing pH near the gypsum/calcite boundary (up to 1812 mg/kg Pb, 2531 mg/kg Cu, and 36 mg/kg Cd), and (iii) precipitation of carbonates (up to 5177 mg/kg Zn and 810 mg/kg Mn; all data corrected to a wet base). The infiltration rate was approximately equal to the discharge rate, thus gypsum and hydroxide precipitation had not resulted in complete clogging of the lake bedrocks.  相似文献   

17.
Lead- and Pb-As-jarosites are minerals common to acidic, sulphate-rich environments, including weathering zones of sulphide ore deposits and acid rock or acid mine drainage (ARD/AMD) sites, and often form on or near galena. The structures of these jarosites are based on linear tetrahedral-octahedral-tetrahedral (T-O-T) sheets, comprised of slightly distorted FeO6 octahedra and SO42− (-AsO43− in Pb-As-jarosites) tetrahedra. To better understand the dissolution mechanisms and products of the break down of Pb- and Pb-As-jarosite, preliminary batch dissolution experiments were conducted on synthetic Pb- and Pb-As-jarosite at pH 2 and 20 °C, to mimic environments affected by ARD/AMD, and at pH 8 and 20 °C, to simulate ARD/AMD environments recently remediated with slaked lime (Ca(OH)2). All four dissolutions are incongruent. Dissolution of Pb-jarosite at pH 2 yields aqueous Pb, Fe and SO42−. The pH 8 Pb-jarosite dissolution yields aqueous Pb, SO42− and poorly crystalline Fe(OH)3, which does not appear to resorb Pb or SO42−, possibly due to the low solution pH (3.44-3.54) at the end of the experiment. The pH 2 and 8 dissolutions of Pb-As-jarosite result in the formation of secondary compounds (poorly crystalline PbSO4 for pH 2 dissolution; poorly crystalline PbSO4 and Fe(OH)3 for pH 8 dissolution), which may act as dissolution inhibitors after 250 to 300 h of dissolution. In the pH 2 dissolution, aqueous Fe, SO42− and AsO43− also form, and in the pH 8 dissolution, Fe(OH)3 precipitates then subsequently resorbs aqueous AsO43−. The dissolutions probably proceed by preferred dissolution of the A- and T-sites, which contain Pb, and SO42− and AsO43−, respectively, rather than Fe, which is sterically remote, within the T-O-T Pb- and Pb-As-jarosite structures. These data provide the foundation necessary for further, more detailed investigations into the dissolution of Pb- and Pb-As-jarosites.  相似文献   

18.
Rio Marina mining district (Elba Island) is characterised by hematite + pyrite ore association and was exploited for iron till 1981, leaving waste rock dumps of several millions m3. The effect of open pit mining activity in this site is to produce acid mine drainage (AMD) processes leading to environmental pollution, testified by all the sampled waters (Giove stream, drainage channels, superficial pools and settling basin) which have pH values ranging from 2.08 to 3.35 and heavy metal concentrations that reach 903.16 mg/l for Fe, 45.02 mg/l for Mn, 10.08 mg/l for Zn and 1.75 mg/l for Cu. In the present work a space and time related approach to geochemical hazard evaluation was applied. The geochemical hazard is mainly related to high heavy metal concentration, acid mine drainage processes development and topographic setting. As all these parameters are related in space, hazard evaluation was performed by geostatistical methods. Fifty-four earth material samples (residual soils, waste rocks or debris materials) were collected in a central aligned 100 m mesh square grid. These were analysed for major elements by XRF, for Cu, Pb, Zn by ICP-AES and for AMD potential following the AMIRA procedure. The concentration of heavy metals was compared with Italian law limits. The overlap of Cu, Pb and Zn content maps show that at least one of these heavy metals exceed law limits in all the area. The AMD test results show that more than 50% of samples have a positive NAPP (Net Acid Producing Potential) that could reach 258.9 kg H2SO4/t. According to the obtained data, three main geochemical hazard classes were established and their distribution in the mining area was assessed. About 51% of the mining area surface belongs to the major hazard class, where AMD process occurs, about 49% belongs to an intermediate hazard class, where AMD process could occur only if certain conditions are met. Finally, the persistence of the AMD process in the Rio Marina area was evaluated on the basis of yearly rainfall, mining waters pH and NAPP values. A complete leaching of the first 0.25 m of the earth materials can retain the current environmental conditions for several centuries.  相似文献   

19.
Fayalite, hypersthene, basalt, and obsidian were dissolved in buffered solutions (25°C; pH 4.5 and 5.5) under air, N2 or O2 atmospheres, in order to follow the kinetics of dissolution. Each dissolved more rapidly at lower pH values, dissolving most rapidly in the initial few days, followed by slower dissolution for periods up to six months. Dissolution was more rapid when air was excluded. In oxygen atmospheres an Fe(OH)3 precipitate armors mineral surfaces, thus inhibiting further dissolution, and further affects the solution by scavenging dissolved silica and cations. Dissolution reactions include initial exchange between cations and H+, incongruent dissolution of silicate structures, oxidation of Fe2+ in solution, precipitation of Fe(OH)3, and scavenging of dissolved silica and cations by Fe(OH)3. Dissolution kinetics may explain weathering of mafic rocks and minerals at the Earth's surface, the formation of Fe-oxide coatings on mineral grains, weathering of submarine mafic rocks and intrastratal solution of mafic minerals in buried sandstones. Early Precambrian weathering would have been more rapid before the appearance of large amounts of oxygen in the atmosphere, and continental denudation rates may have been higher than at present because of this effect and the predominance of mafic igneous rocks at an early stage of continent formation and growth.  相似文献   

20.
The historical disposal of acidic chromium sulfate solutions into unlined lagoons between 1953 and 1970 at an industrial site resulted in formation of a dense aqueous phase liquid (DAPL) plume [specific gravity 1.11 g/cm3, pH 3, up to 4700 mg/L Cr(III), and up to 90,000 mg/L SO4]. The DAPL sank through the shallow glacial till aquifer to an underlying impermeable gneissic bedrock from where it migrated downgradient along buried channels incised in the bedrock. Because of its high density, the plume chemistry is sharply stratified vertically. Chromium(III) predominates in the DAPL because excess Cr(VI) not reduced in the original process has been reduced by Fe(II) derived from silicates, while Cr(OH)3(am) occurs as surface coatings on silicate minerals and as discrete particles mixed with Fe(OH)3(am) and Al(OH)3(am). The solubility of Cr(OH)3(am) accurately describes Cr(III) concentrations in the plume and nearby groundwater, while Al and Fe in solution are also consistent with solubility-controlling oxyhydroxides. Because of these solubility controls, metal cations are attenuated relative to more mobile Cl and SO4, resulting in a chromatographic separation of solutes downgradient from the plume origin. The good agreement between predicted and observed solution concentrations illustrates the utility of equilibrium modeling when interpreting metal transport characteristics and in determining the efficacy of natural attenuation in subsurface systems.  相似文献   

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