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Minerals Engineering 21 (2008) 355365


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Heap bioleaching of chalcopyrite: A review


N. Pradhan *, K.C. Nathsarma, K. Srinivasa Rao, L.B. Sukla, B.K. Mishra
Institute of Minerals and Materials Technology, Bhubaneswar 751013, Orissa, India
Received 21 December 2006; accepted 27 October 2007
Available online 20 February 2008

Abstract
Bioleaching is an emerging technology with signicant potentials to add value to the mining industries so as to deliver attractive environmental and social benets to all the associates. Chalcopyrite, CuFeS2, is the most important copper-bearing mineral in the world and
unlike many other ores it is known to be recalcitrant to hydrometallurgical processing. The main hindrance to the commercial application of biohydrometallurgical processing of chalcopyrite is its slow rate of dissolution.
In this piece of review work, the microbiological and other important aspects of chalcopyrite heap bioleaching processes are discussed.
The modest nutritional requirements of bioleaching organisms may be provided with the aeration of iron- and/or sulfur-containing mineral suspensions in water or the irrigation of a heap, while working in a large scale. This chemolithotrophic metabolism makes the organisms industrially important. The emphasis is given on the biodiversity of microbial community and the factors aecting heap bioleaching.
The cost of bio heap leaching in respect of some existing commercially operating heap bioleaching plants is also included. Application of
chalcopyrite bioleaching in heap/dump leach processes can potentially result in lower cost and reduced environmental impact in copper
production.
2007 Elsevier Ltd. All rights reserved.
Keywords: Heap bioleaching; Chemolithotrophic microorganisms; Chalcopyrite; Copper bioleaching; Thermophilic bioleaching bacteria/archea

Contents
1.

2.
3.

4.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1. Irrigation-based leaching processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2. Agitation based leaching processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
General description of heap bioleaching operations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Heap bioleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Salient features of microorganisms involved in bioleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Microbial diversity in bioheap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Factors affecting heap bioleaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Type of ore material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Aeration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3. Irrigation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5. Some other factors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5.1. Jarosite formation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5.2. Attachment of microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5.3. Build up of metal ion/organic matter concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Corresponding author. Tel.: +91 0674 2584091; fax: +91 0674 2581637.
E-mail address: nilotpala_pradhan@yahoo.co.in (N. Pradhan).

0892-6875/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2007.10.018

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5.
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N. Pradhan et al. / Minerals Engineering 21 (2008) 355365

Thermophilic leaching . . . . . . . . . . . .
Difficulties in heap leaching processes .
Cost of bio heap leaching . . . . . . . . . .
Some examples . . . . . . . . . . . . . . . . .
Conclusion: present and future of heap
References . . . . . . . . . . . . . . . . . . . .

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bioleaching of chalcopyrite
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1. Introduction
Heap and dump leaching oer a number of advantages
embracing simple equipment, low investment and operation cost, and reasonable yields over a period of recirculation. The earliest engineering technology used in dump
leaching was very basic in nature involving dumping a
low-grade (otherwise waste) copper-bearing ore in the form
of large rock/boulder into vast mounds and irrigating it
with dilute H2SO4 to enhance the growth and activities of
mineral-oxidizing acidophiles, i.e., primarily iron-oxidizing
microorganisms. Copper was precipitated from the metalrich streams draining out of the dumps by cementation
with scrap iron. Later developments on the engineering
and hydrometallurgical aspects of biomining have involved
the use of thin layer heaps of refractory suldic ores
(mostly copper, but gold-bearing material) stacked on to
water-proof membranes, and the solubilized copper
recovered using solvent extraction and electrowinning
(SX/EW).
The process permits recovery of copper, zinc and other
metals using the catalytic activity of several strains bearing
ferrous iron and sulfur-oxidizing chemolithotrophic bacteria (Norris, 1990). Generally speaking, industrial-leaching
processes operate with the naturally occurring microorganisms in mine waters and in the ore body. Most of experiments carried out on bioleaching of chalcopyrite are so
far carried out in shake ask level. Scale up of such studies
to an industrial level requires process development through
engineering and process modeling. The ore grade and particle size are the controlling factors while making a choice
of leaching process. Rawling et al. (2003) categorized the
engineering approaches used in biomining in two broad
categories as follows:
1.1. Irrigation-based leaching processes
It can again be categorized depending on the type of
resources to be processed as dump leaching, heap leaching
and in situ leaching. In dump leaching, waste rock, lowgrade ore or concentrator tailings (low grade oxides and
secondary suldes) are leached at the place of disposal.
This is a mature and widely used technology. Heap leaching deals with the newly mined/run-o-the-mine (ROM)
materials (intermediate grade oxides and secondary sul-

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362
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364
364

des) deposited in the form of a heap on an impervious


natural surface or a synthetically prepared pad leached
with circulation, percolation, and irrigation of the leaching
medium. Primary suldes like chalcopyrite are suitable for
this type of leaching. In situ leaching is employed with
abandoned and/or underground mines where the ore
deposits cannot be mined by the conventional methods
since they are either low grade or of small deposits or both.
1.2. Agitation based leaching processes
This is a stirred tank process involving stirred tank bioreactors. The types of resources or raw materials suitable
for this kind of leaching range from intermediate to highgrade ore. Chalcopyrite concentrates are taken in a tank
and leached using mechanical agitation. In stirred tank
processes, highly aerated and continuous-ow reactors
placed in series are used to treat the minerals. From a process-engineering standpoint, the complex network of biochemical reactions encompassed in bioleaching would
best be performed in reactors that would allow a good control of the pertinent variables resulting in a better
performance.
2. General description of heap bioleaching operations
Heap reactors are cheaper to construct and operate and
are therefore more suited to the treatment of lower grade
ores. Commercial bioleaching involving the irrigation of
waste ore dumps can take place economically, for which
it is considered as a low technology process. The metal
extraction process may be made much more ecient by
the construction and irrigation of especially designed heaps
rather than by the irrigation of an existing dump that has
not been designed as per the optimized leaching process.
While building a heap, ore is piled onto an impermeable
base supplied with an ecient leach liquor distribution
and collection system. Acidic leach solution is percolated
through the crushed ore, and the microbes growing on
the mineral surfaces of the heap produce the ferric iron
and acid that result in mineral dissolution and metal solubilization. The microbial population operating in natural
leaching processes does not really have the characteristics
of a pure culture, although environmental conditions

N. Pradhan et al. / Minerals Engineering 21 (2008) 355365

357

Fig. 1. Equipment ow diagram for heap bioleaching of chalcopyrite ore.

principally favour the development of acidophilic Acidithiobacilli and Leptospirilli.


Aeration in such processes can be passive, with air being
drawn into the reactor as a result of the ow of liquids, or
active with air blown into the heap through piping installed
near the bottom. Metal-bearing leach solutions being
drained out from the heap are regularly collected and sent
for metal recovery. Furthermore, although one can rely on
the natural movement of microbes to inoculate the heap,
the initial rates of bioleaching can be improved by the eective heap inoculation; however, this is dicult to achieve.
Fig. 1 shows the equipment ow diagram for heap bioleaching of chalcopyrite.

biooxidation of minerals are those responsible for producing ferric iron (Eq. 2) and sulfuric acid (Eq. 3) required for
the bioleaching reactions. Ferric sulfate, a powerful oxidizing agent, oxidizes the copper sulde minerals leading to
the in situ leaching of copper by the sulfuric acid generated
therein.

3. Heap bioleaching

Another important characteristic is that the microbes


grow autotrophically by xing CO2 from the atmosphere.
These are the iron- and sulfur-oxidizing chemolithotrophic
bacteria and archea (Johnson, 1998). A further advantageous characteristic of mineral biooxidation operations is
that they are not usually subject to contamination by the
generated unwanted microorganisms. Another important
characteristic of the acidophilic chemolithotrophs is their
general tolerance to higher concentrations of metal and
other ions. The levels of resistance show a considerable
strain variation. Adaptation to high levels of resistance to
a metal on exposure is likely to be responsible for much
of the variation. The modest nutritional requirements of
these organisms are provided by the aeration of an iron
and/or sulfur containing mineral suspension in water or
irrigation of a heap in a higher scale of operation. This chemolithotrophic metabolism makes the organism industrially important.

In general, the types of microorganisms found in heap


leaching processes are similar to those found in stirred tank
processes, but the proportion of the microbes may vary
depending on the mineral and the conditions under which
the heaps or tanks are operated. The most important
microorganisms considered for the processes that operate
from ambient to 40 C are to be a consortium of gramnegative bacteria. Among these bacteria, there are species
with an extremely limited substrate spectrum.
3.1. Salient features of microorganisms involved in
bioleaching
Bioleaching microbes have a number of features in common that make their role especially suitable for mineral solubilization. The most important microbes involved in the

CuFeS2 4H O2 ! Cu2 Fe2 2S 2H2 O


4Fe2 4H O2
2S 3O2 2H2 O

Iron oxidizing Bacteria

Sulfur oxidizing Bacteria

4Fe3 2H2 O

2SO
4 4H

CuFeS2 4Fe3 ! Cu2 2S 5Fe2

358

N. Pradhan et al. / Minerals Engineering 21 (2008) 355365

3.2. Microbial diversity in bioheap


A wide variety of microorganisms consisting mainly of
bacteria and archea are found in natural leaching environments such as acid mine drainage. The majority of known
acidophilic microorganisms have been isolated from such
natural environments. These microorganisms are employed
for the leaching of metals from ores in an industrial scale.
The only dierence is that in some cases they have been
selected for rapid growth on the ore or concerned concentrate and in the plant operating conditions. In commercial
processes of bacterial leaching, a wide variety of microorganisms living in symbiotic associations take part. These
microorganisms, whose role can be considered similar to
that of catalysts, may be mesophilic, thermophilic, autotrophic or heterotrophic in nature. Studies had revealed
that microbial bioleaching communities composed of a vast
variety of microorganisms result in complex microbial
interactions and nutrient patterns (Erlich, 1999; Johnson,
1998; Edwards et al., 2000).
Various methods are used for studying microbial diversity in ecological samples as well as in industrial bioheap
leaching plants. There is still widespread uses of enriched
cultures with ferrous iron, sulphur and pyrite as substrates
for isolating acidophiles. Again in some cases this may be
useful, but the enrichment process may be selective for a relatively narrow range of acidophiles that grow better under
the imposed culture conditions to give a false impression of
the relative importance of a particular bacterium in situ.
Recently, detailed investigations based on molecular methods such as DNADNA hybridization, 16S rRNA sequencing, PCR-based methods with primers derived from rRNA
sequencing, uorescence in situ hybridization (FISH), or
immunological techniques are used for assessing biodiversity of leaching community. Fig. 2 shows some of the identied microorganisms involved in the bioleaching processes.
Understanding the microbiology of a bioheap is important for advancement in commercial bioheap applications.
Such knowledge will increase the applications to various
types of ores as well as to the diversity of mineral deposits
that can be processed by bioheap technology. It will also
enable the better control of conditions to improve upon
the leaching rates, metal recoveries and cost of production.
A limited comprehension is available of what actually occurs
in a full-scale microbiologically operated bioheap, despite
the commercial achievement in the copper ore bioheap
leaching. The chemical and physical conditions within the
bioheap change drastically from the time of stacking, inoculation and completion of bioleaching. Redox conditions,
acidity, temperature, oxygen supply and solution chemistry
conditions vary widely during the oxidation period. Such
conditions do likely be selective for microorganisms or
may aect a succession of organisms in dierent portions
of the Bioheap. Bioheap solutions are recycled and the
building up constituents over the time period also aects
the microbiology. Heterotrophic microorganisms build up
during the period may play some role in bioheap leaching.

Copper recovery from the chalcopyrite concentrates was


greater when the native isolates were employed compared
with the reference strains as the former adapts readily to
metal sulphide ores and leaching conditions (Keeling
et al., 2005). Brierley and Brierley (2001) described dierent
chemical, physical and microbiological practices in monitoring commercial bioheaps. He considered dierent conditions that control microbial populations in bioheaps in
addition to the type of ore deposits that could be bioleached. The microorganisms responsible for setting in
proper physico-chemical changes like Eh, pH, temperature
and concentration of metals and metalloids in to the system
leading to mineral oxidation and dissolution are of particular signicance, while the other organisms associated with
the original ore are of minor, or of no importance in the
process of mineral dissolution.
A culture-independent approach based on PCR amplication and denaturing gradient gel electrophoresis
(DGGE) and sequencing of 16S rRNA gene fragments
from both bacteria and archea were used to analyze the
microbial community inhabiting a low-grade copper sulde
run-o-mine (ROM) test heap of a project in Chile
(Demergasso et al., 2005) for one year. Phylogenetic analyses of 16S rRNA fragments revealed that the retrieved
sequences clustered together with Acidithiobacillus ferrooxidans, Leptospirillum ferriphilum, Ferroplasma acidiphilum
and environmental clones related to them. In addition,
some sequences were distantly related (<95% similarity in
the 16S rRNA gene fragment analyzed) to cultured microorganisms from the Sulfurisphaera and Sulfobacillus genera. Thus, the prokaryotic assemblage might be mainly
composed of sulfur- and iron-oxidizing microorganisms.
The temporal distribution of microbial 16S rRNA gene
sequences could be divided in three periods. In the rst
stage of bioleaching cycle, the A. ferrooxidans and Sulfurisphaera-like archea were dominant within each respective
phylogenetic domain. In the second stage of operation
from 255 to 338 days, Leptospirillum and Ferroplasma
groups were mainly detected, respectively. Finally, in the
third period of operation from 598 to 749 days, Sulfobacillus-like microorganisms became predominant, while Ferroplasma was the only archea detected.
Using the analysis of 16 S rDNA amplication products
of total DNA, the sulphur-oxidizing bacterium A. thiooxidans (Kelly and Wood, 2000) and the iron-oxidizing bacterium L. ferrooxidans have been found as the dominant
populations in bioleaching tanks that contain copper ores
leached at low ferrous iron concentration and in a continuous ow biooxidation tank for the treatment of gold bearing arsenopyrite concentrates. At temperatures higher than
40 oC, the moderately thermophilic A. caldus (Kelly and
Wood, 2000) was also present (Espejo and Romero,
1997; Lawson, 1997; Pizarro et al., 1996; Rawlings and Silver, 1995).
A. ferrooxidans and A. thiooxidans play an important
role in the bioleaching process. Experiments showed that
copper extraction in a mixed culture composed of A. ferro-

N. Pradhan et al. / Minerals Engineering 21 (2008) 355365

359

Common Ancestor
Eukaryota

Archebacteria

Crenarchaeota Korarchaeota

Nanoarchaeota

Bacteria

Euryarchrota

Sulfobales
S.acidocaldarius

Ferroplasma acidophilum

S.sulfotaricus

Ferroplasma acidarmanus

Solfolobus

Metallosphaera

M.sedula
A.brierleyi

Acidianus
A.infernus
Sulfurisphaera

Proteobacteria

Proteobacteria

Gram Negative

Proteobacteria

Acidithiobacillus ferrooxidans
Acidithiobacillus thiooxidans
Acidithiobacillus caldus

Thiobacillus

Leptospirillum
Sulfobacillus

Firmicutes

Gram Positive
Acidimicrobium

Actinobacteria

Ferromicrobium
Fig. 2. Identied microorganisms involved in bioleaching.

oxidans and A. thiooxidans is higher than that in a pure culture (Qiu et al., 2005). An important potential of A. thiooxidans to the leaching of chalcopyrite was indicated in which
jarosite accumulation on the substrate is prevented to allow
further dissolution of copper through the action of ferric
ion. The selection of a suitable pH in a leaching solution
would be signicant. In agreement with other reports,
Rawlings et al. (1999) concluded that high Fe3+/Fe2+ ratio
(high redox potential), low pH, and high temperature often
favor L. ferrooxidans over A. ferrooxidans in commercial
leaching operations carried out either in column- or
heap-type, or continuous-ow tank reactors.
Operational constraints like the desirability of decreasing pulp residence times in stirred tank bioreactors can
result in the selection of more ecient bioleaching populations (Dew et al., 1997). The presence of anaerobic micro-

organisms in the lower parts of the heaps is another real


possibility, since the zones of low or zero concentrations
of oxygen are expected to exist. These conditions as well
as the presence of a reducing agent such as organic matter,
anaerobic bacteria (Desulfovibrio desulfuricuns), in the system are capable of reducing the sulphate ions to sulphide
ion with the consequent precipitation of insoluble metallic
compounds which may reduce the metal recovery.
4. Factors aecting heap bioleaching
Bacterial leaching, like any other process involving living beings, is inuenced by environmental, biological and
physico-chemical factors, which aect the yield of metal
extraction (Torma, 1977; Lundgren and Silver, 1980). Optimal conditions of humidity, pH, temperature, energy

360

N. Pradhan et al. / Minerals Engineering 21 (2008) 355365

sources and nutrients have to exist along with the absence


of possible inhibitors for the growth of microorganisms
involved in the process. These conditions are prerequisite
for the growth of microorganisms to favorably aect copper solubilization (Table 1). Correct chemical and physical
conditions must exist for the percolation leaching system to
function: a suitable ore particle size, access of oxygen and
humidity to the mineral surfaces, reduced acid consumption, the presence of sulphides susceptible to bacterial oxidation, and the greatest possible elimination of precipitated
basic ferric salts, which might block the percolation
channels.
In addition, the geometry of heap may also aect the
bioleaching process and rate of recovery. For these leaching systems to function, the medium must be kept in such
conditions that the bacteria requirements are adequately
covered. When the environment can maintain these optimal conditions, an adequate yield of copper can be
obtained.

The eectiveness of bioleaching process depends largely


on the nature of ore material (Munoz et al., 1995) in which
the metal exists. When the medium is alkaline, it is probable that precipitates will be formed that will hinder the natural percolation of leach solution through the heap.
Porosity of ore material allows the solution to penetrate
more into the ore body. Another important aspect of the
mineral/ore is to provide sucient quantity of nutrients
to the microorganisms for growth. Quartzic and garnitic
ore show variable susceptibility to microbial leaching.

aerated, is prone to anaerobic conditions. Aeration of bioheaps can accelerate biooxidation reactions by reducing the
time of leach cycle for which the supply of oxygen is very
important for viability and activity of leaching microorganisms.
Air may be delivered to the system via a network of
pipes installed in a gravel layer at the base of heaps. Air
distribution networks may typically include 500 mm headers and 50 mm diameter laterals at 2 m spacing. Holes are
drilled at the bottom of the 50 mm diameter air distribution
pipes (Brierley and Briggs, 2002). The density of holes is
dependent on the amount of suldesulfur to be oxidized
and the oxidation rate. Air is injected into the heap using
a set of low-pressure high volume fans or blowers. Bioleaching determines the oxygen concentration prole with
respect to the height of the aerated heap. At the bottom
of the pile, where air is forced into the heap, oxygen is close
to saturation, but as the air ows upwards through the void
spaces, the bacteria catalyzing the oxidation of sulphide
consumes oxygen and as a result, the degree of oxygen
depletion near the top of the heap prevails. Appreciable
oxygen concentration exists as a gradient with depth. Heap
oxidative capacity is considered a better indicator of leaching. Copper leaching is directly related to oxygen consumption in the heap. Oxygen consumption, in turn, is related to
bacterial activity and the rate of forced aeration. Increasing
the rate of aeration, may improve copper leaching. This
may be the case when the heap is in a state of oxygen depletion. As oxygen is required for oxidative metabolism, its
depletion has rate limiting eect. If oxygen is suciently
present at all the points of the heap, increase in aeration
does not increase the leaching rate.

4.2. Aeration

4.3. Irrigation

As most of the metal leaching bacteria are aerobic and


chemolithotrophic in nature, aeration takes care of the supply of both O2 and CO2 to the leaching system. Sucient
carbon dioxide in air serves as a source of carbon needed
for biomass generation. Interior of heap, if not properly

Regarding the type of irrigation, continuous or discontinuous, there are dierent trends, although it is generally
thought that discontinuous irrigation favours metal dissolution. In such cases, the attack solution is intermittently
sprayed onto the surface of the heap and is allowed to percolate before a new solution is applied, thus setting up an
inverse capillary eect, which permits the leaching of coarse
ores. During irrigation, the capillary forces draw the liquid
into the mass of the ore. When irrigation ceases, the liquid
drains out from the capillary and remains on the surface
and a new irrigation carries with it the dissolved metal
ion and the process begins again with the introduction of
a fresh liquid into the capillary. In this way, discontinuous
irrigation may be more eective for coarse ores than the
continuous one, since the alternate draining and drying
of the capillaries is considerably faster than the simple ionic
diusion through a static capillary full of uid. Thus, alternate irrigation and drying helps to leach coarse particles
and drain out soluble salts from their surfaces as well as
increasing the diusion of oxygen and carbon dioxide to
the ore surface where active bacteria are located. However,
the frequency of irrigation is an important factor to be

4.1. Type of ore material

Table 1
Factors and parameters aecting heap bioleaching and metal recovery
(Brandl, 2001)
Factor

Parameters aecting bioleaching

Physical and chemical


parameters

Temperature, pH, redox potential, CO2 and O2


content, nutrient availability, oxygen
availability, homogenous mass transfer, Fe (III)
concentration, presence of inhibitors, etc
Microbial diversity, population density,
microbial activities, metal tolerance, spatial
distribution of microorganisms, attachment to
ore particles, adaptation abilities of
microorganisms, and inoculum
Composition, mineral type, acid consumption,
grain size, mineral dissemination, surface area,
porosity, hydrophobic galvanic interactions, and
formation of secondary minerals

Biological parameters

Ore characteristics

N. Pradhan et al. / Minerals Engineering 21 (2008) 355365

considered. Several studies (Aslam and Aslam, 1970) have


demonstrated that daily irrigation in the presence of bacteria is more eective than the irrigation once in a week.
Industrially, the irrigation frequency (cycle) is determined
by the rate of evaporation and the concentration of the
metal in the exiting liquid phase (Bruynesteyn, 1983).
4.4. Temperature
Microorganisms are classied in terms of the temperature range in which they can survive: within optimum temperatures of 3040 C for mesophiles, around 50 C for
moderate thermophiles and above 65 C for extreme thermophiles. Below the optimum temperature the microbes
become inactive, but at temperatures above it, they are rapidly destroyed. Biooxidation of sulde minerals, being an
exothermic process, produces signicant heating in stirred
tank reactors and heaps. Controlling the temperature in
heaps is dicult. Heap height is an important factor for
the rise in temperature, which increases with the square
of heap height (Ritchie, 1997). In industrial operations,
the temperature inside the heap can reach up to 50 C for
which the biological and chemical oxidation reactions cannot be regulated, and the attainment of an excessively high
temperature will obviously inhibit mesophilic bacterial
activity. The heaps get heated up due to the growth of mesophilic microorganisms and the oxidation of sulphides. As
temperature increases more than 40 C, mesophiles are displaced by the moderately thermophilic iron- and sulfuroxidizers (Murr and Brierley, 1978). Extreme thermophiles
may displace moderate thermophiles where temperatures
increase above 60 C. Changes of temperature within a
heap, as a result of seasonal changes, can cause modications in the microbial population while favoring the development of mesophilic or thermophilic bacteria. Thus, the
heap temperature, due to the exothermic reactions, can
be a controlling factor in some commercial operations.
Temperature inside the heap is determined by various
factors, as Petersen and Dixon (2002), through their heat
generation modeling study on chalcopyrite concentrates,
have established a correlation between temperature, aeration and the rates of irrigation. According to them, the
temperature prole within a heap is governed by the generation of heat due to chemical reaction, lowering of heat due
to the owing down of solution, increase of heat due to upow movement of humid air, boundary eects due to solar
radiation and evaporation, and to a lesser extent by the
conduction through rock. Thus, Dixon (2000) has formulated a comprehensive heap-heat conservation model to
show that the ratio of irrigation and aeration rates is critical in determining the proper distribution of temperature
all over the heap.
4.5. Some other factors
Metal oxidation mediated by acidophilic microorganisms can be inhibited by a variety of factors such as organic

361

compounds, surface-active agents, solvents, or specic


metals.
4.5.1. Jarosite formation
The jarosite formation is problematic in bacterial leaching. Once the jarosite is formed, it precipitates on the mineral surfaces and decreases the eectiveness of reagent and
mineral surface interaction, and the inhibition of metal oxidation mediated by acidophilic microorganisms is one such
phenomenon. One of the problems in the leaching of chalcopyrite needs to be overcome is the formation of passivating layer. The inhibition in bioleaching is caused by the
formation of an intermediate sulde passivation layer. It
is believed that the passivation layer is less reactive than
the original chalcopyrite and may inhibit the ow of electrons and oxidants to and from the chalcopyrite. The exact
nature of this passivation layer is complex and it is reported
to have come from one or both the sources: (1) Fe(OH)3
tends to form the jarosite [KFe3(SO4)2(OH)6] which coats
the unreacted material to form a passivating layer and/
or, (2) the elemental sulfur formed during the process tends
to coat the surface. The formation of ferric iron precipitate
and jarosite are highly pH dependent and precipitation of
jarosite is more pronounced within the pH 1.92.2. Use
of thermophilic microorganisms raises the temperature to
60 C or higher to destabilize the passivating layer on chalcopyrite in a high temperature heap bioleaching process
(US Patent No. 6110253, 2000).
4.5.2. Attachment of microorganisms
Attachment of microorganism to the ore particles has
been well proven (Sand et al., 1995). Numerous studies
have demonstrated the presence of bacteria attached to
the ores and/or present in the pregnant leach solutions
(PLS) in commercial operations. Sand et al. (1995) proposed a typical model for the bacterial leaching, which
essentially proceeds by ferric ions complexation by the
secreted extra cellular polymeric substances (EPS). This
model, originally conceived for A. ferrooxidans, has been
applied to L. ferrooxidans, because both iron-oxidizing
bacteria share the quality of EPS enabling the attachment
to solid substrates (Gehrke et al., 1995; Schippers et al.,
1996; Gehrke et al., 1998; Rojas-Chapana and Tributsch,
2004). Addition of ferric ion alone did not induce any form
of local corrosion on pyrite, which indicates that the reactions taking place between the attached bacteria and the
underlying pyrite surface are responsible for the leaching
leading to corrosion (Rojas-Chapana and Tributsch, 2004).
4.5.3. Build up of metal ion/organic matter concentration
During bioleaching of sulphide mineral concentrates,
heavy metals such as copper, zinc, arsenic and iron accumulate in the leach liquor, and beyond certain concentrations
they become toxic to the microorganism, thereby deleteriously aecting the rates of biooxidation. The synergism of
toxic eects due to the presence of multi-metal ions in the
medium on oxidation of ferrous iron by A. ferrooxidans

362

N. Pradhan et al. / Minerals Engineering 21 (2008) 355365

have been demonstrated by Das et al. (1997). Single metal


ion studies show that among Fe3+, Cu2+ and Zn2+, Fe3+
is the most toxic whereas Zn2+ is the least. The inuence
of dierent concentrations of base metal ions such as
Cu2+, Zn2+ and Fe3+, when present alone or in dierent
possible binary and ternary combinations in a 9 K medium,
was studied on the ferrous ion oxidation ability of A. ferrooxidans. The reports indicate that it is technically possible to
induce a change from a chemical leaching process with high
ionic strength to a bacterial leaching process, by dilution of
the irrigation solution (Escobar and Lazo, 2003).
Another frequent problem in the operation of heap
bioleaching, according to the reports, is the high concentration of sulfate and other ions in the re-circulating irrigation
solution on the heaps, after copper has been removed by
solvent extraction. Additionally, the organic compounds
used in copper removal might be introduced into the ranate, generating adverse conditions to bacteria (Rusin
et al., 1995).
5. Thermophilic leaching
Chalcopyrite, the most important ore of copper, is not
successfully bioleached with mesophiles due to passivation
after partial extraction of copper for which Thermophilic
bio-heap leaching may be a feasible low-cost low maintenance alternative, provided the necessary temperature conditions for thermophiles can be achieved and maintained
within the heap. The connection between microbial activity
and heat production in copper sulde ore heaps and dumps
(Olson et al., 2003) suggested the importance of thermophiles in bioheap leaching. Use of thermophiles was found
to improve metal sulde biooxidation in at least two ways
(Brierley and Brierley, 1986); rstly, the reaction rates
increased with increasing temperature and secondly there
was increase in the quantum of metal extraction from certain minerals by the elevated temperature, and most notably this is the case with bioleaching of copper from
chalcopyrite. At higher temperatures the chemistry of mineral solubilization is much faster and in the case of chalcopyrite, temperatures within 7580 C are required to
achieve copper extraction at an economically viable rate.
Dixon (2000) has shown with the aid of his heap-heat conservation model that it is possible to harness the heat of
reaction in a sulphide heap to achieve optimal temperature
distribution within.
During the past few years, it has been detected that the
moderately thermophilic microorganisms are capable of
growing at temperatures of 4550 C attained in the center
of heaps (Hanies et al., 1988). Since 1977, many such
organisms have been detected and the genus Sulfobacillus
is one of them. To these organisms must be added the
extremely thermophilic bacteria capable of oxidizing sulphur, both autotrophically and heterotrophically, and
which can grow at 6080 C (temperatures reached inside
the heap in some industrial operations (Rossi, 1990) and
Sulfolobus is one of these bacteria.

Thermophilic archea/bacteria, with an optimal growth


temperature between 60 and 80 C, have been the subject
of several recent studies because of their capacity to solubilise a number of metallic sulphides. The results obtained
demonstrate a greater eciency than that obtained using
the mesophilic microorganisms for similar processing
times. Thermophilic archea/bacteria possess a series of
characteristics that make them especially suitable for bioleaching. They increase the speed of dissolution of metal
sulphides as a consequence of a higher reaction temperature and in addition, they are capable of dissolving ores
such as molybdenite and chalcopyrite that are dicult to
attack using mesophilic microorganisms. Thermophilic
bio-heap leaching, on the other hand, may be a feasible
low-cost low maintenance alternative, provided the necessary temperature conditions can be achieved and maintained within the heap. Bioleaching processes for
demonstration plants operated within a temperature range
of ambient to 80 C have been achieved. As would be
expected, the types of iron- and sulfur-oxidizing microbes
present dier depending on the temperature range. The
types of microbes found in the processes that operate from
ambient to 40 C tend to be similar irrespective of the mineral, as are those within the temperature ranges of 4555 C
and 7580 C.
Newmont mining companys commercial biooxidation
operation in Nevada has measured temperatures up to
81 C in heaps containing 1.41.8% suldesulfur (Tempel,
2003). Temperatures as high as 66 C were noted in a
960,000 tons test heap of low grade run-o-mine chalcopyrite ore containing 4% pyrite at Kennecott Utah Copper
(Ream and Schlitt, 1997). Moderate thermophiles are cultured from hot heaps (Brierley, 1997; Ream and Schlitt,
1997), but extremely thermophilic archea are much less
commonly detected. However, large populations of extremely thermophilic archea can be maintained in heaps inoculated with these organisms (Tempel, 2003).
6. Diculties in heap leaching processes
Heaps and dumps present a number of advantages such
as simple equipment and operation, low investment and
operation costs, and acceptable yields. On the other hand,
it must be realized that the operation suers from some
severe limitations: the piled material is heterogeneous and
practically no close process control can be exerted, except
for intermittent pH adjustment and the addition of some
nutrients. Compared with tank reactors, heap reactors
are more dicult to aerate eciently and the undesirable
formation of gradients of pH and nutrient levels as well
as liquor channeling are dicult to manage. Moreover,
the rates of oxygen and carbon dioxide transfer that can
be obtained are low, and extended periods of operation
are required in order to achieve sucient conversions
(Acevedo and Gentina, 1989).

N. Pradhan et al. / Minerals Engineering 21 (2008) 355365

7. Cost of bio heap leaching


Copper is recovered from the bio heap leach liquor by
solvent-extraction and electrowinning to produce highgrade copper cathode. There are four major processing
components (Fig. 1):
 A crushing plant reduces ore size.
 A heap-leach operation dissolves copper by using the
chemical and bacteriological agents.
 A solvent extraction plant concentrates and puries the
dissolved copper in leach solutions.
 An electrowinning plant produces high-grade, highquality cathode copper.
Generally, the capital cost of a bioleaching operation is
considerably less than that of a conventional smelting/
rening operation. Quoted operating costs (2002), based
on the current technology for leaching dumps and in-place
ore, and is between US $ 0.18 and US $ 0.22 per pound of
cathode copper, which are competitive with the unit costs
of smelting/rening. Heap leaching has the additional cost
of mining and transporting to the leach pad. In some operations additional costs are incurred wherein the ROM is
crushed and mixed with acid for agglomeration prior to
being deposited in the heap. Because of this, direct production costs vary with the grade of the material being leached.
Whether by bioleaching or conventional acid leaching, the
operating costs for heap leaching for the currently operating or planned projects range between US $ 0.34 and US $
0.60. (Dresher, 2004).
8. Some examples
Copper metal is recovered in the largest quantity by
means of heap reactors, although comparisons are dicult
as data are presented in dierent ways. The bioleaching of
copper sulde ores in heaps is a technology widely developed in Chile, with more than 85,000 tons of ore processed
per day (Brierley, 1999). Examples of large copper leaching
operations are those by Sociedad Contractual Minera El
Abra and the Codelco Division Radimiro Tomic in Chile
producing 225,000 and 180,000 tons of Cu per annum,
respectively.
An excellent example of a current commercial bioleach
application is the Quebrada Blanca operation in northern
Chile (Brierley and Brierley, 2001) located on the Alti
Plano at an elevation of 4400 m, in spite of the thinking
that the leaching bacteria cannot function under the cold
temperatures and low oxygen partial pressure of high altitudes. At Quebrada Blanca 17,300 t/day of sulde ore are
100% crushed to 9 mm size, agglomerated with sulfuric
acid and hot water, and stacked to form 6 to 6.5 m high
heaps. Bacterial activity is facilitated by aeration using an
array of airlines installed beneath the heap and low-pressure fans. Bacterial process monitoring includes the on-site
measurements of respiration. The Quebrada Blanca bio-

363

leach process illustrates the successful evolution of biohydrometallurgy in the mining industry. The plant design at
Quebrada Blanca and other similar operations incorporates the bacterial requirements in the process. Research
ndings on improving bacterial activity are now applied
in commercial operations.
A year-long pilot trial at Copper Mines of Australias
Mt. Lyell operation in Tasmania (Rhodes and Deeplaul,
1998) has demonstrated the technical and commercial viability of using moderately thermophilic bacteria to leach a
nely ground concentrate and recover the solubilized copper with solvent extraction-electrowinning. BHP Billiton
Ltd., has developed BioCOP Process, which is an agitated
tank oxidation and leaching of copper suldes. This process is proposed to be employed by BHP Billiton and Codelco, in a joint venture, Alliance Copper Ltd., in a
demonstration plant at Chuquicamata, in northern Chile,
proposed to produce 20,000 tons of cathode copper a year.
Similarly, BacTech/Mintek Process is an agitated tank oxidation and leaching of copper suldes developed by BacTech Enviromet.
GeoBiotics, LLC has developed and patented several
technologies for biooxidizing or bioleaching of sulde ores
and concentrates in an engineered heap environment. The
two principal technologies are the GEOCOAT and GEOLEACH processes. Both technologies incorporate the patented Hot HeapTM control philosophy to ensure optimum
biological performance. In the GEOCOAT process, sulde otation or gravity concentrate slurry is coated onto
crushed and sized support rock which may be barren or
may contain sulde or oxide mineral values. The coated
material is stacked on a lined pad for biooxidation. The
process is applicable to the biooxidation of refractory sulde gold concentrates and to the bioleaching of copper,
nickel, cobalt, zinc, and polymetallic base metal concentrates. Mesophilic or thermophilic biological systems are
used to catalyze the sulde oxidation reactions. In the
processing of chalcopyrite concentrates, the higher temperatures associated with the use of thermophilic microorganisms have proven highly benecial in increasing the rate
and extent of copper leaching. The GEOLEACH technology is applicable for the whole ore systems where the metals occur as suldes. The driving force behind the
GEOLEACH process is that most sulde whole ore leaching systems have enough energy present in the suldes to
allow the heap to obtain very high temperatures, but poor
heat management prevents signicant temperature rise.
Without signicant increase in temperatures beyond ambient within the heap, sulde-leaching kinetics are extremely
slow and in the case of chalcopyrite, extraction is limited by
passivation. The GEOLEACH technology is designed to
maximize heat conservation through careful control of aeration and irrigation rates. Both the processes are simple,
robust, and ideally suited to operation in remote locations.
Nicico and Mintek are working in Iran, for treatment of
Sarcheshmeh ore. This is taking place at the Sarcheshmeh
copper complex in southern Iran, about 160 km southeast
TM

TM

TM

TM

TM

364

N. Pradhan et al. / Minerals Engineering 21 (2008) 355365

of Kerman, which produces some 170,000 tones of copper


a year. Mintek has indicated that it is possible to recover as
much as 60% copper in the heap material. A test run for
this was done in a six-meter column leach using Sarcheshmeh ore, which is predominantly chalcopyrite, but
also contains chalcocite and other copper bearing minerals.
Agreement includes treating highly refractory copper ores
in which the copper occurs predominantly as the copper
sulphide material, chalcopyrite. This type of copper ore
at Sarcheshmeh accounts for 80% of copper reserves
worldwide.
9. Conclusion: present and future of heap bioleaching of
chalcopyrite
The current scenario of bioleaching in developing countries is quite encouraging. Examination of the current
large-scale bioleaching operations reveals that an important number of plants are located in developing countries.
This is not purely accidental but is due to two important
factors. Firstly, many developing countries have signicant
mineral reserves and mining constitutes one of the main
sources of income and secondly, bioleaching technique,
because of its simplicity and low capital cost, is suitable
for developing countries (DaSilva, 1981; Gentina and
Acevedo, 1985; Acevedo et al., 1993). This is the case for
countries like Chile, Indonesia, Mexico, Peru and Zambia.
These developing countries share over 50% of the world
copper production. Developing countries should increase
their eorts in research and development in bioleaching
technology, as comparatively they have competitive advantages in this area. If not utilized, stacks of low-grade ore
generated during mining, potentially endanger the environment, as the metals they contain may be released to the
environment in hazardous forms due to weathering. This
leads to acid mine drainage and pollution of drinking water
sources like surface/underground/river water.
The application of biohydrometallurgy to metal recovery is likely to grow because with suitable mineral deposit,
it oers advantages of low capital and operating cost, operational simplicity, and shorter construction time that no
other alternative process can provide. Increased concern
regarding the eect of mining on the environment is likely
to improve the competitive advantage in favor of microorganism based metal recovery processes (Rawlings, 2004). It
is expected that in coming years several new commercial
bioleaching plants will be installed. The use of thermophilic
bacteria and archea will get more importance for increasing
the leaching rates and metal recoveries and allowing for the
treatment of recalcitrant chalcopyrite ores. International
cooperation is also important in the establishment of new
operations that can signicantly contribute to the social
and economic developments of developing countries. It is
very likely that heap leaching will continue to be the choice
for low-grade ores and tailings in future, and at the end it is
concluded that the next few years would bring in exciting
prospects in copper bioleaching industry for the treatment

of chalcopyrite ores and concentrates for harnessing the


metal values present in low grade ores in an eco-friendly
and economic way.
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