ACID REQUIREMENTS IN BACTERIAL HEAP LEACHING OF

COPPER SULPHIDE ORES

Sergio Bustos, Jesús M. Casas, Cecilia González

SGS Lakefield Research Chile S.A.
jcasas@lakefield.com

ABSTRACT

Acid plays a significant role in heap leaching of copper ores. Both, acid consumption by the ore as well
as copper dissolution depend on the acid concentration and on the ferric concentration level in the
leach solution. Ferric sulphate participates in the oxidation of copper sulphides and in hydrolytic
precipitation reactions due to local pH changes occurring during the leaching process. These local
reaction processes are influenced by the particular solution flow pattern in heap leaching, which
promotes an acid concentration profile changing in time, as the solution moves from the top to the
bottom of the heap.
The local acid concentration also has control on the bacterial activity. High acid concentration in leach
solutions increases the lag time to reach the exponential growth and the final size of the bacterial
population in the heap. Low acidity moves the system from the wanted oxidation-reduction processes
occurring both at the mineral and biological interphases, to hydrolytic processes leading to pasivation
of the reaction surfaces due to iron precipitation and to a delay in bacterial colonization of the ore.
Acid preconditioning of the ore prior to irrigation allows for faster displacement of the bacterial growth
active zone from the upper sectors near to the irrigation surface down to deeper zones in the ore bed.
This process typically carried out during the agglomeration stage of fine crushed ore charged in heaps
needs to be accomplished by presoaking with acidified water in dump leach operations with ROM ore.
Experimental results from column leach tests suggest the beneficial effect of reducing the size of the
ore down to 5 inches to enhance acid preconditioning by sprinkling the acid on to a belt conveyor prior
to the charge of the ore in the dump. A reduction in leaching time and an increase in copper
concentration in PLS solutions associated to a reduction of about 0.5-1 m3/Ton volume application rate
could be reached when applying this preconditioning as compared to just irrigating with raffinate
solution from the beginning.

INTRODUCTION

Bacterial growth in ore heap or dump leaching operations depends on the existence of pH and
temperature conditions that allow for the occurrence of metabolic reactions at the bacteria-solution
and or bacteria-mineral interphases, leading to copper dissolution from copper sulphide ores (1,2).
These reactions typically correspond to the Fe2+ oxidation through the coupled reduction of the
dissolved oxygen, which acts as the final electron acceptor in the bacterial respiratory chain. The
resulting ferric ion promotes the dissolution of secondary copper sulphide species liberating copper in
the solution and recycling the ferrous ion to the system, thus giving chance for repetition of this cycle as
long as the reducing action of the ore is present. As a result of this bacterial growth, an increase in the
bacterial population occurs reaching concentrations of thousands of millions of bacteria per gram of
ore (3).
This extraordinary bacterial growth can only happen associated with two coupled reaction processes
occurring at two different interphases, one biological at the bacterial surface, which purpose is to
provide the energy for metabolic processes by transferring the electron released by ferrous ion, and the
other one, a totally separated and independent physico-chemical phenomenon occurring at the
mineral surface, which corresponds to the electron transfer from the sulphide mineral species to the
ferric ion in the solution (1). These reactions can be represented by:

½ O2 + 2Fe2+ + 2H+ ---> 2Fe3+ + H2O (1) Bacterial

Cu2S + 2Fe3+ ---> Cu+2 + CuS + 2Fe2+ (2) Physico - chemical

The rate of reaction 1 depends on the number of bacteria present in the system, which in turn depends
on temperature, dissolved oxygen concentration and pH. This reaction consumes acid, however pH
below 1.8 produces inhibition of bacterial activity due to the waste of energy in bacterial adaptation
processes instead of producing biomass, thus reducing the bacterial growth rate (4).
Reaction 2, here represented by chalcocite dissolution, is fast and to some extent depending on ferric
concentration. This reaction changes the reacting solid phase producing a covellite like sulphide, which
has different semiconducting properties as compared to those of the original chalcocite. Therefore,
once all of the chalcocite has been transformed in covellite, the reducing properties of the ore
significantly decrease, the solution remains ferric and the bacterial growth ceases as the energetic
substrate, the ferrous ion is not anymore available.
Depending on the ore grade and mineralisation, and on the temperature and pH conditions present
during the combined cycle of the coupled reactions 1 and 2, the maximum size of the bacterial
population in the ore will differ significantly. Figure 1 presents the dependence of bacterial activity on
temperature, based on the evolution of the “heap oxidative capacity” parameter, expressed as kg
Equivalent Fe3+/ton /day (5). This is very high at the beginning, when chalcocite is being dissolved. This
reaction is mainly associated with the reduction of ferric being fed with the irrigation solution, with
ferric being dissolved from the ore, and with ferrous being chemically oxidised with oxygen. This last
reaction occurs at a very high rate due to the mass action effect generated by the strong reducing
character of chalcocite at the relatively high initial pH. As chalcocite is depleted, the heap oxidation
capacity drops significantly until bacterial activity appears. Temperature plays an important role, both in
determining the lag time to reach a significant bacterial population size and in establishing the level of
equivalent ferric that can be produced from the resulting bacterial activity.

5,0

4,5

4,0
Kg Cu/Ton, Kg Fe+3 /Ton /day

3,5

3,0
Ox capacity + 10
KgFe+3/Ton/día
2,5
Cu extraction, Kg/Ton
2,0

1,5

1,0

0,5

0,0
0 25 50 75 100 125 150
Leaching time, days

Figure 1 – Bacterial activity and copper extraction from secondary sulphides at 20°C
In ferric leaching processes iron participates in several reactions and speciates in free and associated
electrolytes, such as: Fe2+, Fe3+, FeSO4(aq), FeH(SO4)2(aq), FeSO4+, Fem(OH)n+3m-n, etc. The association degree
increases both with temperature and acidity. At pH lower than 2 sulfuric acid speciates as free (H+) and
associate ions (bisulphate HSO4-), which produce a buffer effect and maintain the pH practically
constant in the range of 1.5 to 1.8. At this condition ferric iron is solubilized from the ore and
participates in several leaching reactions with sulphide minerals and gangue components. The increase
of dissolved sulfate species in the solution produces an increase of bisulphate concentration which
reduces the participation of free acid in gangue reactions, resulting in a reduction of net acid
consumption (6).
Based on experimental results obtained in column leach tests with copper secondary sulphide ores at
different crush sizes, it is possible to show the beneficial effect of acid preconditioning of the ore prior
to irrigation. This preconditioning is typically carried out during the agglomeration stage of fine crushed
material, but needs to be applied as presoaking or through sprinkling on to a belt conveyor for the ROM
or coarser size distributions found in dump leaching operations.

EXPERIMENTAL BACKGROUND
Long-term column leach tests in 3–6 m high by 0.2–1.2 m diameter columns with 250–5000 kg of
secondary sulphide ores have been carried out at SGS Lakefield for different testwork programs. The
ores typically assayed 0.6–1.6 kg/ton copper of which about 70% was mainly chalcocite, 20% was oxide
copper and the rest was chalcopyrite. Copper extractions usually higher than 80% were obtained for
fine crushed materials after leaching times ranging from 6–14 months, depending on the ore
characteristics. Copper extractions decreased significantly for coarser size distributions due to poor
liberation but also because of the slower sulphide oxidation rate due to poor bacterial growth
conditions as compared to those present in agglomerated ores.
When dealing with coarser size distributions a faster decrease in effluent solution pH occurs as
compared to that observed for the fine crushed material even when the coarser ore has not been
subjected to any acid preconditioning process. Figure 2 shows that for the same ore the copper
extraction can be very similar at the two crush sizes of 2 inches and ¾ inches. However, a large
difference is observed for the coarse material down to 5 inches. The initial increase in the effluent pH
from 3 to about 3.4 and the subsequent plateau observed for the crushed ores correspond to the
increase in the bacterial activity and to the development of the bacterial population in the ore bed
associated to the first stage of chalcocite dissolution (reaction 1). This phenomenon is slightly observed
in the coarse ore as both the exposed chalcocite grade and the ore reactivity towards the acid is lower.
The copper extraction kinetics for the second stage of covellite dissolution is practically the same for the
three different crush sizes, indicating chemical reaction rate control at the ambient operation
temperature. The effluent solutions show almost the same pH and ferric generation is practically cero
for the coarser and for the finer size distributions, which is consistent with the fact that columns have
been irrigated with recycled solution from SX and iron in the raffinate solution is almost 100% ferric. The
2 inches material shows a better ferric generation behavior suggesting the existence of a possible
optimum size distribution for bacterial growth and activity. Although no apparent change in the copper
dissolution rate was observed, the higher ferric production and lower pH in the effluent solutions might
be the result of pyrite dissolution.
The inclusion of an acid preconditioning step of the ore by irrigating with acidified water prior to
raffinate irrigation improved the initial copper dissolution kinetics and allowed for a significant
reduction in the application rate and time for reaching the expected copper extraction levels. As it is
shown in Figure 3, although pH evolution practically does not differ from the case when the irrigation
was carried out only with raffinate solution, in this case iron hydrolysis is significantly higher thus
supplying the required acid, but producing iron precipitates which reduce the ferric availability to
oxidize the sulphides and produce surface coverage hindering the electron transfer at the mineral
solution interphase.
The testwork results presented here correspond to acid preconditioning by presoaking with acidified
water from the irrigation surface. This acid addition promotes an acid profile which will extend deep
into the heap height depending on the acid consumption of the ore. Although the benefit of this
acidification procedure is apparent, the use of crushed material down to 5 inches gives the possibility
for adding the acid to the ore in a belt conveyor before charging it in the dump. The rest period after
acid preconditioning, whether by presoaking or sprinkling reduces the occurrence of potential high
local acid conditions in the upper sectors of the ore bed, which could hinder the bacterial growth,
promote long lag times and rather small bacterial population in the ore bed.
 9.0

Total Iron Extraction, (kg/ton)

1.0
Copper Extraction, (kg Cu/ton) 8.0
0.5
7.0
6.0 0.0

5.0 -0.5
4.0 -1.0
3.0 -1.5
2.0
-2.0
1.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 Leaching Ratio, (m3/ton)
3
Leaching Ratio, (m /ton) P80 5" P80 2" P80 3/4"
P80 5" P80 2" P80 3/4"

4.0 0.0

Fe(III) generation, (kg/ton)

3.5
pH Effluent Solution

-0.5
3.0
2.5 -1.0

2.0
-1.5
1.5
1.0 -2.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
3
3
Leaching Ratio, (m /ton) Leaching Ratio, (m /ton)

P80 5" P80 2" P80 3/4"

P80 5" P80 2" P80 3/4"

Figure 2 – Column leach test results with secondary sulphide ores at different crush size
 7.0 1.5

Total Iron Extraction, (kg/ton)

Copper Extraction, (kg Cu/ton)

6.5
6.0
5.5 1.0
5.0
4.5 0.5
4.0
3.5
3.0 0.0
2.5
2.0 -0.5
1.5
1.0
0.5 -1.0
0.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3
Leaching Ratio, (m /ton)
Leaching Ratio, (m3/ton)
Presoak Non-Presoak Presoak Non Presoak

4.5 0.5

Fe(III) generation, (kg/ton)

4.0 0.0
pH Efluent Solution

3.5
-0.5
3.0
2.5 -1.0
2.0
-1.5
1.5
1.0 -2.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
3
Leaching Ratio, (m3/ton) Leaching Ratio, (m /ton)

Presoak Non Presoak Presoak Non Presoak

Figure 3 – Column leach test results with secondary sulphide ore at P80 5” and acid preconditionin
PROJECTION TO INDUSTRIAL OPERATION
Significant improvements in heap leaching operations of secondary sulphide ores have been developed
in the last 10 years, particularly in what is concerned to the irrigation strategies, air injection and
remining, which have allowed for obtaining the expected high copper extractions (7). The tendency of
initial heap leaching process designs to crush fine typically down to ¼ inch to reach higher extractions
was changed to about P80 ½ inch to improve percolation both of solution and air in the ore bed.
Although each operation has its own particularities, this change has shown beneficial also in reducing
the fines in the feed (material –100 mesh), and in operating at higher heap heights without
compromising the irrigation flow. Almost all of these operations include the agglomeration step, which
allows for acid preconditioning of the ore, thus producing from the start of irrigation a homogeneous
acidification of the ore in the whole heap height.
The characteristic top-down flow irrigation pattern applied in heap and dump leaching operations
makes the biomass colonization to occur by displacing the bacterial growth active zone from the
initially well suited upper sector near to the irrigation surface down to deeper zones in the ore bed. This
top–down flow pattern also promotes the development of concentration profiles in the heap or dump
height, which control the dynamics of the colonization process.
Oxygen availability has been enhanced through air injection at the bottom of the heaps, but local acid
concentration will depend on the acid consumption of the ore and the way in which it was
preconditioned before starting irrigation. Both factors are more difficult to control in dump leaching
operations with ROM ore having 50–100 m lifts. Here typically low grade ores usually high in
chalcopyrite are irrigated at ambient temperature with a raffinate solution, which is converted to ferric,
provided acid is available to maintain ferric in solution. Even assuming that there is no air restriction, a
relatively small bacterial population is associated to these systems as growing conditions are
characterized by a rather low reducing environment, thus controlled by the lack of enough ferrous ion
availability.
Depending on the pyrite content of the ore and after prolonged leaching times, acid can be produced
by bacterial oxidation of pyrite, which can be consumed by the ore and generate heat which could
make the solution temperature to increase up to a level in which the reducing capability of the ore can
be increased by the change in chalcopyrite reactivity at higher temperature. This process to be effective
needs to be accompanied by a global change in the bacterial population from a mesophilic strain to a
termophilic one, able to growth at 50-60 °C.
The projection of these results and observations to a leaching system which includes a common
solution circuit to irrigate both a heap leach and a dump leach operation suggests the convenience to
reduce the crush size of the dump leach material as much as possible to allow for an acid
preconditioning step. A crush size down to 5 inches might include this acidification process by
sprinkling the acid in a belt conveyor prior to charge the ore in the dump. The acid preconditioning
would reduce the iron retention in the early irrigation stage of the dump and would tend to produce
ferric for the usually larger ferric demands from the heap. The improved conditions for the bacterial
growth should enhance the colonization of the broad dump volume and could result in faster copper
dissolution equivalent to lower volume application rates as high as 0.5-1 m3/ton.
CONCLUSIONS

Similarly to what happens in oxide ore leaching, acid plays a significant role in bioleaching of sulphide
ores as well. It controls the local pH at the different sectors in the ore bed promoting conditions for the
bacterial growth by enhancing ferric ion stability in leach solutions and by supplying protons for the
respiratory chain in bacterial metabolic processes. Agglomeration stages in heap leaching of fine
crushed ores allow for initial preconditioning of the whole ore bed prior to irrigation. As the
agglomeration stage is not included in dump leaching operations, an acid preconditioning stage is
strongly recommended. When dealing with ROM ores this can be done by presoaking of the ore with
acidified water, however coarse crushing of the ore down to 4-5 inches would improve final copper
extractions and could give an opportunity for sprinkling acid on a belt conveyor prior to charging the
ore in the dump. Copper extraction kinetics could be accelerated and a reduction in the volume
application rate of about 0.5-1 m3/ton could be obtained with beneficial effects on leaching time and on
copper concentration in PLS solution.

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•
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•
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•
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