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Applied Geochemistry, Vol. 13, No. 6, pp. 687705, 1998 # 1998 Elsevier Science Ltd All rights reserved. Printed in Great Britain S0883-2927(98)00009-2 0883-2927/98 $ - see front matter

Geochemical, mineralogical and microbiological characterization of a sulphide-bearing carbonate-rich gold-mine tailings impoundment, bec Joutel, Que
David W. Blowes*, John L. Jambor and Christine J. Hanton-Fong
Department of Earth Sciences, University of Waterloo, Waterloo, Ont., Canada, N2L 3G1

Lyne Lortie and W. Douglas Gould

Environmental Laboratory, CANMET, 555 Booth Street, Ottawa, Ont., Canada K1A 0G1 (Received 16 January 1996; accepted in revised form 31 October 1997) AbstractThe results of an integrated geochemical and mineralogical study conducted at the Agnico bec, are correlated with bacterial populations deterEagle gold-mine tailings impoundment, Joutel, Que mined from an enumeration of 3 groups of Thiobacilli. The tailings were determined to contain approximately 5 wt.% sulphideS, predominantly as pyrite, and up to 30 wt.% carbonate minerals, chiey as dolomiteankerite and siderite. The objective of the study was to evaluate the potential for the development of acidic drainage and dissolved-metal migration in carbonate-rich tailings impoundments, and to compare the results of the geochemical and microbiological characterization of the tailings. Sulphide-oxidation reactions have proceeded to a depth of 20100 cm below the tailings surface. Pyrrhotite consistently shows more alteration than pyrite and arsenopyrite. Pyrrhotite is altered mainly through the replacement by goethite. The most abundant Thiobacilli are neutrophilic bacteria of the Thiobacillus thioparus type. The maximum most probable number values for these bacteria occur 2040 cm below the tailings surface, a depth that coincides with the disappearance of oxide coatings. This observation, coupled with the sharp decline in gas-phase O2 concentration, suggests that rapid bacterially-mediated Soxidation is occurring at this depth. The pore-water pH throughout the tailings varies between 6.5 and 8.5; no low-pH waters were observed in the impoundment. These neutral pH conditions are attributed to the eect of acid-consuming carbonate-mineral dissolution reactions, which are also indicated by increased concentrations of Mg and Ca and alkalinity in the shallow zone of the tailings. As a result of these acid-neutralization reactions, dissolved metal concentrations are low. # 1998 Elsevier Science Ltd. All rights reserved

INTRODUCTION

The Agnico-Eagle Au mine, which was in pro bec, duction from 1974 to 1994, is near Joutel, Que approximately 195 km N of Val d'Or (Fig. 1). The Au occurs within sulphide-rich portions of a pyritiferous stratiform ore deposit (Barnett et al., 1982). The adjacent Telbel mine, which shared the same tailings impoundment and ore-processing facilities, began production in 1985. Gold was extracted from the ore by otation of the sulphide portion, followed by cyanidization and Au reprecipitation. The mill has the capacity to process about 1600 t/d, but the recent annual production was 330 000385 000 t, grading about 5.8 g/t Au and 1.8 g/t Ag. Tailings generated at the Agnico-Eagle site were deposited in a 120 ha elevated impoundment W of the mine site (Fig. 1). The impoundment is divided into an older segment in which tailings were deposited from 1974 to 1986, and a newer one in which
*Corresponding author. 687

deposition occurred from 1986 to 1994. The tailings contain 45 wt.% sulphideS, mainly as pyrite [FeS2] and pyrrhotite [Fe(1x)S], with lesser amounts of arsenopyrite [FeAsS]. The carbonate content of the tailings is approximately 20 wt.% as CO3, predominantly as siderite [FeCO3], dolomiteankerite [CaMg(CO3)2-Ca(Fe,Mg)(CO3)2], and calcite [CaCO3]. Sulphide-rich tailings are a potential source of dissolved metals and acidity that results from the microbially-catalyzed oxidation of sulphide minerals, such as pyrite. This study provides specic information regarding the mineralogical and microbiological character and interactions that occur within the Agnico-Eagle tailings. In this study the results of a 1993 eld investigation of the geochemical characteristics of the older tailings are compared with the results of a concurrent mineralogical study and microbiological enumeration (Jambor et al., 1993). To facilitate this comparison, samples were collected at four piezometer-nest locations on the tailings impoundment. The primary objectives of the research program were to determine the potential for release of acidic

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Fig. 1. Plan view of the Agnico-Eagle tailings impoundment.

drainage and dissolved metals from the tailings area, and to determine the types and numbers of Thiobacilli within the impoundment. These objectives were carried out so that an integrated model of biotic and abiotic mechanisms within the Agnico-Eagle tailings could be developed.

described by Blowes et al. (1995). Three general physiological groups of Thiobacilli were enumerated by the most probable number technique (MPN) (Cochran, 1950) in order to enumerate: (1) neutrophilic Thiobacilli (T. thioparus and related species), (2) acid-tolerant S oxidizers (T. thiooxidans), and (3) acidophilic Fe oxidizers (T. ferrooxidans and related species).

METHODOLOGY Microbiological methods Core samples for microbiological study were collected using thin-walled 5.08 cm Al tubing. Thirty-one samples were taken at 1020 cm depth intervals at 4 locations on the tailings impoundment: AE2, AE3, AE4, and AENT (Fig. 1). Of these, the rst 3 are sited on the older portion of the tailings impoundment (deposited before 1986), and AENT is on the new tailings area (deposited since 1986). The cores were stored and shipped in ice-packed coolers, and were delivered to the laboratory at CANMET within 24 h of collection. In the laboratory, the Al casing was cut perpendicular to its long axis and a sample was taken from the center of the tube. Microbiological enumeration was conducted using the techniques and media

Mineralogical methods Core samples for mineralogical study were collected at 4 piezometer nests on the old impoundment: AE1, AE2, AE3, and AE5 (Fig. 1). All cores were obtained using thin-walled Al tubes (5.08 cm in diameter), that were cut into lengths of about 0.5 m after core retrieval. The cores were kept frozen and were split lengthwise with a band saw. One split of each core was extruded from its half-barrel onto a plastic sheet and was allowed to thaw and dry at room temperature (25308C). Similar procedures, which prevent the loss of pore water and minimize the possible dehydration of secondary precipitates, have been successfully used in the mineralogical studies of tailings from several other impoundment sites (e.g., Blowes and Jambor, 1990). Prior to removal of the material selected for mineralogical studies, both the wet and the dried cores were examined for signs of ocherous secondary minerals and

Sulphide-bearing carbonate-rich gold-mine tailings impoundment precipitates that may have formed during drying. The general megascopic features were logged. Most of the samples used for detailed studies consisted of material that had been removed from the center of the core along its length. The resulting samples were then sieved to pass a 300 mm screen. In addition to the selection of these powders, 8 polished thin sections were cut from the ocherous parts of the cores, as these probably represent the most intensely oxidized portion of the tailings. These thin-section portions were kept intact by impregnation of the core with repeated applications of cyanoacrylate adhesive prior to thin-section preparation (Jambor, 1994). In all, 65 polished sections and 9 polished thin sections were examined by optical microscopy using transmitted-light and reected-light techniques. Splits of the screened samples that were used for the polished sections were used for X-ray diractometry. Samples were ground in acetone and the powdered mounts were run with a Rigaku2 diractometer using Co X-radiation. Sixty-four bulk samples corresponding to those used for optical microscopy were processed. Several acid-treated samples were run specically for carbonatemineral determinations. The acid treatments involved dierential dissolution using HCl at various strengths to dissolve the carbonate min-

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erals, thereby conrming the identication of carbonatemineral X-ray peaks by their elimination from diractograms of the acid-treated residues. Acid treatment of calcareous samples also simplied the X-ray patterns by reducing the total number of X-ray peaks. Microbeam analyses were conducted with a JEOL2 820 scanning electron microscope coupled with energy-dispersion facilities for elemental analyses, and a JEOL2 733 electron microprobe with the capacity for energy-dispersion and wavelength quantitative chemical analyses. As the extent of alteration and its intensity in the AgnicoEagle tailings were found to be limited, quantitative analyses were restricted to the determination of the compositions of the carbonate minerals.

Hydrogeochemical study Groundwater ow system. A network of 5 piezometer nests, including 31 individual piezometers, was installed in the tailings (Fig. 1; Table 1) to provide hydraulic head and hydraulic conductivity data for use in the delineation of the groundwater ow system. Water samples collected

Table 1. Piezometer information, including hydraulic conductivity values (calculated from piezometer response tests), measured water levels, and hydraulic head values. Well AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE AE 11 12 13 14 16 19 111 21 22 23 24 25 26 32 33 34 36 38 39 41 42 43 45 46 47 51 52 53 54 55 56 6 7 8 9 10 11 12 13 14 15 Hydraulic conductivity (m/s) 8.3E-08 6.7E-08 3.8E-08 9.7E-09 Static water level below ground surface June 13/93 (m) 0.18 0.29 0.36 0.37 0.51 8.01 8.12 0.33 0.72 1.04 1.02 1.88 n/a 2.07 2.11 2.11 2.19 7.24 9.55 0.52 0.85 0.78 0.92 2.50 6.33 0.54 0.42 0.42 n/a n/a n/a 1.13 1.65 1.68 1.20 1.76 2.06 3.69 2.36 n/a n/a Sept 8/93 (m) 0.91 1.39 1.39 1.40 1.40 2.04 2.65 n/a n/a 2.06 2.15 2.19 4.14 2.18 2.62 2.64 2.69 3.14 9.26 1.00 1.64 1.67 1.69 1.71 5.90 0.69 2.14 1.89 1.90 1.87 1.92 1.77 1.91 1.72 1.73 2.04 n/a 3.20 2.30 1.41 1.83 Hydraulic head June 13/93 (m) 1557.34 1557.23 1557.16 1557.15 1557.01 1549.51 1549.40 1556.11 1555.72 1555.40 1555.42 1554.56 n/a n/a n/a n/a n/a n/a n/a 1557.05 1556.72 1556.79 1556.65 1555.07 1551.24 1554.99 1555.11 1555.11 n/a n/a n/a 1553.99 1551.88 1553.86 1555.64 1555.38 1554.58 1554.48 1554.06 n/a n/a Sept 8/93 (m) 1556.61 1556.13 1556.13 1556.12 1556.12 1555.48 1554.87 n/a n/a 1554.38 1554.29 1554.25 1552.30 n/a n/a n/a n/a n/a n/a 1556.57 1555.93 1555.90 1555.88 1555.86 1551.67 1554.84 1553.39 1553.64 1553.63 1553.66 1553.61 1553.35 1551.62 1553.82 1555.11 1555.10 n/a 1554.97 1554.12 1551.70 1553.98

4.3E-08 2.0E-08 1.6E-08 5.9E-09 3.1E-09 1.1E-07 8.2E-07 3.6E-08 1.8E-08 7.6E-09 1.9E-08 1.6E-08 3.2E-08 9.4E-09 2.5E-09

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D. W. Blowes et al. Quality Laboratory, University of Waterloo. Chemical analyses were performed in the same manner as for the vadose-zone samples. Determinations of pH, Eh, temperature and specic conductance were made at each piezometer using sealed ow-through cells. Alkalinity determinations were made in the eld using a digital titrator.

from these piezometers were also used for geochemical characterization of the impoundment. An additional 10 piezometers were installed as individual water-table wells to provide information on the groundwater ow system. These piezometers were either 3.18 cm diameter PVC drive-point piezometers similar to those used by Dubrovsky et al. (1984a,b), or 1.27 cm diameter stainless steel or PVC drive-point piezometers similar to those described by Coggans et al. (1995). All piezometers were developed by repeated bailing, and the hydraulic conductivity of the tailings was estimated by rising-head response tests, analyzed using the technique of Hvorslev (1951). Hydraulic head measurements were made after water levels in the piezometers had stabilized. The ground surface, top of the casing, and location of each piezometer and water-table well were surveyed and located on the local mine plan. Vadose-zone sampling. Pore water from the vadose zone was extracted from sealed core samples collected in 7.62 cm diameter thin-walled Al casing. The core samples were cut into 25 cm lengths and the ends of the casing tted with O-ring sealed end-plates, isolating the samples from atmospheric O2(g). Pore water was extracted by slowly applied pressure on the end plates using the technique described by Blowes and Jambor (1990). Determinations of pore-water pH (Orion2 Ross 815600 combination electrode) and Eh (Orion2 9678BN combination electrode) were made within 1 minute of pore-water extraction. The performance of the pH electrode was conrmed using pH 4.0 and 7.0 standards (traceable to NIST). The performance of the Eh electrode was conrmed by comparison to Zobell's solution (Zobell, 1946; Nordstrom, 1977) and Light's solution (Light, 1972). All Eh values were corrected to the standard hydrogen electrode (SHE). All samples were ltered through cellulose acetate membranes (0.45 mm pore size), then split into two subsamples. One was acidied to pH <1 with 12 N HCl for cation analysis. The second unacidied sample was used for anion analysis. All samples were refrigerated until analysis. Alkalinity of the samples was determined in the eld, on 410 ml subsamples using a digital titrator and a methyl red-bromocresol green indicator. Samples were returned to the Water Quality Laboratory at the University of Waterloo, where concentrations of Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, and Zn were determined by atomic absorption spectrometry (AAS). Total As concentrations were determined by AAS following hydride generation. Concentrations of SO2 4 , Cl , F , 3 , and PO were determined by ion chromatography. NO 3 4 Analysis of duplicate and prepared spike samples indicates that the estimated error associated with the analytical data is <5% of the measured concentrations. Saturated-zone sampling. Samples of tailings water were collected from all piezometer nests. All samples were passed through 0.45 mm pore-size lters, and samples for cation analysis were acidied to pH < 1 with 12 N HCl. All samples were refrigerated until analysis at the Water

Physical properties The bulk density, particle density, porosity, moisture content, and air-lled porosity were determined at each of the locations sampled. The bulk density and gravimetric moisture content were measured gravimetrically using samples collected in 5.08 cm Al casing, and oven dried at 808C. The particle density of the dry tailings was measured using a Beckman2 Model 930 Air Comparison Pycnometer. Porosity, volumetric moisture content and air-lled porosity were calculated from bulk density, particle density, and gravimetric moisture-content measurements.

Pore-gas sampling Pore-gas concentrations of O2(g) and CO2(g) were measured in the eld using a modication of the technique described by Reardon and Poscente (1984). Narrow diameter (0.63 cm) stainless steel tubes were driven into the tailings at 10 cm vertical intervals. The sampling tubes were connected directly to an O2/CO2 analyzer (Nova2 Model 305LBD). This technique provided measurements of gasphase O2 and CO2 concentrations at the eld site. Separate samples were collected for laboratory analysis by gas chromatography. The detection limit for this technique is 0.1% O2(g) and 0.1% CO2(g).

RESULTS AND DISCUSSION

The groundwater ow system For much of the nal stages of operation at the Agnico-Eagle mine, tailings deposition was directed from a discharge point located near the center of the impoundment (Fig. 2). This deposition technique resulted in a tailings grain-size distribution that is dierent from those observed in most inactive tailings areas. Coarser-grained tailings settled near the discharge point and are now concentrated in the central portion of the tailings area, in the

Fig. 2. Cross section of the Agnico-Eagle tailings impoundment.

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vicinity of piezometer nest AE3 (Fig. 1). Finergrained tailings, which settled distally from the discharge point, have accumulated near the impoundment margins. The distribution of tailings grain sizes is reected in the hydraulic conductivity of the tailings, as estimated from piezometer-response tests (Table 1). In general, the greatest hydraulic conductivity values are observed in the central portion near piezometer nest AE3, at which grain sizes are coarse. The ne-grained tailings located near the tailings margins exhibit high moisture contents and have prevented the extensive drainage of the tailings margins that has been observed at other tailings areas ;. Blowes and (e.g., Waite Amulet, Noranda,z Que Jambor, 1990). As a result, the water table at piezometer nests AE1 and AE2 is within 2 m of the tail-

ings surface. Maintaining high moisture contents is advantageous because the O2 diusivity of saturated tailings is less than that of unsaturated tailings. The high moisture contents, however, slow the rate of consolidation and may increase the potential for uneven settling or dam failure. To prevent these possibilities, the sides of the tailings dam have been armored with waste rock from the open pit and underground operations. Groundwater ow in the impoundment is directed downward and laterally to the impoundment edges. The hydraulic conductivity of the tailings ranges from 2.5 109 m/s to 8.2 107 m/s. Vertical velocities were calculated using this range of conductivity values (Table 2). The measured hydraulic gradients range from 0.03 to 1.0 for the vertical component of ow and 6 104 to 6 103

Fig. 3. Concentrations of dissolved constituents vs depth at piezometer nest AE 1. Filled symbols measured June 1993. Open symbols measured September 1993. Water table indicated by dashed line; Zn, Cu, Pb, Cd by .; Mn, Ni, Co, Cr by R.

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D. W. Blowes et al. Table 2. Comparison of vertical gradients and calculated velocities. Depth to discharge-water Vertical velocity based on recharge-water discharge- and recharge-water interface (m) interface (m/a) 0.31 2.04 2.83 2.10 1.17 0.46 0.29 0.40 0.30 0.17 Vertical velocity based on gradients (m/a) June/93 1.94 0.15 0.51 0.50 Sept/93 0.26 0.65 0.88 4.98

Piezometer nest 0.27 AE 2 AE 3 AE 4 AE 5

Fig. 4. Concentrations of dissolved constituents vs depth at piezometer nest AE 2. Filled symbols measured June 1993. Open symbols measured September 1993. Water table indicated by dashed line; Zn, Cu, Pb, Cd by .; Mn, Ni, Co, Cr by R.

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for the horizontal component. The greatest vertical hydraulic gradients were measured at piezometer nests AE2 and AE5 (Fig. 1). Rates of groundwater ow can be estimated independently by examining the distribution of dissolved sulphide-oxidation products using the approach described by Dubrovsky (1986). Mill discharge-water, slurried into the impoundment within the tailings, contains high concentrations of Na,

and low concentrations of Ca, Mg, SO4, and dissolved metals. Precipitation-recharge water that entered the impoundment after decommissioning has been aected by sulphide oxidation and by carbonate-mineral dissolution. This precipitationrecharge-water contains high concentrations of SO4, Ca, Mg, SO4 and other metals, and has lower concentrations of Na. The depth of the interface between the initial mill discharge-water and the

Fig. 5. Concentrations of dissolved constituents vs depth at piezometer nest AE 3. Filled symbols measured June 1993. Open symbols measured September 1993. Water table indicated by dashed line; Zn, Cu, Pb, Cd by .; Mn, Ni, Co, Cr by R.

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recharge water, which can be observed in Figs. 37 and noted in Table 2, varies from <2 m at location AE5, to 1 3 m at location AE3. Using this interface depth and the fact that tailings deposition in the old impoundment ceased in 1986, vertical velocities are calculated that vary from 0.2 m/a to 0.4 m/a. These vertical velocities are similar to those estimated from the vertical hydraulic gradient and the measured hydraulic conductivity (Table 2).

Sulphidemineral oxidation The results from optical microscopy indicate that pyrite is the most abundant sulphide mineral, followed by pyrrhotite. Marcasite [FeS2] was noted in a few polished sections but, other than pyrite and pyrrhotite, the only other sulphide mineral of consistent and widespread occurrence is arsenopyrite, which occurs in trace amounts. No grains of spha-

Fig. 6. Concentrations of dissolved constituents vs depth at piezometer nest AE 4. Filled symbols measured June 1993. Open symbols measured September 1993. Water table indicated by dashed line; Zn, Cu, Pb, Cd by .; Mn, Ni, Co, Cr by R.

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Fig. 7. Concentrations of dissolved constituents vs depth at piezometer nest AE 5. Filled symbols measured June 1993. Open symbols measured September 1993. Water table indicated by dashed line; Zn, Cu, Pb, Cd by .; Mn, Ni, Co, Cr by R.

lerite [ZnS], galena [PbS], or Au were detected in the mineralogical study. The oxidation of sulphide minerals is the predominant source of acidity and dissolved metals characteristic of the acidic drainage associated with inactive mine wastes. The oxidation of pyrite, the most abundant sulphide mineral present at the Agnico-Eagle mine, can be expressed as:

4Fe2 FeS2s 7 aq 2 O2 g H2 Ol 2SO2 4aq 2H aq

*The Fe2+ (aq) released by sulphide oxidation may be further oxidized, hydrolyzed, and precipitated as an amorphous or crystalline ferric oxyhydroxide through reactions of the form:

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1 5 Fe2 4FeOH 3s 2H aq 4 O2 g 2 H2 Ol aq

expressed as:

2 Alternatively, a ferric hydroxysulphate phase, such as schwertmannite [Fe8O8(OH)6(SO4)] (Bigham et al., 1990, 1994), may precipitate, resulting in the release of dierent amounts of H+ (aq). Oxidation of pyrrhotite, the second most abundant sulphide mineral in the tailings, can be

  x O2 g xH2 Oaq 4 Fe1x Ss 2 2

2 1 xFe2 aq SO4aq 2xH aq

The Fe2+ (aq) released by oxidation of pyrrhotite may be further oxidized and precipitated as shown by equation 2. The oxidation of pyrite, pyrrhotite, and

Table 3. Saturation indices for the oxide mineralsa and gypsum at piezometer nests AE1 to AE5b. Well AE1 nest AE1-V1 AE1-V2 AE1-V3 AE1-V4 AE1-1a AE1-1b AE1-2 AE1-3 AE1-4 AE1-6 AE1-9 AE1-11 AE2 nest AE2-1 AE2-2 AE2-3 AE2-4 AE2-5 AE2-6 AE3 nest AE3-V3 AE3-V4 AE3-V5 AE3-V6 AE3-V7 AE3-V8 AE3-2 AE3-3 AE3-4 AE3-6 AE3-8 AE4 nest AE4-V1 AE4-V2 AE4-V3 AE4-V4 AE4-V5 AE4-1 AE4-2a AE4-2b AE4-3 AE4-5 AE4-6 AE4-7 AE5 nest AE5-2 AE5-3 AE5-4 AE5-5 AE5-6
a b

Depth (m) 0.12 0.38 0.62 0.88 0.92 0.92 1.91 2.95 3.92 6.24 9.55 10.84 1.19 2.04 2.69 3.89 5.17 5.46 0.62 0.88 1.12 1.38 1.62 1.92 2.18 2.83 4.54 6.04 7.93 0.10 0.30 0.50 0.70 0.90 1.00 2.10 2.10 2.73 4.87 5.73 6.39 1.17 1.96 3.23 4.06 5.82

Amorphous Fe(OH)3 4.18 2.22 2.60 0.60 1.02 1.43 0.62 3.08 3.32 4.70 0.96 4.30 0.29 2.94 3.18 2.63 0.79 3.54 3.09 0.75 0.51 2.18 0.21 1.05 3.20 0.36 2.86 3.05 0.15 2.05 0.55 2.69 1.59 2.53 2.64 2.97 3.06 2.85 3.09 0.30 2.77 2.64 3.80 0.88 1.15

Goethite 9.51 7.55 7.93 5.94 6.36 6.77 5.77 8.18 8.42 9.84 6.11 9.45 5.62 8.12 8.31 7.75 5.92 8.70 8.34 5.96 5.70 7.34 5.33 6.14 8.25 5.39 7.92 8.13 4.96 7.37 5.87 8.00 6.89 7.82 7.93 8.14 8.22 8.00 8.18 5.62 7.98 7.78 8.87 5.98 6.25

Lepidocrocite 7.70 5.74 6.12 4.12 4.54 4.95 4.14 6.61 6.84 8.22 4.48 7.82 3.81 6.46 6.70 6.15 4.31 7.06 6.61 4.27 4.03 5.71 3.73 4.57 6.72 3.88 6.38 6.57 3.37 5.57 4.08 6.21 5.11 6.05 6.16 6.49 6.58 6.37 6.61 3.82 6.29 6.16 7.32 4.40 4.67

Jarosite 4.34 0.87 1.80 2.49 2.93 1.70 4.74 1.62 3.30 2.55 12.15 1.09 4.14 1.11 2.09 0.68 4.63 3.58 1.90 5.19 5.37 0.68 6.11 3.33 2.32 5.97 1.04 0.63 11.10 1.23 5.67 0.14 2.23 0.08 1.47 0.34 0.58 0.31 0.88 6.04 0.87 0.75 3.16 4.90 6.36

Gypsum 0.04 0.11 0.04 0.02 0.12 0.14 0.08 0.17 0.12 1.96 2.86 2.64 0.04 0.06 0.09 0.30 0.90 0.30 0.02 0.08 0.12 0.06 0.02 0.04 0.23 0.02 0.08 0.19 1.77 0.02 0.22 0.09 0.26 0.46 0.16 0.29 0.36 0.09 0.31 1.11 1.07 0.32 0.12 0.32 1.32 0.87

Goethite: a-FeOOH; lepidocrocite: g-FeOOH; jarosite: KFe3(SO4)2(OH)6; gypsum: CaSO42H2O. Samples designated by V indicate collection from the vadose zone.

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Fe2+ (aq) may be catalyzed by autotrophic bacteria of the Thiobacillus group (Brock et al., 1984). The acidophilic bacterium Thiobacillus ferrooxidans is generally considered to be the species responsible for the generation of acid mine drainage. Other Thiobacillus species, however, including the acid-tolerant mesophilic bacteria Thiobacillus thiooxidans, which has an observed pH range of growth of 0.5 to 4.0, are also capable of oxidizing reduced S compounds. Thiobacillus thioparus and related species, which can oxidize sulphide, thiosulphate, and other reduced S compounds, have an optimum pH range of 6.08.0 (Kuenen et al., 1992; Gould et al., 1994). Bacterial catalysis accelerates the rate of sulphide oxidation and may maintain oxidation at rates that are limited by the physical transport of the oxidant (O2(g) or Fe3+ (aq)) through the pore space of the tailings by diusion or advection, or limitations may be imposed by oxidized coatings on the mineral grains. Oxidation of sulphide minerals is evident by the brown color of the surcial tailings compared to the dark grey color of the deeper tailings. On the microscopic scale, oxidation is evident in the appearance of goethite [a-FeOOH] and other related Fe oxides or oxyhydroxides. Geochemical calculations conducted using MINTEQA2 (Allison et al., 1990) indicate that the tailings pore-waters are consistently supersaturated with respect to goethite and other ferric oxyhydroxide minerals (Table 3), suggesting that the goethite rimming the primary sulphide grains is stable under the geochemical conditions prevalent in the shallow tailings. Pyrrhotite is commonly considered to be more susceptible to bacterially-catalyzed oxidation than pyrite and other sulphide minerals (Brock et al., 1984). In the vadose zone at the Agnico-Eagle mine, the alteration rims on pyrrhotite are thick and indicate more extensive oxidation of this sulphide than pyrite, which is surrounded by rare, narrow alteration rims (Fig. 8). The thickness of the secondary pyrrhotite alteration rims is indicative of the extent of oxidation since tailings deposition ended. As all sulphide minerals at a single location were exposed to O2 at the same time, the degree of alteration is indicative of the relative susceptibility to oxidation. More rapid oxidation of pyrrhotite, relative to pyrite, inferred from the eld observations is consistent with the results of recent laboratory studies, which also indicate pyrrhotite oxidizes more rapidly than pyrite (Jambor, 1994; Nicholson and Scharer, 1994; Mycroft et al., 1995). Development of partial oxide coatings may change the rate of oxidation of the residual sulphides, but the coatings do not change the dierential in alteration susceptibility. Less extensive alteration of pyrite than pyrrhotite has been observed at other locations such as the . (Blowes Waite Amulet tailings impoundment, Que

and Jambor, 1990; Blowes, 1990) and the Delnite impoundment near Timmins, Ontario (Jambor and Blowes, 1991; Jambor et al., 1991). At other sites, the degree of arsenopyrite alteration was observed to be similar to that observed for pyrite. No altered arsenopyrite grains were observed during the current study, possibly because too few grains of the mineral were seen. The depth of active sulphide oxidation is also indicated by the depletion of gas-phase O2 in the vadose zone of the tailings. Pore-gas O2 concentrations were measured at 3 locations: AE2, AE3, and AE4 (Fig. 1). High moisture contents at AE1 and AE5 prevented pore-gas sampling. At the 3 sites sampled, pore-gas O2 concentrations decrease sharply from atmospheric concentration (20.9 vol.%) at the tailings surface to <0.1 vol.% within the upper 50 cm of the tailings (Fig. 9). Depletion of O2 is accompanied by an increase in CO2 resulting from acid-neutralizing carbonatemineral dissolution reactions. The pore-water pH throughout the vadose zone is near neutral (Figs. 37), indicating that carbonate-mineral dissolution has been sucient to consume the acidity generated by the sulphide-oxidation. Potential limitations on the rate of sulphide oxidation in mine wastes include an insucient supply of oxidant (O2(g) or Fe3+ (aq)) or water to the sulphide-

Fig. 8. Unaltered pyrite (py) surrounded by 3 grains of pyrrhotite showing their greater susceptibility to alteration, here expressed as well-dened rims of Fe oxyhydroxides. Polished section, reected plain light, width of eld 0.5 mm, site AE 3.

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Fig. 9. Gas-phase O2 and CO2 concentrations and most probable number (MPN) values for Thiobacillus ferrooxidans, Thiobacillus thiooxidans, Thiobacillus thioparus and related bacteria (bacteria per g of tailings).

mineral surface, due to physical transport restrictions, and slow reaction rates on the mineral surface (Davis and Ritchie, 1986; Blowes et al., 1991; Cathles, 1994). Restrictions of the supply of O2(g) to sulphide surfaces can include slow diusion of gasphase O2 through the partly water-saturated pore space of the tailings, and diusion of oxidant through the hydroxide or oxyhydroxide rims that surround altered sulphide particles. Oxygen-gas diffusivities are dependent on the porosity and moisture content of the tailings. Numerous empirical expressions have been developed to relate gas diusivity of partly-saturated solids to their porosity and moisture content (Millington and Shearer, 1971; Magnusson and Rassmuson, 1984). Reardon and Moddle (1985) developed the empirical relationship:   e 0:05 1:7 3=2 DO2 3:98 105 T 4 0:95 where DO2 is the oxygen-gas diusion coecient in cm2/s, e is the air-lled porosity, and T is the tem-

perature in Kelvin. This equation was based on column studies conducted with partly-saturated mill tailings from Elliot Lake, Ont. Oxygen-gas diusion coecients calculated for the shallow tailings, using the eld-measured porosity and moisture contents and the relationship of Reardon and Moddle (1985), are tabulated in Table 4. The greatest calculated diusion coecients are from the relatively dry tailings present near the tailings surface at piezometer nest AE3. Increasing moisture contents, and decreasing diusion coecients, are observed with increased depth. In addition to limits imposed by the diusivity of the tailings pore-space, sulphide oxidation may be inhibited by oxidant diusion through the alteration rims that form on the surfaces of tailings particles. Inhibition of oxidation by alteration rims has been observed in heap-leach piles (Cathles, 1994; Jang and Wadsworth, 1994), waste-rock piles (Davis and Ritchie, 1986; Ritchie, 1994), and has been inferred in other tailings areas (Blowes and Jambor, 1990; Blowes et al., 1992). The recognition that surface coatings can inhibit sulphide-mineral oxidation has

Sulphide-bearing carbonate-rich gold-mine tailings impoundment Table 4. Porosities, moisture contents, and diusion coecients for piezometer nests AE2, AE3, and AE4. Depth (cm) AE2 nest 010 1020 2030 3040 4050 5060 6070 7080 8090 90100 100110 110120 120130 AE3 nest 010 1020 2030 3040 4050 5060 6070 7080 8090 90100 100110 AE4 nest 010 1020 2030 3040 4050 5060 6070 7080 8090 90100 100110 110120 Total porosity 0.50 0.50 0.57 0.51 0.52 0.54 0.51 0.57 0.52 0.52 0.49 0.57 0.55 0.52 0.53 0.51 0.49 0.50 0.50 0.50 0.51 0.52 0.52 0.52 0.54 0.52 0.50 0.50 0.54 0.53 0.51 0.50 0.56 Air-lled porosity 0.16 0.23 0.19 0.15 0.12 0.16 0.13 0.22 0.13 0.17 0.16 0.42 0.32 0.40 0.29 0.23 0.19 0.32 0.30 0.32 0.21 0.19 0.19 0.19 0.20 0.19 0.17 0.17 0.18 0.21 0.18 0.21 0.13 % Saturated 68 54 67 70 76 71 75 61 74 67 66 26 41 22 44 54 60 36 41 36 59 63 64 63 63 64 66 65 66 60 64 58 77 Moisture content (Vol.%) 34 27 38 38 36 39 38 38 35 38 35 32 26 15 22 11 23 28 30 22 18 20 18 30 32 33 33 34 34 33 32 36 32 32 29 43 O2 diusion coecient (m2/s) 5.0 107 1.1 106 7.4 107 4.2 107 2.4 107 4.6 107 2.8 107 1.1 106 3.0 107 5.9 107 5.1 107 3.8 106 2.3 106 3.5 106 1.9 106 1.2 106 7.7 107 2.2 106 1.9 106 2.3 106 9.2 107 7.7 107 6.9 107 7.6 107 8.2 107 7.1 107 5.6 107 5.7 107 6.7 107 9.2 107 6.8 107 9.2 107 2.8 107

699

resulted in the development of remediation programs designed to promote the stability and eectiveness of such coatings (Huang and Evangelou, 1994). Extensive alteration rims on oxidized pyrrhotite, and to a lesser extent on pyrite, are observed only in the upper 2040 cm of the impoundment. Deeper in the tailings, alteration rims are absent, and the rate of oxidation probably is controlled by the rate of oxidation at the mineral surface.

BACTERIA

Sulphide oxidation in mine wastes is typically catalyzed by bacteria of the Thiobacillus group. Although Thiobacillus ferrooxidans is generally considered to be the microorganism responsible for catalysis of metal sulphide oxidation, other species may play a role in the initial stages of oxidation (Blowes et al., 1995). Most probable number (MPN) enumeration was conducted for 3 groups of

Thiobacilli: Thiobacillus ferrooxidans and related species, Thiobacillus thiooxidans, and Thiobacillus thioparus and related species. Distribution of Thiobacillus spp. versus depth indicates that the MPN values of the acidophilic group represented by T. ferrooxidans and T. thiooxidans are low throughout the vadose zone, with the exception of high values detected at the surface at piezometer nest AE4 (Figs. 9 and 10). The MPN of T. thioparus and related species, which have an optimum pH range of 6.08.0, are signicantly greater than those of the other species and do not vary signicantly with depth. The populations of T. thioparus are 16 orders of magnitude higher than the population of T. thiooxidans and T. ferrooxidans at most sampling points. The pH values of the tailings are generally close to neutrality, which would tend to favor the growth of the neutrophilic thiobacilli such as T. thioparus. At piezometer nests AE1, AE4 and AENT, high MPN values for T. thiooxidans are observed in the

700

D. W. Blowes et al.

Fig. 10. Most probable number (MPN) values for Thiobacillus ferrooxidans, Thiobacillus thiooxidans, Thiobacillus thioparus and related bacteria (bacteria per g of tailings).

upper 1 m of the tailings. At piezometer nest AE4 the maximum value is observed at a depth that corresponds with the sharp decline in gas-phase O2 concentration. Although unaltered sulphide minerals are present near the tailings surface, where gas-phase O2 concentrations are greatest, the highest MPN values for T. thiooxidans occur 2040 cm below the tailings surface. At location AE4 an increase in the bacterial population of T. thiooxidans corresponds with the depth of diminished alteration rims. This observation suggests that the bacterial population of T. thiooxidans thrives where both gas-phase O2 is high and exposed sulphide surfaces are available. The occurrence of the exposed sulphide surfaces, the sharp increase in bacterial population, and the sharp decline in gas-phase O2 concentration suggest that the bacterially catalyzed sulphide-oxidation reaction is proceeding rapidly in the oxidation zone below the occurrence of signicant alteration rims and above the depth of complete O2(g) depletion. As oxidation proceeds, and alteration rims accumulate, the rate of oxidation in this zone will slow, resulting in O2(g) penetration into the deeper tailings. Acid neutralization mechanisms The oxidation of sulphide minerals releases H+, 2+ SO2 , and other metals to the tailings pore4 , Fe water. Field measurements indicate that the tailings-water pH is near neutral throughout the vadose zone of the tailings (Figs. 37). These results suggest that the acid-neutralizing capacity of the

tailings has been sucient to consume the acidity generated by sulphide oxidation. Mineralogical results indicate that carbonate minerals are abundant throughout the tailings. On the basis of chemical analyses of tailings solids, X-ray diractometry, and microprobe-determined compositions, the carbonate-mineral content of the tailings is estimated to be about 30 wt.%. These carbonate minerals include calcite, dolomite-ankerite, and siderite (Table 5). X-ray diractometry estimates of carbonatemineral abundances suggest that the ratio of siderite:dolomite-ankerite is approximately 1:1, and that calcite is <5% of total carbonate. There is extensive solid-solution substitution in the carbonate minerals at the Agnico-Eagle site, particularly in dolomite, ankerite, and siderite. Among the substitutions is considerable variation of Mn in siderite and ankerite-dolomite (Table 5). At pH above about 6.3, the dissolution of carbonate minerals, such as calcite, consumes one mole of H+ for each mole of calcite consumed:
CaCO3s H 4Ca2 aq aq HCO3aq

As the pH decreases below approximately 6.3, carbonic acid [H2CO3] becomes the dominant carbonate form and the neutralization reaction may be described as:
2 CaCO3s 2H aq FCaaq H2 CO3aq

Carbon dioxide gas will be formed from the decomposition of carbonic acid through the reaction:

Sulphide-bearing carbonate-rich gold-mine tailings impoundment Table 5. Microprobe analyses of Agnico-Eagle carbonate minerals. wt% Fe Ca Mg Mn 39.1 0.4 3.9 2.4 40.1 0.7 2.8 2.2 83.2 1.7 9.7 4.6 99.2 sid 40.3 0.4 3.2 2.3 83.6 1.0 11.1 4.8 100.5 sid 13.7 19.5 5.4 1.9 28.4 48.7 18.7 4.0 99.8 ank 13.3 19.7 5.5 2.5 27.6 49.2 19.1 5.2 101.1 ank 44.4 0.2 0.8 1.5 92.1 0.5 2.8 3.1 98.5 sid 39.5 0.7 3.5 2.3 82.0 1.7 12.1 4.8 100.6 sid 13.7 19.5 3.3 5.9 28.4 48.7 11.5 12.3 100.9 ank 10.8 19.6 5.6 3.5 22.4 49.0 19.4 7.3 98.1 ank 39.0 0.7 3.6 2.3 80.9 1.7 12.5 4.8 99.9 sid 37.3 0.6 4.4 2.9 77.4 1.5 15.3 6.1 100.3 sid 12.8 19.8 5.1 3.3 26.6 49.5 17.7 6.9 100.7 ank 8.0 21.7 8.4 0.8 16.6 54.2 29.1 1.7 101.6 dol 38.7 0.2 4.4 1.8 80.3 0.5 15.3 3.8 99.9 sid 38.2 0.3 4.3 3.5 79.3 0.7 14.9 7.3 102.2 sid 12.4 20.1 5.9 2.2 25.7 50.2 20.5 4.6 101.0 ank 7.9 19.6 8.6 2.6 16.4 49.0 29.8 5.4 100.6 dol 37.6 0.8 3.9 2.5 78.0 2.0 13.5 5.2 98.7 sid 33.7 0.5 5.2 4.6 69.9 1.2 18.0 9.6 98.7 sid 12.4 19.7 6.1 1.8 25.7 49.2 21.2 3.8 99.9 ank 4.0 22.1 11.0 0.1 8.3 55.2 38.2 0.2 101.9 dol 36.4 0.5 4.8 3.4 75.5 1.2 16.7 7.1 100.5 sid 32.9 0.2 6.5 5.0 68.3 0.5 22.6 10.5 101.9 sid 16.0 19.5 4.9 1.0 33.2 48.7 17.0 2.1 101.0 ank 1.9 24.1 10.7 0.3 3.9 60.2 37.1 0.6 101.8 dol 37.8 0.6 3.9 2.9 78.4 1.5 13.5 6.1 99.5 sid 33.6 0.8 7.2 1.2 69.7 2.0 25.0 2.5 99.2 sid 14.6 19.7 5.2 2.0 30.3 49.2 18.0 4.2 101.9 ank 6.3 23.4 8.3 0.2 13.1 58.4 28.8 0.4 100.7 dol 37.7 0.5 3.7 3.6 78.2 1.2 12.8 7.5 99.7 sid 16.6 19.6 4.0 1.5 34.4 49.0 13.9 3.1 100.4 ank 14.2 19.4 4.4 2.5 29.5 48.5 15.3 5.2 98.5 ank 1.2 38.4 0.3 0.2 2.5 95.9 1.0 0.5 99.9 cal 36.8 1.7 3.8 2.6 76.3 4.2 13.2 5.4 99.1 sid 14.8 20.0 4.5 2.2 30.7 50.0 15.6 4.6 100.9 ank 12.2 20.0 5.5 2.5 25.3 50.0 19.1 5.2 99.6 ank 1.2 39.7a 0.2 0.2 2.5 99.2 0.7 0.5 102.9 cal 44.3 0.5 0.4 2.5 91.9 1.2 1.4 5.2 99.7 sid 15.0 20.3 4.1 2.0 31.1 50.7 14.2 4.2 100.2 ank 11.5 19.4 5.9 2.6 23.9 48.5 20.5 5.4 98.3 ank 0.8 40.1a 0.1 0.2 1.7 100.0 0.3 0.4 102.4 cal

701

45.2 0.5 0.4 1.7 93.8 1.3 1.4 3.6 100.1 sid 14.3 19.9 5.0 2.4 29.7 49.7 17.3 5.0 101.7 ank 11.6 19.5 6.0 2.8 24.1 48.7 20.8 5.9 99.5 ank 0.7 39.8 0.1 0.2 1.5 99.4 0.3 0.4 101.6 cal

calc.

FeCO3 81.1 CaCO3 1.0 MgCO3 13.5 MnCO3 5.0 sum 100.6 mineral sid Fe Ca Mg Mn FeCO3 CaCO3 MgCO3 MnCO3 sum mineral Fe Ca Mg Mn 44.2 0.5 0.4 1.9 91.7 1.2 1.4 4.0 98.3 sid 14.2 20.2 4.8 2.1

wt%

calc.

wt%

calc.

FeCO3 29.5 CaCO3 50.4 MgCO3 16.7 MnCO3 4.4 sum 101.0 mineral ank Fe Ca Mg Mn 15.8 19.8 4.0 1.8

wt%

calc.

FeCO3 32.8 CaCO3 49.6 MgCO3 13.9 MnCO3 3.8 sum 100.1 mineral ank

Analyses are of individual grains randomly selected without regard to size or other properties. Analytical conditions: 15 kV, 20 nA, 20 s counts; standards were MgAl2O4, MgCO3, Fe2O3, and apatite. Analyst: D.R. Owens. High totals are thought to be due to high analytical values for Ca.

H2 CO3aq FH2 Oaq CO2 g

The neutralization of H+ in tailings impoundments is commonly accompanied by increased gas-phase CO2 concentrations (Blowes and Jambor, 1990; Blowes et al., 1992). The cation composition of the carbonatemineral suite also aects the potential for acid neutralization. Base cations, such as Ca and Mg, released by carbonate dissolution increase the hardness of the tailings water and can participate in mineral precipitation reactions with dissolved anions. Because these metals tend to form relatively soluble salts (e.g., gypsum [CaSo42H2O]), high concentrations of Ca and Mg remain in solution and are displaced along

groundwater owpaths until they are discharged to the surface-water ow system. Dissolution of carbonate minerals which predominantly contain Ca and Mg increases the pH and decreases the acidgenerating potential of the pore water. Dissolution of carbonate minerals containing multivalent metals such as Fe and Mn also consumes H+. Dissolved Fe(II) and Mn(II) derived from the dissolution of siderite, ankerite, or ferroan dolomite, also tend to remain in solution and to be displaced along the groundwater owpaths. Discharge of Fe(II)-laden water to oxygenated bodies of surface water can result in acidication as Fe(II) is oxidized, hydrolyzed, and precipitated as shown in equation 2 (Morin and Cherry, 1988).

702

D. W. Blowes et al.

Similarly, the oxidation and precipitation of Mn can occur in the surface-water ow system (Hem and Lind, 1994). Controls on the mobility of dissolved constituents Sulphide oxidation and carbonate dissolution release SO4, Ca, Mg, Mn and Fe to the tailings pore-water. These reactions have resulted in the

increased concentrations of these constituents in the shallow tailings-water samples (Figs. 37). Geochemical calculations conducted using the computer program MINTEQA2 (Allison et al., 1990) indicate that the pore water in the deeper tailings is generally undersaturated with respect to siderite and rhodochrosite [MnCO3], and approaches saturation with respect to calcite and dolomite (Table 6). Water collected from piezometers installed into the clay underlying the tailings approaches equilibrium

Table 6. Saturation indices for the carbonate mineralsa at piezometer nests AE1 to AE5b. Well AE1 nest AE1-V1 AE1-V2 AE1-V3 AE1-V4 AE1-1a AE1-1b AE1-2 AE1-3 AE1-4 AE1-6 AE1-9 AE1-11 AE2 nest AE2-1 AE2-2 AE2-3 AE2-4 AE2-5 AE2-6 AE3 nest AE3-V3 AE3-V4 AE3-V5 AE3-V6 AE3-V7 AE3-V8 AE3-2 AE3-3 AE3-4 AE3-6 AE3-8 AE4 nest AE4-V1 AE4-V2 AE4-V3 AE4-V4 AE4-V5 AE4-1 AE4-2a AE4-2b AE4-3 AE4-5 AE4-6 AE4-7 AE5 nest AE5-2 AE5-3 AE5-4 AE5-5 AE5-6
a

Depth (m) 0.12 0.38 0.62 0.88 0.92 0.92 1.91 2.95 3.92 6.24 9.55 10.84 1.19 2.04 2.69 3.89 5.17 5.46 0.62 0.88 1.12 1.38 1.62 1.92 2.18 2.83 4.54 6.04 7.93 0.10 0.30 0.50 0.70 0.90 1.00 2.10 2.10 2.73 4.87 5.73 6.39 1.17 1.96 3.23 4.06 5.82

Calcite 1.04 0.39 0.52 0.86 0.69 0.71 0.31 0.80 1.17 0.77 0.87 0.64 0.01 0.21 0.58 0.71 0.07 0.16 0.56 0.46 0.28 0.46 0.30 0.81 0.24 1.03 0.92 0.52 0.18 0.39 0.61 0.68 0.22 0.34 0.11 0.09 0.16 0.18 0.47 0.01 0.66 0.40 0.59 0.92 0.14 0.40

Dolomite 1.97 0.01 0.40 1.53 0.56 0.56 0.84 1.65 2.61 1.52 1.33 0.95 0.50 0.25 1.20 1.71 0.26 0.55 1.23 1.25 1.29 1.39 0.07 1.14 0.02 2.07 2.31 1.37 0.28 0.65 0.91 1.80 1.32 0.14 1.07 0.39 0.46 0.50 1.13 0.29 1.92 1.02 1.67 2.26 0.37 0.33

Siderite(C) 0.10 1.05 1.73 1.17 1.43 1.02 0.55 2.30 1.64 1.32 0.44 1.09 0.84 1.60 2.52 0.79 0.96 0.23 0.62 0.20 1.32 0.55 0.13 1.68 1.34 1.84 3.16 2.97 0.04 1.48 1.21 1.12 0.17 1.40 1.65 3.72 3.63 3.68 1.97 1.25 3.63 2.38 0.91 0.99 0.66

Siderite(D) 0.65 1.60 2.28 1.72 1.98 1.56 0.04 2.89 2.24 1.91 0.15 0.50 0.28 2.18 3.11 1.38 0.37 0.36 1.19 0.77 0.74 1.14 0.73 2.27 1.94 2.45 3.76 3.57 0.55 2.03 1.76 1.67 0.73 1.96 2.21 4.30 4.22 4.26 2.57 0.70 4.20 2.97 1.51 0.40 0.06

Rhodochrosite 0.51 1.48 1.92 1.88 1.47 1.58 1.26 2.20 2.40 0.26 0.61 1.20 1.70 1.86 1.84 0.99 0.85 0.23 0.30 0.39 0.51 1.66 2.30 1.09 2.58 2.25 1.79 0.65 0.29 0.88 0.17 0.69 1.42 0.92 1.17 1.29 1.24 1.72 0.44 1.04 1.19 1.62 1.81 0.79 0.48

Siderite(C): Crystalline, Ksp from Nordstrom et al. (1990) and Ptacek (1992). Siderite(D): Disordered, Ksp from Singer and Stumm (1970). Compositions: calcite CaCO3, dolomite CaMg(CO3)2, siderite FeCO3, rhodochrosite MnCO3. Samples designated by V indicate collection from the vadose zone.

Sulphide-bearing carbonate-rich gold-mine tailings impoundment

703

with respect to calcite, dolomite and siderite, but remains undersaturated with respect to rhodochrosite. In the shallow portion of the impoundment, where the water has been aected by sulphide oxidation, many samples approach saturation with respect to calcite and siderite, and vary from nearsaturation to slightly supersaturated with respect to dolomite. All but the shallowest samples remain undersaturated with respect to rhodochrosite. These observations suggest that the carbonate minerals dissolve to saturation in the near-surface zone. Release of Ca, HCO3, and Mg by calcite and dolomite dissolution may favor precipitation of secondary dolomite, but because of kinetic hindrances, dolomite precipitation does not occur and the condition of supersaturation is maintained. Sulphideoxidation and acid-neutralization reactions release SO4 and Ca to the tailings water, resulting in the precipitation of gypsum. Gypsum occurs throughout the tailings, and geochemical calculations consistently indicate near-saturation with respect to gypsum (Table 3). In addition to Fe and SO4, sulphide oxidation releases other dissolved elements, such as As, to the tailings pore-waters. Analyses of tailings-water samples indicate that concentrations of dissolved As are consistently <50 mg/l. The concentrations of dissolved As are less than those observed in an inactive impoundment of Au-mine tailings near Timmins, Ont., at which dissolved As concentrations exceed 20 mg/l (Blowes, 1990). Mineralogical examination of core samples collected from the Agnico-Eagle site indicates that the arsenopyrite grains are sparse and show little sign of alteration, suggesting that little As has been released to the tailings pore-water. Concentrations of dissolved metals are consistently low and are restricted to depths near the tailings surface (Figs. 37). Maximum concentrations of the dissolved metals Cu, Ni, Zn, Co, Cr, Cd, and Pb are lower than observed in base-metal tailings impoundments at which low-pH conditions prevail (Dubrovsky et al., 1984a,b; Blowes and Jambor, 1990; Blowes et al., 1992). The maximum concentrations of these metals occur within the upper 2 m of the tailings surface. In the Agnico-Eagle tailings, the maximum concentrations of Cd, Co, Cr and Cu are consistently <0.2 mg/l, and the concentrations of Ni, Pb and Zn exceed 0.2 mg/l in only 2 or 3 samples. The maximum concentration of Zn, 1.83 mg/l, occurs near the tailings surface at piezometer nest AE1. The maximum concentration of Ni is <0.5 mg/l, and the maximum concentration of Pb is 0.24 mg/l. The adsorption of these metals to ferric oxyhydroxide phases is expected to be extensive under the neutral to slightly basic pH conditions that are observed in the tailings (Leckie et al., 1980). It is probable that adsorption along the groundwater

owpath will result in further decreases in the concentrations of these metals.

CONCLUSIONS

Oxidation of sulphide minerals occurs in the upper 20100 cm, which is the zone of active oxidation in the Agnico-Eagle tailings impoundment. Sulphide oxidation is indicated by the depletion of sulphide minerals at the tailings surface, by the formation of alteration rims surrounding primary sulphide particles, and by a sharp decrease in the gasphase O2 concentrations. Pyrrhotite is the most intensely altered sulphide mineral, followed by pyrite. The tailings are rich in carbonate minerals, containing calcite, dolomiteankerite and siderite. The pore-water pH, measured throughout the tailings impoundment, is near-neutral. This observation suggests that the dissolution of the abundant carbonate minerals has been sucient to consume the acidity released by sulphidemineral oxidation. The concentrations of dissolved metals, including Fe, in the tailings pore-water are low. Because of the high pH conditions present in the impoundment, and because the concentrations of dissolved Fe have remained low, there is little potential for net acid generation. Acidic drainage is detected in drainage ditches surrounding the impoundment, but the source of this acidity seems to be the waste rock used to armor the dam and to enhance impoundment stability. The dominant group of sulphideoxidizing bacteria present in the tailings are the neutrophilic Thiobacilli such as T. thioparus, which have an optimum pH range of 6.58.0. The populations of the acidophilic species such as T. thiooxidans and T. ferrooxidans are much lower. This observation suggests that the neutrophilic Thiobacilli have a major role in sulphide oxidation. The maximum MPN values for T. thiooxidans occur 2040 cm below the tailings surface, at a depth that coincides with the depth of active oxidation as indicated by the sharp decrease in gas-phase O2 concentration.

Acknowledgements We thank Y. Sylvestre of Mines e for his assistance. W. D. Robertson, Agnico-Eagle Limite T. A. Al, M. J. Baker, K. J. De Vos, and M. C. Moncur provided technical assistance in the eld. Financial support was provided through grants from Mines Agnico e, the Canada Centre for Mineral and Energy Eagle Limite Technology (CANMET), and the Natural Science and Engineering Research Council of Canada (NSERC). The manuscript beneted greatly from the comments of reviewers D. B. Levy and D. Runnells. Editorial handling:D. D. Runnells

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