Hydrometallurgy 76 (2005) 25 36

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Pyrite behaviour in a tailings pond

C. Garcaa,*, A. Ballesterb, F. Gonzalezb, M.L. Blazquezb
a

Departamento de Tecnologa Industrial, Escuela Poltecnica Superior, Universidad Alfonso X el Sabio, Avda. de la Universidad,
1. 28691 Villanueva de la Canada, Spain
b
Departamento de Ciencia de los Materiales e Ingeniera Metalurgica, Facultad de Ciencias Qumicas,
Universidad Complutense, 28040 Madrid, Spain
Received 20 November 2003; received in revised form 24 February 2004; accepted 22 July 2004

Abstract
This paper deals with the behaviour in a tailings pond of the residues produced during the flotation of a complex sulphide
ore. The composition of the tailing was essentially pyrite (63.4%) with minor amounts of Cu, Pb and Zn sulphides (1.4, 0.5 and
0.8, respectively). In addition, sulphite ion and other thiosalts were present in the liquid phase. These reducing products were
added at the flotation plant in order to prevent undesirable oxidations. The presence of these reducing products controlled the
redox potential of the system, inhibiting oxidation reactions. A laboratory column was used to simulate the evolution of the
tailings in the pond. Distilled water was added at the top of the column; the water flowed across the tailings and finally was
collected at the bottom for its chemical and microbiological analysis. The actual situation in the industrial site was reproduced
by a model consisting of tow columns: one (column S) was the part of the ore under water, and the other (column HS) was the
part of the ore subject to humidity and dryness cycles. These two tests reproduced the system very well: the submerged pyrite
did not produce acidic water but the ore exposed to humidity and dryness cycles generated drainages with pH near to 2. The
metal and sulphate concentrations were consistent with this.
The influence of two other factors was also studied: bacterial activity and the height of solid residue inside the columns. The
tests showed that the presence of active bacteria intensified the weathering of the residue and that, when the height of the ore in
the column decreased, solid weathering also intensified.
Finally, a third factor taken into account was the presence of products with reducing activity associated with the ore as a
consequence of the flotation process. This combined action affected the behaviour of the residue, which was also reproduced
successfully with the assayed laboratory columns.
D 2004 Published by Elsevier B.V.
Keywords: Tailing pond; Weathering; Microbiological oxidation; Laboratory column; Acid rock drainage; Acid mine drainage

1. Introduction

* Corresponding author.
0304-386X/$ - see front matter D 2004 Published by Elsevier B.V.
doi:10.1016/j.hydromet.2004.07.010

The terms acid rock drainage (ARD) and acid mine

drainage (AMD) refer to liquid effluents, which occur

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C. Garca et al. / Hydrometallurgy 76 (2005) 2536

as a result of natural oxidation of sulphide minerals

contained in rocks exposed to air and water. Such
minerals are chemically (and biologically) stable in
situations where both oxygen and water are excluded;
however, when exposed to both moisture and air,
sulphide-containing minerals will oxidise spontaneously, with either molecular oxygen or ferric ion
acting as the oxidant. Metals such as cobalt, copper,
iron, nickel, lead, zinc, cadmium, etc. are released
when sulphides of these metals are exposed to the
weathering conditions found in mines, tailing
impoundments and waste rocks. The dissolution of
iron sulphide minerals leads to the production of acid,
as indicated by the following reactions (Johnson and
Hallberg, 2003):

FeS2 6Fe3 3H2 OY7Fe2 S2 O2

3 6H

4Fe2 O2 4H Y4Fe3 2H2 O

2
S2 O2
3 2O2 H2 OY2H 2SO4

Fe3 3H2 OYFeOH3 3H

In order to prevent exposure to air and water and
consequent oxidative dissolution of sulphidic minerals,
tailings are frequently stored under water (Johnson and
Hallberg, 2003).
The oxidation of ferrous iron in AMD is controlled
by indigenous microbes and oxygen concentration,
and is limited by the availability of nutrients (Kevin
and Johnson, 2003). It is therefore also essential to
investigate the microbiology associated with AMD.
AMD communities are generally characterised by a
very limited number of distinct species (AMD
communities contain fewer prokaryotic lineages than
many other environments), probably due to the small
number of metabolically beneficial reactions available
(Baker and Banfield, 2003). The metabolisms that
underpin these communities include organoheterotrophic and autotrophic iron and sulphur oxidation. Other
metabolic activity is based on anaerobic sulphur
oxidation and ferric iron reduction. There are two
recent reviews on microbiology associated with these
environments (Johnson and Hallberg, 2003; Baker
and Banfield, 2003).
Kinetic factors influencing the release and migration of these metals have been studied using various
leaching tests such as shake flasks, columns and

lysimeters (Doepker and Drake, 1991). Factors such

as the availability of oxygen, amount of water in the
tailing pores, pH of the natural leaching agents, ionic
strength of solutions, type of ions in the medium, etc.,
have been found to be of major importance.
Techniques for predicting acidity of drainages from
mine wastes have been classified as static or kinetic.
Static methods measure the theoretical total capacity of
the waste to generate and to consume acid. Kinetic
tests address the rate of acid production and consumption (Lapakko, 1990). Kinetic tests permit
identification of some factors affecting acid-producing
materials based on the pH of laboratory drainage. The
pH of mine waste drainage is determined largely by the
dissolution of the minerals present in the waste.
The main objective of leaching studies is to obtain
information on the release of environmental pollutants
from tailings more quickly than by hydrogeochemical
research. They are also useful for determining the
factors affecting industrial bioleaching, in that the
bioleaching rate can be improved by optimising
reactor design and such improvement is supported by
a good understanding of both the biological activity
and the dynamics of the bacterial populations (Foucher
et al., 2003). Bioxidation of ferrous iron in solution
also has industrial applications in the regeneration of
ferric iron as a leaching agent, and in fact it has been
studied under these conditions (Mazuelos et al., 2001).
Laboratory studies of tailings using various leaching techniques under controlled physical conditions
during a predetermined test period are compared with
on-site hydrogeochemical measurements to determine
the relationship between laboratory and field test data
(Stromberg and Banwart, 1999). For this information
to be useful as a guide in the prediction of future
conditions, data should be reproducible and should
correlate with actual environmental conditions.
Column leaching tests yield more accurate kinetic
data and provide a closer approximation to field
conditions, although they are less reproducible than
shake flask tests. Large-scale field test cells and
laboratory lysimeters produce the most accurate data,
but they are the most difficult and expensive to
maintain under controlled conditions.
The purpose of the present study was to analyse the
influence of the final disposal of a pyritic flotation
waste in a tailing pond and various other factors on
the evolution of that waste from the standpoint of

C. Garca et al. / Hydrometallurgy 76 (2005) 2536

AMD generation. A laboratory column was used for

this purpose, adapted as required by the different
conditions to be reproduced. The model experimental
system was also used to determine the influence of
specific factors such as bacterial oxidation and bed
height on acid drainage generation.

2. Materials and methods

2.1. Site
The system studied was a pyritic tailing pond for
the storage of waste produced during the flotation of a
complex sulphide ore. The pond belongs to a mine
located in the Pyritic Belt of Southwest Spain. The
waste collected in the pond was produced in a flotation
plant where three different concentrates of zinc, copper
and lead were obtained from the complex sulphide.
The waste was sent to the pond for liquidsolid
separation by way of a 3-km open-air channel taking
advantage of gravity. The final disposal of the pulp in
the pond caused the solids to settle at the bottom,
giving rise to two different oxygen gradient zones: an
anaerobic zone at the bottom of the pond, and an
aerobic zone of surface solids and waters (Fig. 1). The
pond was sampled as a whole taking a large and

27

representative number of samples. A complete description of it is given by Garcia et al. (1996).

2.2. Sampling
The pond was sampled as a whole to characterise
the system. Thirteen sludge samples and 10 of water
were taken at the bottom and also at the water surface.
Bottom samples were taken using a sampler supplied
by Ballcheck KB, specifically designed to take
samples of sludge without mixing water layers.
2.3. Chemical and mineralogical analysis
2.3.1. Solid samples
The solids contained in the pulp samples were
characterised by X-ray diffraction (Philips XPertMPD) and granulometric analysis (Microtac FRA).
The chemical composition was determined after acid
digestion of the samples; the subsequent analysis of
the metals in solution was performed by atomic
absorption spectrophotometry (AAS; Perkin Elmer
1100B). The sulphur content was determined using a
Leco automatic analyser.
To determine the composition of the samples, 0.5 g
of material was taken which was treated with 5 mL of a
HNO3/HCl medium (3:1 v/v) during 20 min and

Fig. 1. Simulation of the system.

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C. Garca et al. / Hydrometallurgy 76 (2005) 2536

heating with a hot-plate. After the digestion period, the

sample was diluted to 250 mL and the metals were
determined by AAS.
2.3.2. Liquid samples
pH evolution was monitored by a Crison 2001
electrode. A photocolorimeter (Metrohm 662) was
used to determine the turbidity of barium sulphate
precipitates formed by reaction of sulphate ion with
barium chloride for sulphate analysis (AWWA-APHAWEF, 1998). The concentration of sulphite ion was
measured using a Metrohn automatic titroprocessor to
register the pH at which the reaction between sulphite
ion and iodine took place (Bhaskara and Rao, 1955;
AWWA-APHA-WEF, 1998). The metals contained in
the liquid samples taken from the pond and in the
successive drainages from the columns were likewise
monitored by AAS. Eh was measured using an Ag8/
AgCl reference electrode. Fe2+ was determined by
photocolorimetry using o-phenanthroline as colorimetric reagent in acetic medium. A Metrohm 662
photocolorimeter was also used in this case (AWWAAPHA-WEF, 1998; Herrera et al., 1989). Fe3+ was
measured by difference between total Fe and Fe2+.
2.4. Microbiology
Samples taken from different points in the system
and the pulp sample used for the weathering experiments, were characterised microbiologically. The
following culture mediums were used to isolate
microorganisms.

was also used as control test. The samples were

inoculated in a solid medium for microorganism
isolation. In the case of the heterotrophic microorganisms, plates of media A and Y were used, and
plates with 9K medium supplemented with one of the
different energy sources were prepared for isolation
of lithotrophic microorganisms. Enrichment cultures
for the growth of anaerobic bacteria were prepared in
Postgates C medium at pH 7 and the same medium
at double concentration was used for liquid samples.
The concentration of inoculum was 10% in both
cases.
Microorganism counting was carried out by the
most probable number (MPN) method (AWWAAPHA-WEF, 1998).
2.5. Laboratory column
The design of the weathering columns was
conceived in such a way that the water drainage
percolating through the ore placed in the column
could be analysed. Thus, the column was watered at
the top and the solutions were collected through a
drainage pipe situated at the bottom of the column
(Fig. 2) (Doepker and Drake, 1991; Hood and
Oertel, 1984; Ritcey, 1991; Ritcey and Silver,
1982). The solid was supported by a body of
small silica stones (height 20 cm) situated at the
bottom of the column to prevent clogging and loss
of solid.

2.4.1. Aerobic
Chemolithotrophs: 9K medium (Silverman and
Lundgren, 1959) containing one of the following
compounds as energy source: ferrous iron (33.3 g/L),
tetrathionate (5 g/L), thiosulphate (5 g/L) or elemental
sulphur (a spatula tip).
Heterotrophs (bacteria, yeasts and fungi): (1)
medium A at pH 3 with 10 g/L glucose, 5 g/L yeast
extract and 15 g/L agar; (2) medium Y (9K medium at
pH 3 with 0.5 g/L bactotrypona, 1 g/L malt extract, 10
g/L glucose and 15 g/L agar).
2.4.2. Anaerobic
Postgates C medium was used (ASTM D 441284). The same medium but with sodium molybdate

Fig. 2. Experimental design of weathering columns.

C. Garca et al. / Hydrometallurgy 76 (2005) 2536

Several glass columns (height 30 cm, diameter

6 cm) were prepared so as to monitor the solid
weathering and study the influence of different
variables. A total of 300 g of tailings was placed in
each column. These were periodically irrigated with
200 mL of distilled water (Doepker and Drake,
1991; Hood and Oertel, 1984; Lapakko, 1990;
Silver, 1985; Rose and Daub, 1994). The watering
regimen consisted of cycles of humidity and dryness. The methodology was as follows: the column
was irrigated with 200 mL of distilled water, which
remained in contact with the ore for 48 h (humidity
period). The column was then drained and left to
dry for 120 h. The length of the humiditydryness
cycles was constant, but the influence of long dryness
cycles, long humidity cycles, different times of water/
ore contact and other factors was also taken into
account. The models tested were: submerged ore,
inoculated system and different height of ore bed.
2.5.1. Submerged ore
In the actual system under study (tailing pond),
most of the ore is located under water. In order to
reproduce the evolution of the waste in this zone and
compare the results with the evolution of the ore
exposed to the air, two columns were designed: in the
first, the ore was totally submerged in water (S) and,
in the second, the ore was subjected to humidity
dryness cycles (HS) (Fig. 1).
2.5.2. Inoculated column
Two columns (L and Li) were assembled and
loaded with 300 g of dry and finely dispersed tailings
from the original sample. The first column (Li) was
inoculated with 20 mL of a mixed culture containing
iron- and sulphur-oxidising bacteria obtained from an
enrichment culture grown from the tailings themselves. For the mineral weathering, both columns
were watered intermittently following the cycle
system described before.
2.5.3. Columns with different bed height
Two 15-cm diameter glass columns, one 50 cm in
height (h33) and the other 100 cm in height (h66),
were assembled to study the influence of the bed
height on tailings weathering (Fig. 2). The column
bed heights were 33 and 66 cm, containing 700 and
1400 g of solid, respectively.

29

2.6. Control of the experiments

The weathering tests were followed by analysis of
different variables related to column drainage. The
chemical variables were: pH, Eh, and iron, copper,
zinc and sulphate concentration in solution. Light
microscopy was also used to detect the possible
presence of bacteria in the column effluents.

3. Results and discussion

3.1. System description
The composition of the initial poured tailing met the
specifications of a pyrite pulp with 30% solids. The
chemical composition of the aqueous phase of this
pulp is shown in Table 1 (AMD initial). As described,
the solid waste was sent to the pond through a 3-km
open-air channel taking advantage of gravity. Once in
the pond, solids and liquid from the pulp were
separated, and different chemical and microbiological
transformations took place (Garca et al., 1996). As a
consequence, the initial liquid residue (AMD initial)
was not the same as the final liquid residue (AMD
final), whose composition is shown in Table 1.
The main transformation was the acidification of
the liquids, which produced a considerable increase in
the metal and sulphate concentrations in solution, and
a decrease in the sulphite concentration. The disposition of the pulp in the pond gave rise to a chemical
gradient (Table 2): the surface water was acidic, with a
high concentration of metals and sulphate, whereas
Table 1
Chemical analysis of both the aqueous phase in the initial poured
tailing (AMD initial) and the aqueous phase in the tailing pond
(AMD final)
pH
Eh (mV)
SO2+
4 (mg/L)
Sulphite (mg/L)
Cu2+ (mg/L)
Fetotal (mg/L)
Zn2+ (mg/L)
Pb2+ (mg/L)
Ca2+ (mg/L)
Mg2+ (mg/L)

AMD initial

AMD final

910
(20)(+10)
500650
88120
0.10.2
0.42
0.12
0.10.2
400450
1520

2.53.5
220350
18002000
23
0.40.8
5055
3050
56
400450
5055

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C. Garca et al. / Hydrometallurgy 76 (2005) 2536

Table 2
Chemical gradient in the tailing pond

pH
Eh (mV)
SO2
4 (mg/L)
Cu2+ (mg/L)
Zn2+ (mg/L)
Fetotal (mg/L)

Table 4
Chemical composition of the mud (% w/w)

Superficial
waters

Samples of mud
from the pond bottom

Cu

Pb

Zn

Fe

Mn

Ca

Mg

0.45

1.70

0.10

39.0

0.12

0.01

0.23

39.30

2.53.5
220350
18002000
0.40.8
3050
5055

67
(45)(3)
400500
0.30.6
0.10.3
3.35

The rest until 1008 corresponds to silica and other minor elements.

the samples taken from the pond bottom had neutral

pH and appreciably less metals and sulphate.
As well as this chemical gradient, there was a
microbiological gradient (Table 3). Aerobic iron- and
sulphur-oxidising bacteria were detected in the surface
water. However, anaerobic sulphate reducing bacteria
were isolated in the sludge from the bottom of the
pond (Kuyucak et al., 1991). The chemical and
mineralogical composition of the sludge is given in
Tables 4 and 5. This composition clearly coincides
with the composition of a pyrite.
3.2. Column weathering tests
For experimental purposes, two 30-L samples of
pyritic pulp (P1 and P2) were taken. The composition
of both samples was similar although chemical
characterisation revealed some differences (Table 6).
The chemical composition of the solids indicated a
dominance of pyrite. Their average particle size was
23 Am for P1 pulp and 42 Am for P2 pulp (additional
information about particle size of the pulps can be
obtained from Table 7). The composition of the pulp
waters was similar (Table 8), i.e., basic with a low
concentration of metals and a similar amount of
solids.
Microbiological characterisation of the pulp
showed associated iron-oxidising and sulphur-oxidising microorganisms. Heterotrophic bacteria were also
present (Table 9).
Table 3
Microbiological gradient in the tailing pond (MPN g1)
Location

Chemolithotrophs
aerobic bacteria

Anaerobic
bacteria

Total
heterotrophs

Superficial
waters
Deep mud

1.11027.0103

1.0103

2.51019.5102

1.71022103

6.0101

3.2.1. Influence of humiditydryness cycles and

behaviour of submerged ore
The evolution of pH in columns S and HS is
shown in Fig. 3. The weathering of the submerged
pyritic residue did not produce acid drainage. The
water situated over the solid acted as a barrier for
oxygen because both the diffusion and the solubility
of the gas were very low in these conditions. In fact,
storage of this type of waste under water is a very safe
way of avoiding sulphide oxidation (Doepker and
Drake, 1991; East et al., 1994; Lapakko, 1994; Ritcey,
1991). In contrast, the waste subject to humidity
dryness cycles (HS column) produced acid waters.
Therefore, the submerged pyrite was not oxidised and
is not a source of acid drainage.
The concentration of metals and sulphate ion
was consistently lower in S column drainage than
in HS column drainage (Figs. 4 and 5). In the
latter column, two important peaks were detected
both in the metals/sulphate concentration and in the
pH. These abnormalities in the curves were related
to long periods of dryness (2 weeks without
irrigation), which confirms that weathering is
appreciably increased after a long period of dryness
(Doepker and Drake, 1991). The concentration of
iron and zinc in the solutions from S remained
between 20 and 80, and 25 and 80 ppm, respectively. In column S, copper was not dissolved. On
the other hand, the concentration of sulphate ion,
like iron ion, was higher initially (6000 ppm) in the
solutions than in subsequent drainage. After several
weeks, the sulphate concentration stabilised at about
1400 ppm.
Table 5
Mineralogical composition of the mud
Mineral

% (w/w)

Chalcopyrite
Galena
Sphalerite
Pyrite
Silicates

1.44
0.46
0.77
63.37
33.95

C. Garca et al. / Hydrometallurgy 76 (2005) 2536

Table 6
Chemical composition of solids in pulps P1 and P2

31

Table 8
Chemical composition of water in pulps P1 and P2

Pulp

Cu
(%)

Pb
(%)

Zn
(%)

Fe
(%)

S
(%)

Ag
(g/t)

Sb
(g/t)

Pulp

Eh
(mV)

pH

Fe
(mg/L)

Cu
(mg/L)

Zn
(mg/L)

SO2
4
(mg/L)

SO2
3
(mg/L)

P1
P2

0.5
0.2

2
1.3

2
1.4

38
36

37
38

45
25

970
448

P1
P2

892
52

6.9
9.2

0.2
0.4

0.2
0.1

4.0
0.8

2940
1800

246
180

The concentrations of metals and sulphate measured in the waters produced in column S were
consistently lower than in the water of the tailing
pond, indicating that in the pond some additional
factor increased the residue weathering. This behaviour in the pond must be related to the chemical and/
or microbiological transformation of the residue
exposed to the atmosphere since the oxidation of
the submerged pyrite is negligible in spite of the
large volume of pyrite under water.
In addition, the concentrations of iron, copper and
zinc from column HS oscillated, respectively,
between 3000 and 5000, 200 and 400, and 1000 and
7000 ppm. Tall these concentrations, then, were
higher than in column S. Nevertheless, the metal
and sulphate levels in the tailing pond were consistently lower than in column HS, indicating that there
was some other factor in the pond that masked the
chemical and microbiological oxidation of the residue.
This additional factor was the presence of sulphite ion
and other thiosalts with reducing capacity, which
came from the flotation plant and inhibited the
oxidation reactions (Cotton and Wilkinson, 1995;
Greenwood and Earnshaw, 1998). The Eh values
measured in column S drainage were consistently
lower than 0 mV, whereas the Eh values in column H
S were consistently higher than more or less +300 mV.
The percentage of Fe2+ versus Fe3+ was about 60% in
column S and about 0.5% in column HS, confirming
that the conditions were reducing when the residue
was submerged and oxidising when the solid was
exposed to the air.
In conclusion, column S reproduced the part of the
system (tailing pond) corresponding to the submerged
pyrite, while column HS reproduced the part of the

pond exposed to oxidising conditions (Fig. 1). The Eh

values measured at the bottom of the pond were
consistently negative and the pH values were close to
7; on the other hand, the potential measured in the
surface waters was consistently positive and the pH
close to 3. This laboratory column can therefore be
used to reproduce the chemical conditions in the
tailing pond.
3.2.2. Influence of bacterial oxidation
Bacteria of the genus Acidithiobacilli are able to
catalyse the oxidation of sulphide ores and are
therefore highly detrimental to the quality of waters
flowing from different types of mine residues. It has
been demonstrated that these bacteria are present in
the system under study and that they can oxidise the
pyrite residue (Garca et al., 1996).
Following this line of reasoning, two new glass
columns (height 30 cm, diameter 6 cm) were loaded to
study the effect of bacterial activity on pyrite
oxidation. The first (L) was used to examine the
effects of chemical leaching; the second (Li) was used
to quantify the role of bacteria in the weathering of
residues, by inoculating the column with a mixed
culture originally grown from the same ore.
Fig. 6 shows the evolution of pH measured in the
drainage of both columns. The starting pH value in Li
was clearly lower, but the acidifying tendency was
similar in both cases. Although surprising, this result
is explicable if we consider that column L contained a
natural microflora that was associated with the ore and
grew when conditions were favourable. Thus, the
microorganisms in column L catalysed pyrite oxida-

Table 9
Initial number of microorganisms in pulps P1 and P2 (MPN g1)

Table 7
Granulometric distribution of the samples P1 and P2
Sample

D-80

D-50

D-10

P1
P2

29.62
36.65

12.75
19.73

1.39
4.36

Pulp

Fe-oxidising

S-oxidising

Heterotrophs

SRB

P1
P2

50

183.25102
20103

806.310
73410




: negative growth, SRB: sulphate reducing bacteria.

32

C. Garca et al. / Hydrometallurgy 76 (2005) 2536

Fig. 5. Sulphate concentration evolution in columns HS and S

drainage.
Fig. 3. pH evolution in columns HS and S drainage.

tion much as the inoculated bacteria oxidised the ore

in column Li.
The sulphate concentration was slightly higher in
the effluents of column Li, although in both cases this
tended to increase up to 14,000 ppm; also, there was a
considerable increase in the sulphate concentration,
paralleling a sharp decrease in the drainage pH
(Fig. 7). Both these facts point to the response of
the system after long periods of drynessnamely that
weathering of the residues increased considerably
after 2 weeks without irrigation.
The levels of iron, copper and zinc in the drainage
of both columns demonstrated considerable weathering and, as in the case of sulphate concentration,
were slightly higher in the effluents of column Li
(Fig. 8). Nevertheless, around the fourth week of
weathering, as with sulphate concentration and pH,
there was a major increase in the concentration of
metals in solution in both columns. Again, this

Fig. 4. Metals concentration from columns HS and S drainage.

increase coincided with the irrigation of the system

after a long period of dryness.
The main conclusion from these tests is that the ore
itself contained a microflora that catalysed pyrite
oxidation. When bacteria were active, the pH and
the concentration of metals and sulphate measured in
the drainage exceeded the values found in the pond
waters. This means that the system studied has
sufficient capacity to generate acid drainage in the
classical sense, but that in the present case other
factors, such as the presence of sulphite ions in the
medium, are essential in preventing complete oxidation of the residue.
3.2.3. Influence of the bed height inside the column
The last factor studied was the height of ore in each
column, and to that end h33 and h66 columns were
designed. The evolution of pH in the effluent of each
column is shown in Fig. 9. The first conclusion was

Fig. 6. pH evolution in columns L and Li drainage.

C. Garca et al. / Hydrometallurgy 76 (2005) 2536

33

Fig. 7. Sulphate concentration evolution in columns L and Li

drainage.

that solid weathering increases as the ore height in the

column decreases; for instance, in cycle 8 (17 weeks
of weathering), the effluent pH from column h33 was
2.0 and the effluent pH from column h66 was 4.9.
The differentiating factor between the columns
was facility of oxygen diffusion and the time during
which the ore was wet. There are two fundamental
factors determining the possibility of sulphuric acid
production by solid wastes containing sulphide
sulphur and the consequent mobilisation of metals:
the presence of oxygen, and water covering the solid
but not bathing it (Doepker and Drake, 1991). Thus,
if the ore height in the column is increased, it will
take longer to drain the column and therefore the
solid will be bathed by the water for longer.
Consequently, it will be more difficult for oxygen
to penetrate the spaces between particles. In a watersaturated column, the oxidation rate is lower and, in
these conditions, pyrite oxidation only takes place in
surface areas where the presence of oxygen is
possible.

Fig. 8. Metals concentration from columns L and Li drainage.

Fig. 9. pH evolution in columns h33 and h66 drainage.

The evolution of metal concentrations in the

effluents of both columns and the influence of dryness
periods are shown in Fig. 9. As the figure shows,
waste weathering was much higher in column h33
because the concentration of metals in the effluent
was also higher. Whereas iron and zinc concentrations
reached up to 30,000 and 10,000 ppm, respectively, in
column h33, in column h66 only zinc was appreciably
dissolved but not iron (only up to 100 ppm). In both
cases, there was no significant dissolution of copper.
The percentage of copper in the initial pulp composition was also smaller (Table 6). Iron dissolution
from column h66 was insignificant when compared
with the iron dissolved from column h33, and the
same was true of zinc and copper (Fig. 10).
The influence of long cycles of dryness was studied
in columns h33 and h66 as in previous tests (columns
HS/S and L/Li). Another additional factor was tested:

Fig. 10. Metals concentrations from columns h33 and h66 drainage.

34

C. Garca et al. / Hydrometallurgy 76 (2005) 2536

the influence of humidity cycles in which the contact

time between water and ore was longer (1 week instead
of 48 h). Humidity periods were achieved by frequent
irrigation and dryness periods by infrequent irrigation.
The influence of dryness and humidity cycles was
observable in both columns, although the effect was
more evident in column h33 where waste weathering
was higher. In both cases, the dryness cycles
provoked an increase in pyrite weathering which, as
expected, was detected through high concentrations
of metals and sulphate in solution and a decrease in
the column drainage pH. However, long humidity
periods produced a decrease in the oxidation rate of
the ore (Figs. 911). The influence of both periods is
clearly observable in Fig. 9: a long dryness period
produced a decrease in pH, while a humidity period
caused slower oxidation of the solids. At the same
time, the concentration of metals in the effluents
increased after a long period of dryness but did not
vary appreciably after a humidity period (Figs. 10
and 11). Neither effect was detected when irrigation
was carried out at the normal frequencies.
Sulphate concentration in the effluents (Fig. 11)
was again consistently higher in column h33. However, the level of this ion was quite uniform and was
high in each column from the beginning of the
experiment. This effect is related to pyrite oxidation,
which produces a uniform flux of ion sulphate as a
function of oxygen availability and particle size of the
solid (reaction surface) (Donovan, 1994). The difference between columns h33 and h66 was basically the
availability of oxygen for oxidation, which was

Fig. 11. Sulphate concentration evolution in columns h33 and h66

drainage.

greater in column h33 because this is smaller; but

these factors in the same column were constant during
weathering, and therefore the sulphate concentration
was approximately constant as well. The observed
variations indicate that some leached metal could
reprecipitate in the more reducing conditions at the
bottom of the column essentially by sulphate reduction. The sulphate results (Fig. 11) may suggest this.
Long dryness cycles are useful for reproducing
natural conditions during seasons such as summer
when long dry periods are followed by rainstorms.
This causes severe environmental problems in areas
where sulphide residues are exposed to the action of
the atmosphere. In the system studied (tailing pond),
this effect could occur where the pyrites are in direct
contact with the atmosphere.

4. Conclusions
Pyritic wastes became largely separated in the
pond, determining the global behaviour of the system.
This distribution, with solids at the bottom of the pond
and water on top, was accompanied by a chemical and
a biological gradient. The water at the surface was
acidic, but at the bottom of the pond the pH was near
alkalinity. As a result, acidophilic aerobic sulphur
oxidising bacteria were isolated from water samples
and anaerobic sulphate reducing bacteria were isolated
from the sludge. Also, the sulphite concentration in
the pond decreased during storage of the pulp.
The laboratory column reproduced the behaviour
of the pyritic tailings in the pond. Column S
reproduced the part of the system (tailing pond)
corresponding to the submerged pyrite, while column
HS reproduced the part of the pond exposed to
oxidising conditions. Weathering of the submerged
pyritic residue did not produce acid drainage (column
S). In contrast, the waste subjected to humidity
dryness cycles (HS column) produced acid waters.
This indicates that the submerged pyrite was not
oxidised and was not a source of acid drainage. The
Eh values measured at the bottom of the pond were
consistently negative and the pH values were close to
7, while the potential measured in the surface waters
was consistently positive and the pH close to 3. This
laboratory column can therefore reproduce the chemical conditions in the tailing pond.

C. Garca et al. / Hydrometallurgy 76 (2005) 2536

The ore itself had associated microflora which

catalysed oxidation of the pyrite. When bacteria were
active, the pH and the concentration of metals and
sulphate measured in the drainage were higher than in
the pond waters. This means that the system studied
had sufficient capacity to generate acid drainage with
the classic features of these effluents; in the present
case, however, other factors such as the presence of
sulphite ions in the medium were instrumental in
preventing complete oxidation of the residue.
It was demonstrated that solid weathering
increased when the height of the ore in the column
decreased.
Dryness cycles intensified pyrite weathering, but
prolonged humidity caused the rate of oxidation of the
ore to decrease.

Acknowledgements
The authors wish to thank the Spanish Government
Comision Interministerial de Ciencia y Tecnologa
(CICYT) and ALMAGRERA S.A. for funding this
work.

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