Cases and solutions
Mobilization and attenuation
of heavy metals within a nickel
mine tailings impoundment near
Sudbury, Ontario, Canada
R. G. McGregor 7 D. W. Blowes 7 J. L. Jambor 7 W. D. Robertson
Abstract The oxidation and the subsequent disso-
lution of sulfide minerals within the Copper Cliff
tailings area have led to the release of heavy metals
such as Fe, Ni, and Co to the tailings pore water.
Dissolved concentrations in excess of 10 g/l Fe and
2.2 g/l Ni have been detected within the shallow
pore water of the tailings, with increasing depth
these concentrations decrease to or near analytical
detection limits. Geochemical modelling of the
pore-water chemistry suggests that pH-buffering
reactions are occurring within the shallow oxidized
zones, and that secondary phases are precipitating
at or near the underlying hardpan and transition
zones. Mineralogical study of the tailings confirmed
the presence of goethite, jarosite, gypsum, native
sulfur, and a vermiculite-type clay mineral. Goe-
thite, jarosite, and native sulfur form alteration
rims and pseudo-morphs of the sulfide minerals.
Interstitial cements, composed of goethite, jarosite,
and gypsum, locally bind the tailings particles,
forming hardpan layers. Microprobe analyses of the
goethite indicate that it contains up to 0.6 weight
% Ni, suggesting that the goethite is a repository
for Ni. Other sinks detected for heavy metals in-
clude jarosite and a vemiculite-type clay mineral
which locally contains up to 1.6 weight % Ni. To
estimate the mass and distribution of heavy metals
associated with the secondary phases within the
shallow tailings, a series of chemical extractions
was completed. The experimental design permitted
four fractions of the tailings to be evaluated inde-
pendently. These four fractions consisted of a wa-
ter-soluble, an acid-leachable, and a reducible frac-
tion, as well as the whole-rock total. Twenty-five
percent of the total mass of heavy metals was re-
Received: 9 April 1997 7 Accepted: 21 July 1997
R. G. McGregor (Y)
Water Technology International, PO Box 50 68, Burlington,
Ontario L7R 4L7, Canada
Tel.: 905 336 4855 7 Fax: 905 336 4765
D. W. Blowes 7 J. L. Jambor 7 W. D. Robertson
Department of Earth Sciences, University of Waterloo,
Waterloo, Ontario N2L 3G1, Canada
moved in the acid-leaching experiments, and 100%
of the same components were removed in the re-
duction experiments. The data suggest that precipi-
tation/coprecipitation reactions are providing an ef-
fective sink for most of the heavy metals released
by sulfide mineral oxidation. In light of these re-
sults, potential decommissioning strategies should
be evaluated with the recognition that changing the
geochemical conditions may alter the stability of
the secondary phases within the shallow tailings.
Key words Sulfide oxidation 7 Mine tailings 7
Heavy metals 7 Metal attenuation
Introduction
The Copper Cliff tailings area is approximately 5 km west
of Sudbury, Ontario, Canada, between the towns of Cop-
per Cliff and Lively (Fig. 1). The tailings area, one of the
largest repositories of tailings in Canada, covers approxi-
mately 2200 ha (Puro and others 1995). Tailings have
been deposited in the basin since the 1930s. The basin is
designed to receive tailings until the 2020s, at which
point the basin will hold more than 700 million tonnes
(Puro and others 1995). The basin is divided into nine
areas (Fig. 1); areas A, C–D, M, P and Q contain tailings
that were deposited between 1936 and 1989.
To reduce wind erosion and help stabilize the tailings, a
revegetation program was undertaken in 1957 on the C–
D and M areas (Peters 1984). Dolostone (8.8 t/ha) and
fertilizer (0.45 t/ha) were applied to the tailings surface to
help stimulate growth at the time of planting and addi-
tional dolostone and fertilizer were applied periodically
to help maintain growth. The R-areas are currently ac-
tive, with R1 receiving pyrrhotite concentrate and areas
R-2 and R-3 receiving low-sulfide tailings. Area R-4 is
currently under development.
Previous studies by Coggans and others (1991) on the M
area tailings and McGregor and others (1995, 1998) on
the M and P area tailings have shown that the oxidation
and the subsequent dissolution of sulfide minerals within
the shallow tailings have led to the release of heavy me-
tals such as Fe, Ni, and Co to the tailings pore water.
Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag 305
 Cases and solutions

Fig. 2
Cross section of the P (B-Bb) impoundment, showing
piezometer network and stratigraphy of the tailings. Piezometer
intakes are marked as solid circles

60 ml were obtained from most core sections. After col-

lection, the pore-water samples were filtered through
Fig. 1 0.45-mm cellulose-acetate filters and split into two sub-
Location of the Copper Cliff Tailings disposal area samples. The first subsample was acidified with 12 N,
analytical-grade HCl to a pH less than 1.5 for cation anal-
ysis, whereas the second subsample was left unacidified
Dissolved concentrations in excess of 10 g/l Fe and 2.2 g/l and was analyzed for anions. All samples were refriger-
for Ni have been detected in the shallow tailings, but ated until analysis.
with depth these concentrations quickly decrease to or Pore-water samples from the saturated zone were col-
near detection limits (McGregor and others 1998). The lected from drive-point piezometers installed at regular
objectives of this paper are to discuss the reactions re- intervals (1–2 m) within tailings between the water table
leasing the heavy metals to the pore water and to deter- and the base of the impoundment (Fig. 2). A combina-
mine the mechanisms that control the mobility of the tion of PVC and stainless steel piezometers was used. All
heavy metals within the shallow tailings. piezometers were purged dry prior to sampling by using
a peristaltic pump and high-density polyethylene tubing.
Pore-water samples were collected using a peristaltic
pump, high-density polyethylene tubing and a sealed
Methods of investigation flow-through cell as described by Coggans and others
(1991). Measurements of pH, EH, and temperature were
Pore water made in the sealed flow-through cell maintained at
Samples for pore-water analysis were extracted from the groundwater temperature. Pore-water samples were col-
vadose zone within the P area (IN14 and IN15, Fig. 2) lected and filtered with a 0.45-mm cellulose-acetate filter,
during the summers of 1990 and 1992 by collecting cores and were split into two subsamples for analysis of cations
in 7.62-cm-diameter, thin-walled aluminum tubing. The and anions. The subsample for cation analysis was acidi-
collected cores were then cut into 25-cm lengths and fied using 12 N analytical-grade HCl to below pH 1.5. The
squeezed using a method similar to that described by samples were then refrigerated until they were analyzed.
Patterson and others (1978), as modified by Smyth Prior to each reading, the pH electrode (Orion Ross com-
(1981). The main advantage of this method is that the bination pH electrode, Model 815600) was calibrated us-
tailings within the core are isolated from atmospheric ing pH 2.0, 4.0, and 7.0 buffers (traceable to NIST stand-
oxygen, thus minimizing the oxidation of Fe(II) during ards) maintained at pore-water temperature (5–10 7C).
pore-water sample collection. Measurements of pore-wa- Calibration was reconfirmed after each measurement. The
ter pH, EH, ferrous iron (Fe(II)), temperature, and alka- EH electrode (Orion platinum redox electrode, Model
linity were made in the field immediately after sample 967800) was checked prior to each reading with Zobell’s
collection. Pore-water sample volumes of between 20 and solution (Zobell 1946; Nordstrom 1977) and Light’s solu-

306 Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag

 Cases and solutions

tion (Light 1972). The acidified pore-water samples from content of the tailings was determined using a modified
both the vadose and saturated zones were analyzed for method of Barker and Chatten (1982) as described by
Al, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Si, and McGregor (1994). A subsample was submitted to Activa-
Zn by atomic absorption spectrophotometry (AAS), and tion Laboratories, Ancaster, Ontario, for whole-rock ana-
the unacidified samples were analyzed by ion chromato- lyses using a variety of analytical techniques that in-
graphy (IC) for Cl, NO3, PO4, and SO4 at the Water Qual- cluded instrumental neutron activation (INAA), induc-
ity Laboratory at the University of Waterloo. Total dis- tively coupled plasma emission spectroscopy (ICP), in-
solved As concentrations were determined using AAS af- ductively coupled plasma emission spectroscopy with
ter hydride generation. The accuracy of the laboratory re- mass spectroscopy (ICP/MS), and X-ray fluorescence
sults was assessed by including blanks and replicate sam- spectroscopy (XRF). Tailings samples were then subjected
ples and by performing charge-balance calculations on all to chemical extractions to determine three fractions: wa-
samples. All pore-water samples tested had a charge bal- ter-soluble, acid-leachable, and reducible. The method
ance difference of less than 8%. Pore-water alkalinity was and reagents used for the chemical extractions are pro-
determined by using standardized H2SO4, methyl red, vided by McGregor and others (1995).
bromocresol green indicator (Greenberg and others
1992), and a Hach Chemical Company digital titrator. Data interpretation
Pore-water ferrous iron (Fe(II)) concentrations were de- The geochemistry of the pore water was interpreted with
termined using the potassium dichromate titration tech- the aid of the geochemical speciation mass transfer mod-
nique of Waser (1966). Whenever possible, duplicate el MINTEQA2 (Felmy and others 1983; Allison and others
measurements were made for Fe(II) and alkalinity. 1990). A modified version of MINTEQA2 was used to
make its data base consistent with the WATEQ4F data-
Tailings solids base (Ball and Nordstrom 1991). Solubility data for K,
Duplicate cores of tailings solids were collected at both Na, and H3O jarosites were changed to the values recom-
IN14 and IN15 in thin-walled aluminum casing, 5.08 cm mended by Alpers and others (1989). The revised data
in diameter, using a modified version of the technique base also includes calculated or estimated ion-association
described by Starr and Ingleton (1992). Continuous cores constants for Fe(II), Fe(III), Ca(II), and Al(III) bisulfate
of the tailings were taken to depths of 9 m at IN14, and complexes that were not included with the original MIN-
13 m at IN15, thus encompassing the complete oxidation TEQA2 data base. Additional solubility data for siderite
profile. The cores were immediately sealed and one of the were added to the data base on the basis of the work of
duplicate cores was frozen to minimize exposure to at- Nordstrom and others (1990) and Ptacek (1992). Because
mospheric oxygen during transportation. The unfrozen of the relatively high Ni concentrations in the pore water,
core was sampled at regular intervals (10 cm) for deter- solubility constants for the nickel sulfate phases NiSO4,
minations of moisture content, grain size, porosity, bulk, NiSO47H2O, and NiSO474H2O were added (DeKock 1982)
and particle density. The bulk density, porosity, and to the data base. Solubility constants for NiSO473Ni(OH)2
moisture content were determined by gravimetric and and (NiSO4) 74Ni(OH)2 (Wagman and others 1982) were
3

volumetric techniques. Using a known volume of dry and also entered into the MINTEQA2 data base. Rizkalla and
wet weights of an undisturbed sample, the moisture con- Choppin (1988) reported an error in the Gibb’s free ener-
tent and bulk density can be calculated. Combining the gy value for (NiSO4)374Ni(OH)2, but as they made no
bulk density with the particle density allows the porosity suggestion for a new value, the previous value was re-
of the tailings to be calculated using the method of Dan- tained. Thermodynamic data were also added to the data
ielson and Sutherland (1986). Particle-density measure- base for cobaltocalcite (CoCO3) (Papelis and others 1988),
ments were obtained using a Beckman Model 930 air bieberite (CoSO477H2O) (DeKock 1982), and heterogenite
comparison pycnometer. Grain-size analyses were per- (CoOOH) (Wolery 1979). Sulfide-oxidation reactions were
formed on tailings samples using sieve techniques at the modelled using the approximate analytical solution by
Quaternary Laboratory at the University of Waterloo. Davis and Ritchie (1986).
Tailings samples for thin sections were collected and pre-
pared. The thin sections were then subjected to a minera-
logical study at the University of Waterloo, and at the
Mineral Sciences Laboratories at CANMET in Ottawa. Results and discussion
The mineralogical study included microscopic examina-
tion under reflected and transmitted light as well as ex- Tailings stratigraphy
amination by scanning electron microscopy (SEM), X-ray Two cores were obtained from the P tailings area in du-
diffraction (XRD), and electron microprobe. plicate (IN14 and IN15, Fig. 2). These tailings, deposited
The duplicate core was thawed and dried at 60 7C, and from 1960 to 1988, cover approximately 380 ha to a max-
was submitted for analysis of whole-rock chemistry in- imum depth of approximately 28 m. Grain-size analyses
cluding total sulfur, total carbon, acid-digestible carbon, show that the tailings are a fine-to-medium-grained, well-
and chemical extractions. The total sulfur and total car- sorted sand (Fig. 3). Porosity measurements below 0.25 m
bon were determined by Leco induction furnace equipped have an arithmetic mean of 0.49 (sample sizep56, stand-
with an infra-red detector. The acid-digestible carbon ard deviationp0.050). Particle density measurements

Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag 307

 Cases and solutions

Fig. 4
Schematic showing the geochemical and hydrogeologic zones
associated with the Copper Cliff tailings area

goethite, jarosite, and gypsum are abundant within this

zone. A fourth, but discontinuous, zone occurs within the
tailings. At IN15, a 0.2-m-thick layer of cemented tailings
occurs at a depth of 0.70 m, whereas at IN14 a 0.3-m-
thick layer of cemented tailings occurs at 1.4 m depth,
well within the unoxidized tailings. The fifth and deepest
zone is composed of unweathered tailings. At both IN14
and IN15, significant amounts of magnetitic and hematit-
ic slag and calcine (`20 weight %) occur in thin, con-
centrated layers within the upper 1.5 m.

Fig. 3 Tailings mineralogy

Grain-size distribution of tailings within the P impoundmentThe minerals of the P tailings area may be classified into
for IN14 and IN15 four groups in accordance with the classification system
of Jambor and Owens (1993). Primary minerals are those
that constituted the ore and gangue assemblages, and
have an arithmetic mean of 3.07 g/cm 3 (sample which were processed through the mill and deposited in
sizep217, standard deviationp0.194). The tailings in the the tailings area. The primary minerals include oxide and
P area had been exposed to atmospheric oxygen for ap- silicate minerals such as quartz, chlorite, pyroxene, etc.,
proximately 5 years at the time of sampling. Based on and sulfide minerals such as pyrrhotite and pyrite. Sec-
visual and mineralogical observations of the sulfide and ondary minerals precipitate within the tailings impound-
secondary minerals, the tailings may be divided into five ment due to oxidation and dissolution/precipitation reac-
geochemical zones (Fig. 4). The first zone is a thin sur- tions at or near the surface of the tailings. The secondary
face layer into which fertilizer and agricultural dolostone minerals include such phases as gypsum, goethite, and ja-
have been amalgamated as part of the revegetation pro- rosite. Tertiary products are those that crystallize after
gram. This layer is usually confined to the upper 0.25 m the tailings samples have been removed from the tailings
of the tailings. The second zone is a highly oxidized zone impoundment. The elements in the tertiary minerals ori-
in which all of the sulfide minerals have been completely ginale in the pore water of the core. An example of ter-
replaced. The tailings at IN14 and IN15 have been exten- tiary formation is the precipitation of fine-grained gyp-
sively oxidized to depths of 0.23 and 0.44 m, respectively. sum or ferrous sulfates during drying of the core. The fi-
Within this zone the sulfide minerals have been con- nal group of minerals form by superficial oxidation dur-
sumed by oxidation, and some of the silicate minerals, ing the storage of the dried cores. This group of minerals
particularly biotite, show evidence of dissolution and are is classified as quaternary products. These minerals may
coated by goethite and jarosite. The third zone, the thick- be distinguished by the appearance of surface blooms, al-
est (up to 0.78 m) within the alteration zone, consists of though the distinction between tertiary and quaternary
alternating layers, 3–5 mm thick, of oxidized and unoxid- efflorescences may be difficult in some cases. In this pa-
ized tailings. The oxidized tailings are coarser grained per discussion of the tailings mineralogy will be limited
than the unoxidized layers. Secondary minerals, including to the primary and secondary minerals.

308 Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag

 Cases and solutions

Optical microscopy and whole-rock analyses of the unox- Table 1

idized tailings from IN14 and IN15 indicated that the sul- Electron-microprobe analyses amphibole, Copper Cliff tailings.
fide content in the tailings is approximately 10 volume % (All concentrations in wt. %. Standard deviation calculated
using 0.05 wt. % when concentrations are below the detection
as sulfur. This value is significantly higher than the 4 vol- limit.)
ume % as sulfur reported by Peters (1984) for the adja-
cent M tailings area. The increase in the sulfide content grain grain grain grain grain aver- std.
in the younger P area tailings is due to changes in the 1 2 3 4 5 age dev.
milling procedures (Puro and others 1995). The bulk of
sulfide mineral grains (`95%) observed are pyrrhotite Na 1.3 1.1 1.1 0.4 0.9 1.0 0.3
(Fe1PxS); the remaining F5% sulfides are, in decreasing K 0.3 0.5 0.3 0.2 0.5 0.4 0.1
Mg 3.5 3.3 4.2 8.8 5.2 5.0 2.3
order of abundance, chalcopyrite CuFeS2, pentlandite Ca 7.9 8.0 8.2 8.3 8.4 8.2 0.2
(Fe,Ni)9S8, pyrite FeS2, marcasite FeS2, and galena PbS. Fe 18.1 17.8 15.7 10.4 15.2 15.4 3.1
Chalcopyrite is typically included within silicates, whereas Mn 0.3 0.2 0.3 0.1 0.3 0.2 0.09
pentlandite occurs mainly as anhedral grains and as exo- Ti 0.2 0.2 0.2 0.4 0.6 0.3 0.2
lution flames within pyrrhotite. Marcasite and pyrite are Al 7.6 7.9 8.2 3.4 5.3 6.5 2.1
present only in trace amounts, occurring more variably Si 18.8 19.0 19.3 22.8 20.3 20.0 1.6
as free grains, as inclusions in silicates, and in association Cl 0.4 0.4 ~0.1 ~0.1 ~0.1 0.2 0.2
with other sulfide minerals. Within the shallow tailings at
IN14 and IN15 (~0.3 m) no sulfide minerals were ob-
served. Examination of polished sections of the shallow are pseudo-morphed by cristobalite (or opal). An analysis
tailings revealed them to consist largely of hematitic slag, of one of the pseudo-morphs gave FeO 2.8%, MgO 0.3%,
magnetite, and nonsulfide gangue minerals. Al2O3 0.9%, SiO2 79.4%, sum 83.4%. The low total is at-
Examination of thin sections and X-ray diffractometer tributed to the presence of water. Table 3 lists micro-
patterns of the tailings indicated that the primary gangue probe compositions for four altered phlogopite-biotite
minerals are chlorite, mica (phlogopite-biotite), amphi- grains. Microprobe analyses of several cores and rims of
bole, quartz, and plagioclase. Minor amounts of ilmenite, altered phlogopite-biotite grains indicate that K in the
potassium feldspar, apatite, orthopyroxene, clinopyrox- grain rims is depleted relative to the K in the cores of the
ene, titanite, and talc were also detected. Electron micro- grains. In order to show the transformation of the mica
probe analyses of five grains of amphibole and eight relative to a constant reference point for the four mica
grains of mica determined that the variation in amphi- grains analyzed, the formulas were calculated on the ba-
bole and mica compositions is substantial. Tables 1 and 2 sis of Sip3.00 (Table 3). The general character of the al-
provide the analyses of the amphibole and mica grains, teration is shown in Fig. 5.
respectively. Analyses of the amphibole grains suggest The principal secondary minerals within the tailings are
that the amphiboles range in composition from a ferron goethite (aFeOOH), K-dominant jarosite
pargasite (grain 1) to magnesio-hornblende (grain 4) to (KFe3(SO4)2(OH)6), native sulfur (S 0), and gypsum
ferro-hornblende (grain 5), assuming that the Fe is as (CaSO472H2O). Lesser amounts of covellite (CuS), marca-
Fe 2c (Table 1). site (FeS2), siderite (FeCO3), cristobalite (SiO2), and a ver-
The microprobe analyses of the mica grains indicate that miculite-type phase were detected by optical microscopy
the proportions of Mg and Fe in the grains are highly and X-ray diffraction. X-ray diffraction patterns indicate
variable with the most Fe-rich members extending that goethite and jarosite are confined to the oxidation
beyond the phlogopite-biotite field to annite (Table 2). and hardpan zones, whereas gypsum occurs throughout
Microprobe analyses also revealed that, upon alteration, the tailings profiles (Fig. 6). Microprobe analyses of jaro-
K is being depleted in the mica and ultimately the grains site-bearing oxidation rims in the shallow tailings are

Table 2
Electron-microprobe analyses phlogopite-biotite, Copper Cliff tailings area. (All concentrations in wt. %. Standard deviation
calculated using 0.05 wt. % when concentrations are below the detection limit.)

grain grain grain grain grain grain grain grain average std.
1 2 3 4 5 6 7 8 dev.

K 7.3 6.4 7.0 7.6 7.6 6.7 7.5 7.6 7.2 0.5
Mg 6.0 5.2 9.2 5.6 5.8 5.1 6.1 1.8 5.6 2.0
Fe 16.9 17.9 12.0 17.2 18.3 19.4 16.8 25.5 18.0 3.7
Mn 0.1 0.1 0.1 0.2 0.1 0.1 0.1 0.2 0.1 0.05
Ti 0.9 1.0 2.0 0.7 1.2 1.2 1.2 0.7 1.1 0.4
Al 8.2 8.3 6.3 8.1 8.7 8.8 8.9 9.7 8.4 1.0
Si 16.3 15.7 17.1 15.9 16.8 16.5 16.7 15.5 16.3 0.6
Cl 0.3 0.1 0.4 0.2 P P P P 0.2 0.1

Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag 309

 Cases and solutions
Table 3
Microprobe compositions of rims and cores of altered
phlogopite-biotite grains
grain calculated formula
ideal biotite K(Mg,Fe 2c)3(Al,Fe 3c)Si3O10(OH,F)2
grain 1 core K0.36(Mg0.61Fe1.06)S1-67(Al0.96Ti0.11)Si3.00
rim K0.04(Mg0.14Fe0.69)S0.83(Al0.24Ti0.05)Si3.00
grain 2 core K0.32(Mg0.57Fe1.89)S2.46(Al0.91Ti0.11)Si3.00
rim K0.05(Mg0.17Fe0.72)S0.89(Al0.30Ti0.05)Si3.00
grain 3 core K0.37(Mg0.59Fe1.21)S1.80(Al0.99Ti0.11)Si3.00
rim K0.04(Mg0.12Fe0.59)S0.71(Al0.21Ti0.04)Si3.00
grain 4 core K0.34(Mg0.55Fe1.48)S2.03(Al0.80Ti0.12)Si3.00
rim K0.01(Mg0.09Fe0.60)S0.69(Al0.14Ti0.05)Si3.00
given in Table 4. The first two analyses listed in Table 4
correspond to K0.48(Fe2.94Al0.11)S3.05(SO4)2.00 and
K0.57(Fe3.49Al0.08)S3.57(SO4)2.00. The first analysis on a thin
layer corresponds well with jarosite stoichiometry if it is
assumed that hydronium is the predominant cation in
the alkali position. The second analysis, however, has ex-
cess Fe, likely indicating admixed goethite. The last anal-
ysis in Table 4 gives the formula
310 Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag
K0.55(Fe4.03Al0.31)S4.34(SO4)2.00, also indicating the presence
of admixed goethite.
Native sulfur occurs both as pseudo-morphs after pyrrho-
tite, and as rims around pyrrhotite grains. X-ray diffrac-
tograms also suggest that the vermiculite-type alteration
associated with mica shown in Fig. 6 is limited to the ox-
idized zones of the tailings.
Sulfide oxidation
The oxidation of pyrrhotite (Fe1PxS), the predominant
sulfide mineral within the Copper Cliff tailings, has pro-
duced elevated concentrations of SO4, Fe, and other hea-
vy metals within the tailings pore water. McGregor and
others (1997) observed sulfide mineral depletion in the
shallow tailings, where pore-gas O2 concentrations were
near atmospheric levels. As the intensity of sulfide altera-
tion decreases with depth, the pore-gas O2 concentration
Fig. 5
Backscattered electron image of altered mica. Corresponding
X-ray maps for Fe, Si, and K show the depletion of K and Fe,
and enrichment in Si. Bar scale represents 25 mm
 Cases and solutions

Fig. 6
X-ray diffractograms of tailings from the
upper 75 cm of IN14. Labels correspond
to 1B 18 cm depth, 2T 32 cm depth , 2B
43 cm depth, 3T 56 cm depth, and 3B 68
cm depth. Abbreviations are ch: chlorite,
v: vermiculite-type mineral, mi: mica,
am: amphibole, gy: gypsum, fs: feldspar,
j: jarosite (two peaks, indicated by dots),
q: quartz, H: hematite, M: magnetite,
and sid: siderite

Table 4 may be catalyzed by the presence of bacteria such as

Analyses of jarosite-bearing mixtures in the Copper Cliff Thiobacillus ferrooxidans (Singer and Stumm 1970). Nor-
tailings area. (All concentrations are in wt. %.) ris and Parrott (1986) confirmed that T. ferrooxidans can
thin layer on thick layer on zones layer on
catalyze the oxidation of Fe(II) in pyrrhotite/pentlandite-
silicate silicate silicate rich systems.
The oxidation of pyrrhotite, by either O2 or Fe(III), may
zone 1 zone 2 only proceed to partial completion, resulting in the for-
mation of native sulfur (S 0) through the reactions:
Fe 32.7 36.2 38.1 34.4

1 2 2 O c2(1Px) H
K 3.7 4.1 3.1 3.3 1Px c
Al 0.6 0.4 1.7 1.3 Fe(1Px)Sc 2

Si ~0.1 ~0.1 0.2 0.2

] (1Px) Fe 2ccS 0c(1Px) H2O (4)
S 12.8 11.9 8.8 9.8
Fe(1Px)ScFe 3c3⁄4 O2c5⁄2 H2O
] 2FeOOHcS 0c3H c (5)
0
decreases and the sulfur content increases (McGregor and The presence of native S as pseudo-morphs of pyrrhotite
others 1998). At depths at which the sulfide grains are in the Copper Cliff tailings was confirmed by mineralogi-
unaltered, the pore-gas O2 concentration decreases to be- cal analyses (Fig. 7). The pyrrhotite grains in the oxidized
low the detection limit (~0.01 volume %). The complete and transitional zones are rimmed by an innermost layer
oxidation of pyrrhotite by oxygen may be described as: of native sulfur, followed by a layer of goethite, which in
turn is surrounded by an outermost layer of SO4-bearing
1 2
x
Fe(1Px)Sc 2 P O2cH2O goethite (McGregor and others 1998). Jambor and Owens
2 (1993) indicated that significant accumulations of S 0 also
] (1Px) Fe 2ccSO42P2!H c (1) occur within the Nickel Rim tailings impoundment, near
The Fe(II) produced through reaction (1) may then react Sudbury, Ontario.
with O2 and be oxidized to Fe(III) (Nordstrom 1982). The The native sulfur may be further oxidized by O2 through
Fe(III) may act further as an oxidant for pyrrhotite and the reaction:
release more Fe(II) to the pore water as follows: S 0c3⁄2 O cH O ] 2H ccSO 2P (6)
2 2 4
4Fe 2ccO2c4H c v 4Fe 3cc2H2O (2)
The Fe(III) produced through reaction (2) may be hydro-
Fe(1Px)Sc(8P2x) Fe 3cc4H2O lyzed and precipitated as a ferric (oxy)hydroxide or ferric
] (9P3x) Fe 2ccSO42Pc8H c (3) sulfate. Three possible reaction paths for the precipitation
of Fe(III) are the formation of amorphous ferric hydrox-
The rate of oxidation of pyrite by Fe(III) at low pH may
ide (nominally Fe(OH)3), goethite (aFeOOH), and jarosite
be faster than the rate of oxidation by O2 (Nordstrom
(KFe3(SO4)2(OH)6). The following reactions illustrate the
1982). At pH ~4.5, the oxidation of Fe(II) to Fe(III) is
formation of each phase:
slow and is therefore the rate-determining step in the
abiotic oxidation of pyrrhotite at low pH. The reaction Fe 3cc3H2O ] Fe(OH)3c3H c (7)

Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag 311

 Cases and solutions
Fig. 7
Backscatter images of pyrrhotite (po), pentlandite (pn) and
native sulfur pseudo-morphs (S), and corresponding X-ray
maps for Ni, Fe, and S. The alteration rim on the pyrrhotite
grain is mainly native sulfur with some goethite. Between the
two pentlandite grains is a slightly zoned grain of native sulfur,
typical for pseudo-morphs after pyrrhotite. Bar scale represents
100 mm
Fe 3cc2H2O ] aFeOOHc3H c
c c
K cFe 3c
c2SO 2P
4 c6H2O ] KFe3(SO4)2(OH)6c6H
Mineralogical studies of the Copper Cliff tailings have
confirmed the presence of goethite and jarosite within
the tailings (Coggans and others 1991; McGregor and
others 1998). The predominant secondary Fe phases with-
in the shallow tailings are goethite and jarosite that occur
as interstitial cements, alteration rims, and fracture infill-
ings. McGregor and others (1998) calculated the satura-
tion indices for the iron (oxy)hydroxide solid phases
[amorphous Fe(OH)3, goethite aFeOOH, and lepidocro-
cite gFeOOH] and determined that the pore water, except
that in the shallow zone at IN14, is supersaturated with
respect to these three phases. The shallow pore water at
IN14 is undersaturated with respect to Fe(OH)3 but is su-
persaturated with respect to the crystalline iron oxyhy-
droxide minerals goethite and lepidocrocite. As depth
and pH increase, the pore water becomes saturated with
312 Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag
respect to Fe(OH)3, indicating that poorly crystalline
Fe(OH)3 may provide a solid-phase control on Fe(III)
concentrations in the tailings pore water.
The oxidation of sulfide minerals, such as pyrrhotite,
pentlandite, pyrite, chalcopyrite, and galena, has depleted
the sulfide and pore-gas oxygen content in the shallow
tailings while releasing metals to the pore water. Measur-
ements of Stotal in the tailings solids ranged from detec-
tion limit (0.1 weight %) in the shallow tailings, to 6.4
(8) weight % (17.5 weight % as FeS) in the unweathered tail-
ings (Fig. 8). Sulfate, derived from the oxidation of pyr-
(9)
rhotite and from the process water, was detected at con-
centrations of up to 39.3 g/l (McGregor and others 1998).
Equilibrium calculations performed using MINTEQA2
suggest that the pore water throughout the tailings is at
or near saturation with respect to gypsum (McGregor
and others 1998). The equilibrium calculations suggest
that gypsum is an important solid-phase control on the
mobility of SO4. Other secondary phases that might in-
fluence the mobility of SO4 are jarosite KFe3(SO4)2(OH)6,
natrojarosite NaFe3(SO4)2(OH)6 hydronium jarosite
(H3O)Fe3(SO4)2(OH)6, and melanterite FeSO477H2O.
Equilibrium calculations suggest that the pore water is
supersaturated with respect to natrojarosite, jarosite, and
hydronium jarosite in the shallow tailings, and that the
pore water remains undersaturated with respect to me-
lanterite (McGregor and others 1998). Mineralogical ana-
lyses confirmed the presence of jarosite. Calculations sug-
 Cases and solutions

Table 5
Constant parameters for the analytical solution of Davis and
Ritchie (1986)

parameter value source

D2 2.60!10 P10 m 2/s 2

u0 0.265 kg/m 3 1
a 0.00002–0.000045 m 3
ε 1.995 3
ρs 23–415 kg/m 3 3
g 0.03 1
u 0.48–0.49 3
d 2.996 3
Source: 1) Davis and Ritchie (1986)
2) Blowes and Jambor (1990)
3) Measured

Fig. 8
Total sulfur contents of the tailings at IN14 and IN15. Hatched culated using two methods. The first involved adjusting
area represents a hardpan layer, and the inverted triangle the bulk oxygen-diffusion coefficient until the modelled
represents the water-table level at the time of sampling
oxidation front matched the observed oxidation front
(Fig. 9). This method has the effect of averaging the
moisture contents throughout the history of the tailings.
gest that hydronium may be present in substitution for
The second method used to calculate the bulk oxygen-
potassium, and this solid solution is also inferred from
diffusion coefficient relates the air-filled porosity (ε ) to
the microprobe analyses.
the bulk oxygen-diffusion coefficient in the following
McGregor and others (1998) report maximum concentra-
equation (Reardon and Moddle 1985):
tions of dissolved metals, up to 2.24 g/l Ni, 32.2 mg/l Co,
24.9 mg/l Zn, 0.5 mg/l Pb, 0.21mg/l Cu, and 0.16 mg/l Cd, D(O2)p3.98!10 P5 [(ε P0.05)/0.95] P1.7 T 3/2 (10)
for the shallow pore water. The concentrations of these
where T is temperature in Kelvin. The air-filled porosity
metals decrease sharply as a result of adsorption reac-
is calculated by determining the difference between the
tions and mineral-precipitation reactions that occur as
water-filled volume and a known solid volume of sample.
the pH increases near the base of the oxidized zones.
The bulk diffusion coefficients determined in the field
vary by approximately one order of magnitude, generally
Sulfide oxidation modelling
decreasing as the saturated zone is approached. It should
To model the oxidation rates of the pyrrhotite, a series of
be noted that these values represent the bulk oxygen-dif-
analytical and numerical solutions developed by Davis
fusion coefficients only for a specific time and are not
and Ritchie (1986, 1987) was used. The solutions are
based on the hypothesis that the rate of sulfide oxidation
is controlled by both the diffusion of oxygen to the sul-
fide grain (bulk oxygen diffusion) and the diffusion of
oxygen through a thin layer of water at the sulfide miner-
al surface. Davis and others (1986) undertook a compari-
son of the analytical and numerical solutions and con-
cluded that the results of the two are similar when the
particle diameter is less than 2 mm. At the Copper Cliff
site the D50 grain size of the tailings is less than 0.2 mm,
and grain-size distribution is narrow (Fig. 3); therefore,
the analytical solution was used to model the rate of sul-
fide oxidation.
The model assumes that the tailings grains are spherical
and have a single particle size. A constant bulk oxygen-
diffusion coefficient is also assumed to exist throughout
the vadose zone. Previous studies by Blowes and others
(1991) and Coggans and others (1991) used the analytical
solution to describe the rate of sulfide oxidation at var- Fig. 9
ious mine tailings sites, including at Copper Cliff. Table 5 Comparison of measured (solid circles and squares) and
provides a list of parameters used in the analytical solu- modelled (solid line) oxygen concentrations in the pore gas at
tion. The bulk oxygen-diffusion coefficient (D1) was cal- sites IN14 and IN15. Hatched area represents a hardpan layer

Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag 313

 Cases and solutions

Table 6 and the Nordic Main tailings in Elliot Lake, Ontario

Comparison of measured and modelled oxygen-diffusion (Dubrovsky and others 1984).
coefficients The release of these heavy metals to the pore water is the
site measured modelled difference
result of sulfide oxidation and subsequent dissolution
coefficients coefficients reactions within the oxidized zone of the tailings. The
(m 2/s) (m 2/s) mobility of each metal is a function of the chemistry of
the pore water and solids in the tailings. As the pore wa-
IN14 1.38!10 P6 1.35!10 P5 9.6 ter migrates along the groundwater flowpath, through the
IN15 2.56!10 P6 9.00!10 P6 3.5 transition zone, it reacts with the surrounding phases in
a series of dissolution and attenuating reactions. The me-
tals that are released by sulfide oxidation are attenuated
representative of the conditions that existed before and by precipitation, coprecipitation, and adsorption reac-
after the measurements were taken. A comparison be- tions. The following sections discuss the mechanisms in-
tween the measured bulk oxygen-diffusion coefficients volved in the release of each dissolved constituent to the
and the coefficients determined by modelling the oxida- pore water, and identify the probable solid-phase controls
tion fronts shows good agreement (Table 6), with the on each constituent.
modelled coefficients being greater than the measured McGregor and others (1998) reported maximum pore-wa-
coefficients by a factor of up to 9.6. The difference be- ter Ni concentrations of 2.24 g/l within the P area. Figure
tween the two values may be attributed to variations in 10 shows a micrograph of several slag particles and a
moisture content, fluctuations in the water-table levels, grain of pyrrhotite taken within the shallow tailings at
infiltration events, and the formation of cemented layers IN14. The corresponding X-ray map indicates that the
within the tailings. pyrrhotite is slightly nickeliferous and that Ni is erratical-
To evaluate long-term oxidation conditions the modelled ly distributed in the slag particles. Microprobe analysis of
bulk oxygen-coefficient (D1) was used along with the pa- the edge of a slag particle within the micrograph gave 0.4
rameters listed in Table 5. A water oxygen-diffusion coef- weight % Ni, and analysis of the most Ni-rich portion of
ficient (D2) of 2.60!10 P10 m 2/s was used in the solution. the particle gave a value of 43 weight % Ni. Calculations
This value is based on the diffusion of oxygen in water indicate that 43 weight % Ni cannot be accommodated as
and the effect of tortuosity on the diffusion of oxygen. A substitution for Fe 2c in a magnetite structure (that is
similar value for the water oxygen-diffusion coefficient FeO7Fe2O3 ] NiFe23cO4) which has a limit of 25 weight %
was used by Blowes and Jambor (1990) and Blowes and Ni. Thus, if the Ni occurs in a magnetite-type or hematite
others (1991). structure, there must be partial substitution for ferric
Estimated times to complete the oxidation of the vadose iron which suggests that the Ni more likely occurs as
zone at IN14 and IN15 varied between 29 and 263 years, some other high-temperature-derived oxide. The high
respectively. These times are conservative because the values of Ni within the slag suggest that the slag is prob-
model assumes that the bulk oxygen-diffusion coefficient ably the most important source of dissolved Ni. Although
remains constant throughout the vadose zone. As the ox- the Ni contents of the pyrrhotite are low, substantial
idation front approaches the water table or capillary amounts of this mineral have been replaced, thereby pro-
fringe, the air-filled porosity will decrease, causing the viding another but lesser source of pore-water Ni. Pent-
bulk oxygen-diffusion coefficient, and rate of oxidation, landite, as well as nickeliferous pyrite and marcasite, are
to decrease. In addition, if the water-table position is also sources of pore-water Ni, but the concentrations of
raised or lowered, the times for complete oxidation will these minerals in the tailings are too low to be of impor-
be affected. tance relative to the slag and pyrrhotite.
McGregor and others (1998) noted that the distribution
Mobility of heavy metals of Ni within the shallow tailings closely follows the distri-
The dissolved concentrations and mobilities of heavy me- bution of Fe, and suggested that the Ni is coprecipitated
tals in the Copper Cliff tailings area are controlled by a with the jarosite and ferric (oxy)hydroxide. Geochemical
complex series of oxidation, precipitation-dissolution, co- modelling, using MINTEQA2, indicated that the pore wa-
precipitation, solid-solution substitutions, and adsorp- ter is undersaturated with respect to all of the Ni-bearing
tion/desorption reactions. On the basis of the aqueous phases in the amended data base (McGregor and others
and whole-rock chemistry profiles, the mobility of the 1998). Mineralogical study of the tailings failed to isolate
trace metals within the Copper Cliff tailings area follows any discrete Ni phases, but Ni was found to be incorpo-
a sequence of: rated in interstitial goethite and in altered biotite grains.
The principal solid-phase repository for secondary Ni was
FepMnpNipCo`CdpZn`CrpPb`Cu
determined to be goethite that forms an interstitial ce-
Similar mobility trends have been noted at other sulfide ment. Microprobe analysis of two areas of the goethite
tailings impoundments including the adjacent M area at both gave 0.6 weight % Ni. Other studies on the parti-
Copper Cliff (Coggans and others 1991), the Nickel Rim tioning of Ni between pore water and oxide surfaces have
tailings near Sudbury (Johnson 1993), the Waite Amulet shown that Ni may be adsorbed or coprecipitated with
tailings at Noranda, Quebec (Blowes and Jambor 1990), iron (oxy)hydroxides (Theis and Richter 1980; Rai and

314 Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag


Fig. 10
Backscattered electron image of pyrrhotite (po) and porous
hematitic slag particles from IN14. Corresponding X-ray map
shows the distribution of Ni in the two phases. Bar scale
represents 25 mm
Fig. 11
Backscattered electron image and X-ray dot-map for Ni of a
large grain of altered biotite-phlogopite amidst silicate grains
(mainly Na-Ca plagioclase) and porous, hematitic slag in IN14.
Accompanying X-ray map shows that Ni has been incorporated
in the mica pseudo-morph which consists largely of Si with
minor Fe`Al`Mg plus trace S, Ti, and K. Bar scale represents
100 mm
Cases and solutions
others 1984; Cornell 1991). Microprobe analysis of several
silica-replaced mica grains gave up to 1.5 weight % Ni,
but most of the grains did not contain detectable Ni. Fig-
ure 11 shows an altered mica grain for which microprobe
analysis gave up to 1.3 weight % Ni.
Chemical extractions completed on the tailings solids by
McGregor and others (1995) indicated that up to 25% of
the total Ni mass is associated with the acid-leachable
fraction, and up to 100% of the total Ni mass is asso-
ciated with the reducible fraction within the shallow tail-
ings.
Dissolved Co concentrations within pore-water samples
from IN14 and IN15 are likely the result of oxidation and
dissolution of pentlandite. Arnold and Malik (1974) re-
ported that Co is associated with pentlandite within the
Sudbury ores. Dissolved concentrations of up to 32.3
mg/l Co were reported by McGregor and others (1998).
These high concentrations of dissolved Co quickly de-
crease to below detection limits (~0.05 mg/l) as the pH
Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag 315
 Cases and solutions
of the pore water increases to near neutral levels (McGre-
gor and others 1997). Equilibrium calculations indicated
that the pore water within the tailings is undersaturated
with respect to all of the Co-bearing phases in the
amended MINTEQA2 data base. Mineralogical examina-
tion of the tailings also failed to identify any discreet Co-
bearing phases.
Chemical extractions completed on the tailings indicated
that up to 25% of the total Co mass within the shallow
tailings is associated with the soluble fraction (McGregor
and others 1995). The acid-leachable concentrations of Co
are approximately equal to the soluble-fraction concen-
tration within the shallow tailings, suggesting that Co is
not effectively attenuated by the precipitation of jarosite.
The reducible fraction of Co accounts for up to 100% of
the total mass of Co within the shallow tailings, indicat-
ing that Co is being removed from the pore water by the
precipitation of goethite and other reducible phases. Bi-
bak and others (1995) and Cornell (1991) indicated that
Co can be incorporated into the structure of goethite.
The degree of attenuation seems to be approximately the
same as observed for Ni, with Co being coprecipitated or
adsorbed to goethite.
Dissolved Mn is probably derived from the dissolution of
Mn-bearing pyroxenes, chlorite, amphiboles, and carbon-
ates. Dissolved Mn reaches a maximum concentration of
58.6 mg/l within the shallow pore water, and shows a
mobility similar to that of Co, Fe, and Ni (McGregor and
others 1998). Geochemical modelling of the pore water
indicates that the predominant species in solution is
Mn(II), and that only the Mn-bearing carbonate phase
rhodochrosite (MnCO3) approaches saturation (McGregor
and others 1998).
Manganese seems to be partly attenuated by coprecipita-
tion and adsorption reactions with goethite. McGregor
and others (1995) reported that up to 30% of the total
Mn within the shallow tailings is associated with the re-
ducible fraction, suggesting that Mn is partly attenuated
by adsorption and/or coprecipitation with Fe (oxy)hy-
droxides. Rai and others (1984) reported that Mn may be
weakly absorbed onto Fe (oxy)hydroxides. Studies by Ta-
kematsu (1979), McKenzie (1980), and Cornell and Giova-
noli (1987) also showed that Mn may be absorbed onto
Fe (oxy)hydroxide surfaces or substituted with Fe oxyhy-
droxides.
Cadmium mobility within the Copper Cliff tailings is less
than that of Co, Fe, Mn, and Ni. Possible sources of Cd
include hawleyite (CdS) and sphalerite (ZnS) which have
been detected in the Copper Cliff ores by Coats and
Snajdr (1984). A maximum dissolved concentration of
0.16 mg/l was detected within the shallow pore water by
McGregor and others (1998). Geochemical modelling of
the pore water completed by McGregor and others (1998)
suggests that the pore water is undersaturated with re-
spect to amorphous Cd(OH)2. Mineralogical study of the
tailings did not detect any Cd-bearing phases within the
oxidized, hardpan, or transition zones. Chemical extrac-
tions completed on the tailing solids did not detect Cd in
the acid-leachable or reducible fractions (McGregor and
316 Environmental Geology 36 (3–4) December 1998 7 Q Springer-Verlag
others 1998). However, because of the relatively low con-
centrations of Cd within the tailings, it is not unexpected
that Cd is below the extraction detection limits (~0.003
mg/g). Studies by Kinniburgh and others (1976) and Bal-
istrieri and Murray (1982) have shown that Cd adsorbs to
Fe (oxy)hydroxide surfaces.
Dissolved Zn is derived from the oxidation and dissolu-
tion of sphalerite which occurs in trace amounts within
the Sudbury ore assemblage (Coats and Snajdr 1984).
McGregor and others (1998) report maximum dissolved
concentrations of 24.9 mg/l which decrease to detection
limits (~0.02 mg/l) as the pH increases. Comparison of
the pore-water chemistry profiles suggests that the mobil-
ity of Zn is similar to that exhibited by Cd and Pb within
the pore water. Equilibrium calculations completed by
McGregor and others (1998) suggest that the pore water
is undersaturated with respect to the Zn-bearing phases
smithsonite ZnCO3, boyleite ZnSO474H2O, and amor-
phous zinc hydroxide Zn(OH)2. Mineralogical study of
the tailings did not detect any discrete Zn-bearing phases.
Chemical extractions completed for the shallow tailings
suggest that the Zn present is associated with secondary
phases such as jarosite and goethite (McGregor and oth-
ers 1995). McGregor and others (1995) determined that
the water-soluble fraction of Zn can be attributed to the
redissolution of pore-water precipitates. The acid-leacha-
ble fraction for Zn within the shallow tailings accounts
for approximately 20–25% of the total Zn mass, and the
reducible fraction accounts for the remainder of the Zn
mass within the shallow tailings. Dutrizac and Dinardo
(1983) and Scott (1987) have reported that jarosite may
incorporate significant amounts of Zn and, in addition,
numerous authors have documented that Zn readily ad-
sorbs to iron (oxy)hydroxide surfaces (Kinniburgh and
others 1976; Benjamin and Leckie 1981; Balistrieri and
Murray 1982; Rai and others 1984). The solid-phase con-
trol on the mobility of Zn within the Copper Cliff tailings
appears to be coprecipitation and adsorption reactions
with goethite. Smaller masses of Zn may also be atte-
nuated by coprecipitation with jarosite and adsorption
onto vermiculite and altered biotite grains.
The dissolution of magnetite (Fe3O4) and ilmenite (Fe-
TiO3) are likely the primary sources of Cr within the tail-
ings pore water. Gasparrini and Naldrett (1972) reported
that the magnetite in the Sudbury ores may contain up to
9 weight % Cr2O3, and ilmenite may incorporate up to
1.1 weight % Cr2O3 into its structure. McGregor and oth-
ers (1995) showed profiles of the tailings that suggest that
Cr is being depleted within the zones of active and past
sulfide oxidation. The profiles also indicate that Cr is be-
ing enriched at or near the hardpan layers and near the
base of the oxidized zones at which secondary phases are
being precipitated. Pore-water concentrations for Cr
reach a maximum of 0.3 mg/l in the shallow tailings, and
then decrease to below detection limit (~0.05 mg/l) as
the pH rises above 6.0 (McGregor and others 1998).
Equilibrium calculations using MINTEQA2 suggest that
the pore water is supersaturated with respect to Cr(OH)3
in the pore-water samples in which Cr was detected

(McGregor and others 1998). Mineralogical analyses of
the Copper Cliff tailings did not detect any Cr-bearing
phases. Microprobe analyses of goethite at the nearby
Nickel Rim tailings impoundment detected the presence
of Cr within the goethite (Jambor and Owens 1993). Sass
and Rai (1987) observed that an amorphous solid-solu-
tion phase (CrxFe(1Px)(OH)3) readily formed at room
temperature and controlled the dissolved concentration
of Cr within solution. This phase maintained Cr concen-
trations several orders of magnitude lower than when in
equilibrium with Cr(OH)3 alone.
Extraction experiments by McGregor and others (1995)
suggest that up to 15% of the Cr within the shallow tail-
ings is associated with the acid-leachable fraction of the
tailings. In addition, up to 100% of the mass of Cr is as-
sociated with the reducible fraction of the shallow tail-
ings. On the basis of the results of extraction, pore-water,
and solids chemistry data, the mobility of Cr seems to be
controlled by the coprecipitation of secondary ferric (ox-
y)hydroxide phases and by adsorption onto these phases.
The phase most likely controlling the mobility of Cr is
goethite.
The Pb within the pore water is the result of oxidation
and dissolution of galena (PbS) which occurs as a trace
sulfide within the tailings. The maximum dissolved con-
centration of Pb detected within the tailings is 0.5 mg/l,
which quickly decreases to below detection limits (~0.01
mg/l) with depth (McGregor and others 1998). Equili-
brium modelling indicates that the pore water is undersa-
turated with respect to the Pb-bearing phases within the
MINTEQA2 data base (McGregor and others 1998). Mi-
neralogical analyses of the tailings did not detect any sec-
ondary Pb-bearing phase.
Chemical extractions by McGregor and others (1995)
failed to detect any Pb associated with the acid-leachable
or reducible fractions. Because of low concentrations of
Pb within the tailings and the relatively high detection
limit for Pb (0.01 mg/g), the failure to detect any Pb dur-
ing the chemical extractions was expected. These results
do not mean that Pb is not being attenuated by second-
ary phases, such as goethite and jarosite, but instead in-
dicate that Pb is not present within the secondary phases
at high enough concentrations (`0.01 mg/g) to be de-
tected using these techniques. Previous studies have
shown that Pb may be incorporated into jarosite (Dutri-
zac and Dinardo 1983) and adsorbed on Fe (oxy)hydrox-
ides (Benjamin and Leckie 1981; Balistrieri and Murray
1982; Rai and others 1984).
The oxidation and dissolution of chalcopyrite (CuFeS2)
release Cu to the pore water. McGregor and others (1998)
report maximum dissolved concentrations of Cu 0.21 mg/
l within the oxidized zone, which quickly decrease to be-
low detection limits (~0.05 mg/l) in the unweathered
tailings. Geochemical modelling of the pore-water chem-
istry suggests that the pore water is undersaturated with
respect to the Cu-bearing hydroxide and sulfate phases in
the MINTEQA2 data base (McGregor and others 1998).
Mineralogical study of the tailings identified covellite
(CuS) at the base of the oxidized zones, suggesting that
Cases and solutions
covellite is controlling the dissolved concentration of Cu
within the tailings pore water. Covellite has been ob-
served to control the dissolved concentration of Cu at
other sites, including the Nickel Rim tailings, near Sud-
bury (Johnson 1993), and at the Waite Amulet tailings in
Quebec (Blowes and Jambor 1990).
Chemical extractions determined that the acid-leachable
Cu mass accounted for up to 15% of the total Cu within
the shallow tailings (McGregor and others 1998). The
acid-leachable Cu concentrations are generally depleted
in the strongly oxidized tailings, with peak concentra-
tions occurring at or near the hardpan layers and at the
base of the oxidized zones, suggesting that Cu is either
coprecipitated with or adsorbed onto jarosite and goe-
thite. The reducible concentrations of Cu account for up
to 100% of the total Cu mass within the shallow tailings,
thus suggesting that covellite and the Fe (oxy)hydroxides
are being dissolved through reductive dissolution.
Conclusions
The mobility of heavy metals within the Copper Cliff tail-
ings pore water is dependent upon pH, which is con-
trolled by a series of pH-buffering reactions (McGregor
and others 1998) as well as secondary-phase precipitation
and coprecipitation/adsorption reactions. Iron, Mn, Ni,
and Co exhibit similar mobilities within the tailings pore
water. Geochemical modelling and mineralogical exami-
nation of the tailings indicate that dissolved ferric Fe is
controlled by the precipitation of goethite and jarosite.
Ferrous iron (Fe(II)) is possibly limited by precipitation
of siderite in pore waters where the pH is above 6.8. No
secondary phases were isolated for Mn, Ni, or Co during
the mineralogical examination of the tailings, but micro-
probe analyses of the goethite and altered mica indicated
that both phases are locally Ni-bearing. The mobilities of
the other trace metals, Cd, Cr, Cu, Pb, and Zn are less
than those of Fe, Mn, Ni, and Co, and are strongly de-
pendent on pH. With the exception of Cu, geochemical
calculations and mineralogical examination of the tailings
did not detect any secondary phases that may be con-
trolling the mobilities of these metals within solution.
Covellite occurs at the base of the oxidized tailings, cor-
responding to abrupt decreases in dissolved Cu concen-
trations. The mobilities of the remainder of the metals
seem to be dependent on adsorption/desorption and co-
precipitation reactions with jarosite and goethite.
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