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1.
Monitoring wells are often installed in aquitards to verify effectiveness for preventing migration of surface contaminants to underlying aquifers. However, water sampling of aquitard wells presents a challenge due to the slow recovery times for water recharging the wells, which can take as long as weeks, months or years to recharge depending on the sample volume needed. In this study, downhole profiling and sampling of aquitard wells was used to assess geochemical changes that occur in aquitard wells during water level recovery. Wells were sampled on three occasions spanning 11 years, 1 year and 1 week after they were purged and casing water showed substantial water chemistry variations. Temperature decreased with depth, whereas pH and specific conductance increased with depth in the water column after 11 years of water level recovery. Less stable parameters such as dissolved O2 (DO) and Eh showed strong zonation in the well column, with DO stratification occurring as the groundwater slowly entered the well. Oxidation of reduced till groundwater along with degassing of CO2 from till pore water affects mineral solubility and dissolved solid concentrations. Recommendations for sampling slowly recovering aquitard wells include identifying the zone of DO and Eh stratification in the well column and collecting water samples from below the boundary to better measure unstable geochemical parameters.  相似文献   

2.
《Applied Geochemistry》1999,14(4):485-498
Fine grained (ca. 15 μm), arsenopyrite-bearing mine tailings have been exposed to drying and oxidation for 4 a pending relocation. The tailings are still partly covered by a pond of decanted pore waters. The water table in drying tailings has lowered by 1–3 m and desiccation cracks up to 2 cm wide have formed on the 1 m scale, extending through the unsaturated zone. Tailings in the unsaturated zone have similar pore water contents to saturated tailings: typically 16–32 wt% water. Saturated tailings retain alkaline pH (ca. 10) from the mine cyanidation plant, but pH lowers progressively towards ca. 7 near the surface, or near desiccation cracks, in the unsaturated zone. The redox state of the tailings changes in parallel with pH, with an empirical relationship: Eh(mV)=−55 pH+290. Water in the remnant decant pond reflects this relationship also. Unsaturated tailings have variable but low permeabilities, typically 10−3 to 10−4 m/day, and more permeable horizons have allowed incursion of oxygenated air and/or rain water from desiccation cracks. Sulphide grains in all tailings examined are unaltered. Sulphides and solutions in the tailings are out of thermodynamic equilibrium predicted from the redox–pH conditions, due to kinetic constraints. Incursion of rain water locally facilitates deposition from pore waters of insoluble Fe oxide and arsenate minerals, thus fixing As in the dry unsaturated tailings.  相似文献   

3.
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   

4.
《Geochimica et cosmochimica acta》1999,63(19-20):3379-3394
The proposed JEB Tailings Management Facility (TMF) to be emplaced below the groundwater table in northern Saskatchewan, Canada, will contain uranium mill tailings from McClean Lake, Midwest and Cigar Lake ore bodies, which are high in arsenic (up to 10%) and nickel (up to 5%). A serious concern is the possibility that high arsenic and nickel concentrations may be released from the buried tailings, contaminating adjacent groundwaters and a nearby lake. Laboratory tests and geochemical modeling were performed to examine ways to reduce the arsenic and nickel concentrations in TMF porewaters so as to minimize such contamination from tailings buried for 50 years and longer. The tests were designed to mimic conditions in the mill neutralization circuit (3 hr tests at 25°C), and in the TMF after burial (5–49 day aging tests). The aging tests were run at, 50, 25 and 4°C (the temperature in the TMF). In order to optimize the removal of arsenic by adsorption and precipitation, ferric sulfate was added to tailings raffinates1 having Fe/As ratios of less that 3–5. The acid raffinates were then neutralized by addition of slaked lime to nominal pH values of 7, 8, or 9.Analysis and modeling of the test results showed that with slaked lime addition to acid tailings raffinates, relatively amorphous scorodite (ferric arsenate) precipitates near pH 1, and is the dominant form of arsenate in slake limed tailings solids except those high in Ni and As and low in Fe, in which cabrerite-annabergite (Ni, Mg, Fe(II) arsenate) may also precipitate near pH 5–6. In addition to the arsenate precipitates, smaller amounts of arsenate are also adsorbed onto tailings solids.The aging tests showed that after burial of the tailings, arsenic concentrations may increase with time from the breakdown of the arsenate phases (chiefly scorodite). However, the tests indicate that the rate of change decreases and approaches zero after 72 hrs at 25°C, and may equal zero at all times in the TMF at 4°C. Consistent with a kinetic model that describes the rate of breakdown of scorodite to form hydrous ferric oxide, the rate of release of dissolved arsenate to tailings porewaters from slake limed tailings: (1) is proportional to pH above pH 6–7; (2) decreases exponentially as the total molar Fe/As ratio of tailings raffinates is increased from 1/1 to greater than 5/1; and (3) is proportional to temperature with an average Arrhenius activation energy of 13.4 ± 4.2 kcal/mol.Study results suggest that if ferric sulfate and slaked lime are added in the tailings neutralization circuit to give a raffinate Fe/As molar ratio of at least 3–5 and a nominal (initial) pH of 8 (final pH of 7–8), arsenic and nickel concentrations of 2 mg/L or less, are probable in porewaters of individual tailings in the TMF for 50 to 10,000 yrs after tailings disposal. However, the tailings will be mixed in the TMF, which will contain about 35% tailings with Fe/As = 3.0, and 65% tailings with Fe/As = 5.0–7.7. Thus, it seems likely that average arsenic pore water concentrations in the TMF may not exceed 1 mg/L.  相似文献   

5.
The distribution of As, Mo, Ni and Se in the aqueous and solid phases of U mine tailings in the Deilmann Tailings Management Facility (DTMF), located at the Key Lake mine in northern Saskatchewan, Canada, was defined using as-discharged tailings samples collected monthly starting in 1996 and core samples collected from the DTMF from 3 locations on 3 occasions between 2004 and 2009. These data indicated that the DTMF can be divided into two geochemical zones; tailings generated from the Deilmann ore body between 1996 and 2000 and tailings from the McArthur River ore body, mined after July 2000. The Deilmann tailings solids are generally characterized by greater elemental concentrations than those in the McArthur River tailings, particularly for As, Co and Ni. These elevated concentrations are attributed to the abundance of Ni–Co–As–S minerals in this ore. The mean aqueous concentrations of As, Mo, Ni, and Se are 3.7, 23.2, 0.14, and 0.02 mg L−1, respectively, in the Deilmann porewaters and 0.20, 4.16, 0.06, and 0.03 mg L−1, respectively, in the McArthur River porewaters. Similarly, the mean As, Mo, Ni, and Se solid phase concentrations are 5.89 × 103, 69.9, 3.20 × 103, and 17.4 μg g−1, respectively, for the Deilmann tailings and 440, 13.6, 551, and 3.03 μg g−1 in the McArthur River tailings. Statistically, pH remained unchanged from the time of discharge while Eh values have remained oxic with no significant change between the two tailings types over 15 a of residence time. Results from sequential extractions, thermodynamic modeling, and results of complimentary research indicated that ferrihydrite solubility is the dominant control on aqueous As concentrations and also plays a role in controlling dissolved Mo, Ni and Se.  相似文献   

6.
《Applied Geochemistry》2005,20(3):639-659
The oxidation of sulfide minerals from mine wastes results in the release of oxidation products to groundwater and surface water. The abandoned high-sulfide Camp tailings impoundment at Sherridon, Manitoba, wherein the tailings have undergone oxidation for more than 70 a, was investigated by hydrogeological, geochemical, and mineralogical techniques. Mineralogical analysis indicates that the unoxidized tailings contain nearly equal proportions of pyrite and pyrrhotite, which make up to 60 wt% of the total tailings, and which are accompanied by minor amounts of chalcopyrite and sphalerite, and minute amounts of galena and arsenopyrite. Extensive oxidation in the upper 50 cm of the tailings has resulted in extremely high concentrations of dissolved SO4 and metals and As in the tailings pore water (pH < 1, 129,000 mg L−1 Fe, 280,000 mg L−1 SO4, 55,000 mg L−1 Zn, 7200 mg L−1 Al, 1600 mg L−1 Cu, 260 mg L−1 Mn, 110 mg L−1 Co, 97 mg L−1 Cd, 40 mg L−1 As, 15 mg L−1 Ni, 8 mg L−1 Pb, and 3 mg L−1 Cr). The acid released from sulfide oxidation has been extensive enough to deplete carbonate minerals to 6 m depth and to partly deplete Al-silicate minerals to a 1 m depth. Below 1 m, sulfide oxidation has resulted in the formation of a continuous hardpan layer that is >1 m thick. Geochemical modeling and mineralogical analysis indicate that the hardpan layer consists of secondary melanterite, rozenite, gypsum, jarosite, and goethite. The minerals indicated mainly control the dissolved concentrations of SO4, Fe, Ca and K. The highest concentrations of dissolved metals are observed directly above and within the massive hardpan layer. Near the water table at a depth of 4 m, most metals and SO4 sharply decline in concentration. Although dissolved concentrations of metals and SO4 decrease below the water table, these concentrations remain elevated throughout the tailings, with up to 60,600 mg L−1 Fe and 91,600 mg L−1 SO4 observed in the deeper groundwater. During precipitation events, surface seeps develop along the flanks of the impoundment and discharge pore water with a geochemical composition that is similar to the composition of water directly above the hardpan. These results suggest that shallow lateral flow of water from a transient perched water table is resulting in higher contaminant loadings than would be predicted if it were assumed that discharge is derived solely from the deeper primary water table. The abundance of residual sulfide minerals, the depletion of aluminosilicate minerals in the upper meter of the tailings and the presence of a significant mass of residual sulfide minerals in this zone after 70 a of oxidation suggest that sulfide oxidation will continue to release acid, metals, and SO4 to the environment for decades to centuries.  相似文献   

7.
Models of geochemical controls on elements of concern (EOCs; e.g., As, Se, Mo, Ni) in U tailings are dominated by ferrihydrite. However, the evolution of aqueous concentrations of Al and Mg through the Key Lake (KL) U mill bulk neutralization process indicates that secondary Al and Mg minerals comprise a large portion of the tailings solids. X-ray diffraction, Al K-edge XAS, and TEM elemental mapping of solid samples collected from a pilot-scale continuous-flow synthetic raffinate neutralization system of the KL mill indicate the secondary Al–Mg minerals present include Mg–Al hydrotalcite, amorphous Al(OH)3, and an amorphous hydrobasaluminite-type phase. The ferrihydrite present contains Al and may be more accurately described as Al–Fe(OH)3. In the final combined tailings sample (pH 10.5) collected from the model experiments using raffinate with Al, Mg, and Fe, solid phase EOCs were associated with Al–Fe(OH)3 and Mg–Al hydrotalcite. In model experiments using raffinate devoid of Fe, aqueous EOC concentrations decreased greatly at pH 4.0 (i.e., where ferrihydrite would precipitate) and largely remained in the solid phase when increased to the terminal pH of 10.5; this suggests Al–Mg minerals can control aqueous concentrations of EOCs in the raffinate in the absence of Fe. Maximum adsorption capacities for individual and mixtures of adsorbates by Mg–Al hydrotalcite were determined. A revised model of the geochemical controls in U mill tailings is presented in which Al and Mg minerals co-exist with Fe minerals to control EOC concentrations.  相似文献   

8.
《Applied Geochemistry》2005,20(5):947-959
At the McClean Lake Operation in the Athabasca Basin of northern Saskatchewan, the untreated acid raffinate solutions associated with U mill tailings contain up to 700 mg/L dissolved As. To reduce the concentration of As and other contaminants in acid tailing slurries at the JEB mill at McClean Lake, ferric sulfate may be added to the acid raffinates to assure that their molar Fe/As ratio equals or exceeds 3. Tailings slurries are then neutralized with lime to pH 4, and subsequently to pH 7–8. The neutralized tailings contain minerals from the original ore, which are chiefly quartz, illite, kaolinite and chlorite, and precipitated (secondary) minerals that include gypsum, scorodite, annabergite, hydrobasaluminite and ferrihydrite. Most of the As is associated with the secondary arsenate minerals, scorodite and annabergite. However, a few percent is adsorbed and/or co-precipitated, mainly by ferrihydrite. Of major concern to provincial and federal regulators is the risk that significant amounts of As might be released from the tailings to pore waters after their subaqueous disposal in the tailings management facility. A laboratory study was performed to address this issue, measuring readily desorbed As using a method known as equilibrium partitioning in closed systems (EPICS). The EPICS method was selected because it employs a leaching solution that, except for its As concentration, is identical in composition to the neutralized raffinate in contact with the tailings. Laboratory experiments and modeling results demonstrated that the As that could be readily released to pore waters is about 0.2% of the total As in the tailings. Long-term, such releases may contribute no more than a few mg/L of dissolved As to tailings pore waters.  相似文献   

9.
This study was conducted to define the geochemical controls on 226Ra during raffinate (pH = 1.2) neutralization to pH 10 at the Key Lake U mill in northern Saskatchewan, Canada. High activities (120–150 Bq/L) of aqueous phase 226Ra are present in raffinate produced during milling of U ore. The solubility control of 226Ra in the SO4-rich, hydrometallurgical raffinate solutions often involves the addition of BaCl2 to form a radium-barite co-precipitate (Ba(Ra)SO4). As such, neutralization experiments were conducted with samples of mill raffinate using Ca(OH)2 or NaOH with and without the addition of BaCl2. Radium-226 activity decreased from 150 to <4 Bq/L for all combinations of neutralizing agents with Ca(OH)2 + BaCl2 being the most effective combination (final activity ∼1.0 Bq/L; ∼99.3% removal). In the absence of BaCl2, Ca(OH)2 more efficiently removed 226Ra than NaOH between pH 4 and 8, due to the co-precipitation of 226Ra with gypsum. Overall, neutralization with the addition of BaCl2 reduced 226Ra activities at lower pH values (by pH 4.5), due to co-precipitation of 226Ra with BaSO4. At varying concentrations of BaCl2, aqueous phase activities of 226Ra converged, but did not attain steady-state values during neutralization and would continue to decrease with time. Sequential extractions indicated that 226Ra in precipitates formed during neutralization of the mill raffinate is dominated by amorphous and crystalline Fe hydroxide phases, consistent with raffinate neutralization experiments that showed that adsorption onto ferrihydrite can remove most 226Ra in the raffinate. Data generated in this study are being used to define the long-term geochemical controls on 226Ra in U mill processes and tailings.  相似文献   

10.
《Applied Geochemistry》2002,17(8):1105-1114
Tailings from the Macraes Au mine cyanidation process are stored in an impoundment about 0.6 km2 and 80 m deep whose pH is maintained near 8 by the neutralizing capacity of the gangue minerals. The tailings are sandy (>50 μm particles), have a hydraulic conductivity of about 10−2 m/day, and contain 0.1–1.0 wt.% S and 0.1–1.5 wt.% graphitic C from the primary deposit. Concentrations of As in the pore water of the mixed tailings, which are a combination of various tailings types, range from 0.1 to 20 ppm, HCO3- is 100 to 200 ppm, and dissolved SO4 is 100–1700 ppm. The mixed tailings will be stored in this impoundment in perpetuity after mining ceases. Confidence in the long-term pH stability of these tailings can be gained from examination of mineralogically and chemically similar geological analogues in the immediate vicinity. A sequence, typically about 5 m thick, of sands and gravels derived from the Macraes mineralized zone 12–28 ka ago contains rounded detrital sulfide mineral grains which are unoxidized despite their close proximity to the surface and the occasional incursion of oxygenated waters. These sediments have a hydraulic conductivity of about 10−4 m/day. Saturating water pH is currently 7–8. Sands with 0.2–0.8 wt.% organic C host SO4-reducing bacteria (SRB), and local cementation by authigenic framboidal pyrite has occurred. SRB were found in water-saturated sediments with decreased hydraulic conductivity and alkaline and anoxic conditions. These bacteria are involved in the formation of authigenic framboidal pyrite, reducing the cycling of dissolved Fe in the sediments. Carbon is not a limiting factor in this process as organic matter is present in the sandstone and ground water contains up to 180 ppm HCO3-. Comparison of the 28 ka old sediments with the modern tailings suggests that the chemical behaviour of the two will be similar, possibly with the crystallization of authigenic pyrite in the tailings over the long term. As long as the present slightly anoxic and circumneutral pH environmental conditions are maintained in the mixed tailings impoundment, sulfide decomposition and acidification are unlikely.  相似文献   

11.
Mineralogical, geochemical and microbial characterization of tailings solids from the Greens Creek Mine, Juneau, Alaska, was performed to evaluate mechanisms controlling aqueous geochemistry of near-neutral pH pore water and drainage. Core samples of the tailings were collected from five boreholes ranging from 7 to 26 m in depth. The majority of the 51 samples (77%) were collected from the vadose zone, which can extend >18 m below the tailings surface. Mineralogical investigation indicates that the occurrence of sulfide minerals follows the general order: pyrite [FeS2] >> sphalerite [(Zn,Fe)S] > galena [PbS], tetrahedrite [(Fe,Zn,Cu,Ag)12Sb4S13] > arsenopyrite [FeAsS] and chalcopyrite [CuFeS2]. Pyrite constitutes <20 to >35 wt.% of the tailings mineral assemblage, whereas dolomite [CaMg(CO3)2] and calcite [CaCO3] are present at ?30 and 3 wt.%, respectively. The solid-phase geochemistry generally reflects the mineral assemblage. The presence of additional trace elements, including Cd, Cr, Co, Mo, Ni, Se and Tl, is attributed to substitution into sulfide phases. Results of acid–base accounting (ABA) underestimated both acid-generating potential (AP) and neutralization potential (NP). Recalculation of AP and NP based on solid-phase geochemistry and quantitative mineralogy yielded more representative results. Neutrophilic S-oxidizing bacteria (nSOB) and SO4-reducing bacteria (SRB) are present with populations up to 107 and 105 cells g−1, respectively. Acidophilic S-oxidizing bacteria (aSOB) and iron-reducing bacteria (IRB) were generally less abundant. Primary influences on aqueous geochemistry are sulfide oxidation and carbonate dissolution at the tailings surface, gypsum precipitation–dissolution reactions, as well as Fe reduction below the zone of sulfide oxidation. Pore-water pH values generally ranged from 6.5 to 7.5 near the tailings surface, and from approximately 7–8 below the oxidation zone. Elevated concentrations of dissolved SO4, S2O3, Fe, Zn, As, Sb and Tl persisted under these conditions.  相似文献   

12.
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   

13.
The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO4·2H2O), ferric arsenates, arseniosiderite (Ca2Fe3(AsO4)3O2·3H2O), Ca-Fe arsenates, pharmacosiderite (KFe4(AsO4)3(OH)4·6-7H2O), jarosite (K2Fe6(SO4)4(OH)12) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%.Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As5+in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 Å and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides.The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore.  相似文献   

14.
An industrial area contaminated by As was studied to determine the source of this element and its speciation in As-bearing solids and in run-off waters. Mineral precipitates and water samples were collected and analyzed to assess processes controlling As mobility at this site. The integrated study of a contaminated industrial area allowed identification of the source of the As and of the nature of secondary As-bearing phases. The results obtained both on solid and water samples were used to model As behavior during waste leaching on carbonate rocks. At the upper end of a topographic transect across the site, run-off waters (pH=7.9) interact with surficial waste piles (containing arsenolite, arsenopyrite and pyrite), becoming acidic (pH=2.2) and concentrated in dissolved arsenate species (As5+) (ΣAs ranging from 0.961 to 3.149·10−3 mol/l). Those acidic waters interact with the limestone substratum, providing dissolved Ca which reacts with As to precipitate 1:1 Ca arsenates (weilite CaHAsO4, haidingerite CaHAsO4.H2O and pharmacolite CaHAsO4.2H2O) and, in minor amounts, Ca–Mg arsenates (picropharmacolite (Ca,Mg)3(AsO4)2 6H2O). The 1:1 Ca arsenates identified are known to precipitate at low pH (3–6) and seem to be stable in media with high dissolved CO2, in comparison with other types of Ca arsenates. However, due to their high solubilities, they are not strictly relevant candidates to immobilize As in contaminated surficial environments. Although reported solubilities decrease to values close to the French and US drinking standards in Ca-rich solutions, a thorough examination of the precipitation/dissolution kinetics of Ca arsenates should be undertaken to assess their long-term stability and their efficiency in rapidly immobilizing As in contaminated surficial environments.  相似文献   

15.
The pore-water geochemistry and mineralogy of tailings derived from a granitic tungsten deposit were characterized by collecting pore-water samples at discrete depth intervals throughout the tailings for the analysis of major and minor element concentrations. Mineralogical samples from the oxidation zone were analyzed by X-ray diffraction, scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM/EDS), electron microprobe (EMP) combined with wavelength dispersive X-ray spectroscopy (WDS), and transmission electron microscopy (TEM). The oxidation of sulfide minerals in the near-surface tailings leads to a decrease in pore-water pH and elevated SO4, As, and metal concentrations. The unusual mineralogy of this deposit, compared with that of commonly studied base-metal and gold deposits, results in several unique geochemical characteristics. The dissolution of fluorite releases F into the pore water; the F forms strong complexes with Al and enhances the dissolution of aluminosilicate minerals within the oxidation zone. As a result, high Al concentrations (up to 151.7 mg/L) are detected in the near-neutral pore water in the oxidation zone. The combined dissolution of aluminosilicates and carbonate minerals maintains the pH near 10 in the pore water at depth. Elevated concentrations of W (up to 7.1 mg/L) are detected in the pore water throughout the tailings, likely as a result of the dissolution of wolframite. Consistent with geochemical model calculations, results from SEM/EDS, EMP/WDS and TEM/EDS analyses indicate that secondary minerals, which occur as orange-brown coatings on grains of primary-minerals, are Fe oxyhydroxides. Examples of these secondary minerals display a fibrous habit at high resolution in the TEM. One of these minerals, which contains substantial amounts of Al, As, and Si as impurities, was identified by selected-area electron diffraction (SAED) analyses to be goethite. Another mineral contains relatively high amounts of Si, Pb, Bi, and As, and SAED analyses suggest that the mineral is two-line ferrihydrite.  相似文献   

16.
Generation of dust particles from the Owens Lake playa creates a severe air pollution hazard in the western United States. Much of the dust produced from the dry lakebed is derived from salts formed by evaporation of saline groundwater that often contains high concentrations of dissolved arsenic (As). The objectives of this research were to study the spatial distribution of dissolved arsenic in the shallow groundwater, and to examine factors affecting arsenic solubility and speciation. Evapoconcentration, redox potential, pH, and mineral solubility were examined as factors regulating arsenic biogeochemistry. Dissolved arsenic concentrations ranged from 0.1 to 96 mg L−1 and showed a general increase from the shoreline to the center of the lakebed. Arsenic concentrations were strongly correlated to electrical conductivity (EC) and δD suggesting that evapoconcentration is an important process regulating total As concentrations. Arsenite [As(III)] was the dominant form of inorganic arsenic at Eh values less than about −170 mV while arsenate [As(V)] was predominant at higher Eh values. Organic arsenic was negligible (<0.21%) in all shallow groundwater samples. Dissolved arsenic concentrations do not appear to be strongly regulated by solid-phase reactions. Solid-phase arsenic concentrations generally ranged between 4.0 and 42.6 mg kg−1 and a maximum concentration range (20 to 40 mg kg−1) was reached as solution concentration increased up to 80 mg L−1, indicating minimal sorption and/or precipitation of arsenic. Chemical equilibrium modeling indicated that orpiment (As2S3) was the only solid phase with a positive saturation index (indicating over-saturation), but only at high arsenic and sulfide concentrations. The findings of this research are important for assessing the potential environmental impacts of elevated arsenic concentrations on dust mitigation efforts taking place at Owens Dry Lake.  相似文献   

17.
Detailed field sampling and analyses and laboratory-based diffusion-cell experiments were used in conjunction with 3-D reactive transport modeling (MODFLOW and MT3D99) to quantify the fate and long-term (10 ka) transport of As in the Rabbit Lake In-pit Tailings Management Facility (RLITMF), northern Saskatchewan, Canada. The RLITMF (300 m × 425 m × 90 m thick) was engineered to ensure solute transport within the RLITMF is dominated by diffusion. Concentrations of As in the tailings pore fluids ranged from 0.24 to 140 mg/L (n = 43). Arsenic speciation analyses indicate 90% of this arsenic exists as As5+. This observation is supported by pH–Eh measurements of pore fluids (n = 135). Geochemical analyses yielded a strong inverse correlation between the Fe/As molar ratio in the tailings solids and the corresponding concentration of dissolved As, which is attributed to the adsorption of As to secondary 2-line ferrihydrite present in the tailings. Diffusion-cell testing yielded values for the effective diffusion coefficient, sorption coefficient, and effective porosity of As in the tailings of 4.5 × 10−10 m2/s, 2–4 cm3/g and 0.36, respectively. Reactive transport simulations using the field and laboratory data show adsorption of As to the tailings and diffusive transport of dissolved As in the tailings should reduce the source term concentration of As to between 40% and 70% of the initial concentrations over the 10 ka simulation period. Based on these simulations, the As concentrations in the regional groundwater, 50 m down gradient of the tailings facility, should be maintained at background concentrations of 0.001 mg/L over the 10 ka period. These findings suggest the engineered in-pit disposal of U mine tailings can provide long-term protection for the local groundwater regime from As contamination.  相似文献   

18.
《Applied Geochemistry》2000,15(8):1097-1119
The Rabbit Lake U mine in-pit tailings management facility (TMF) is located in northern Saskatchewan, Canada. The tailings body is approximately 425 m long×300 m wide and 91 m thick at its centre. An investigation of the TMF was performed to collect tailings samples from depth to quantify the distribution of As and Ni in the tailings with respect to ore type and assess the distribution of As and Ni with respect to tailings mineralogy. The tailings body consists of alternating layers of ice, frozen tailings and unfrozen tailings which varied in texture from a slurry to a firm silty sand. The tailings solids are predominately composed of quartz (16–36%), calcium sulphate (0.3–54%) and illite (3 and 14%). Arsenic and Ni concentrations in the tailings show similar patterns with depth which were strongly related to historical changes in As and Ni concentrations in the mill feed. Mineralogy of the ore bodies indicated that As and Ni in the mill feed occurred primarily as 1:1 molar ratio arsenides such as niccolite and gersdorffite. Arsenic and Ni concentrations in the tailings were also measured at a near 1:1 molar ratio. Mill process records showed that an average of 71% of the As in the mill feed was solubilized during leaching. SEM analysis suggested that solubilized As is precipitated as Ca2+, Fe3+ and Ni2+ arsenates during the neutralization process. Mill records indicated that 17,000 tonnes of As were discharged to the TMF of which approximately 88% was as arsenates and 12% as primary arsenides.  相似文献   

19.
This study reports on the mobility and retention of trace elements in cassiterite tailings at the inactive Jumna mill, tropical north Queensland. Since the 1980s, the uncapped tailings have developed laterally discontinuous Fe-rich hardpans, which are located in the higher parts of gently sloping tailings masses and at the top (<50 cm) of the tailings piles. Hardpan-cemented tailings comprise thin layers (typically ∼0.2–2 mm thick) of HFO (hydrous ferric oxides) and sulfate efflorescences cementing tailings grains. In comparison to the tailings, the hardpan-cemented tailings contain significantly higher median As, Ca, Cd, Co, Cu, Fe, In, Mn, Mo, Stotal, Th, U, Y and Zn values. Partial leaching studies of tailings and pond water analyses indicate that wetting and acidification of Fe-cemented tailings removes significant proportions of trace elements into pore and surface waters. Tin shows no mobility due to the presence of weathering-resistant cassiterite (SnO2) and, As and Pb display limited mobility possibly due to their coprecipitation with jarosite-type phases and HFO materials at the top of the tailings profile. By contrast, the trace elements Cd, Ce, Cu, La, Ni, Pb, U and Zn display the greatest mobility, possibly due to their incorporation in soluble sulfate efflorescences and sorption onto mineral and HFO surfaces. Hence, the Fe-rich hardpans do not protect the sulfidic tailings from further oxidation nor do they cause permanent sequestration of trace elements.  相似文献   

20.
Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site in Raymond, New Hampshire, USA, showed evidence of locally enhanced As mobilization in relatively reducing (mixed oxic-anoxic to anoxic) conditions as determined by redox classification and other lines of evidence. Redox classification was determined from geochemical indicators based on threshold concentrations of dissolved oxygen (DO), nitrate (NO 3 – ), iron (Fe2+), manganese (Mn2+), and sulfate (SO 4 2– ). Redox conditions were evaluated also based on methane (CH4), excess nitrogen gas (N2) from denitrification, the oxidation state of dissolved As speciation (As(III) and As(V)), and several stable isotope ratios. Samples from the residential-supply wells primarily exhibit mixed redox conditions, as most have long open boreholes (typically 50–100?m) that receive water from multiple discrete fractures with contrasting groundwater chemistry and redox conditions. The methods employed in this study can be used at other sites to gauge redox conditions and the potential for As mobilization in complex fractured crystalline-rock aquifers where multiple lines of evidence are likely needed to understand As occurrence, mobility, and transport.  相似文献   

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