Kinetic and equilibrium effects in

gold ore cyanidation

M.I. Brittan
Head consulting metallurgist, Gold Fields, International Development Projects, Englewood, Colorado

Abstract
Cyanide leaching of two West African gold ores was studied in multiple laboratories to provide process-engineering
data for plant design purposes. Unusually slow leach extraction kinetics were observed using routine cyanide
leach test procedures with pregnant solution monitoring. Carbon-in-leach testing, however, showed normal rapid
kinetic behavior, with the same ultimate gold extractions being reached in much shorter elapsed times. Kinetic
curves based on washed solids assays also exhibited more typical leaching characteristics. The results bore all
the hallmarks of some equilibrium inhibition of the leaching. It was surmised that ore gangue components were
responsible for weakly adsorbing gold-cyanide complex reaction product, thereby holding up soluble gold in
the solid phase. The term “preg-borrowing” was coined to describe the reversible phenomenon and distinguish
it from irreversible preg-robbing. The two ores investigated may represent an extreme form of a more general
effect that in most instances might pass unnoticed. The effect can lead to misinterpretation of kinetic leach curve
data and underestimation of calculated ore head grades.
Key words: Gold Processing, Cyanide leaching, Carbon-in-leach, Kinetics, Equilibrium

Introduction commissioned in late 2004. The mill is now undergoing

A project was launched in 2002 to determine the best
processing option to expand production at Gold Fields’
Tarkwa Mine in Ghana. The open pit operation was started
in 1998 with 100% heap leach production. By 2002, the
question at issue was whether to expand the heap leach or
to install a mill to process the harder ore of lower porosity
that would be encountered at depth in the pits.
Test work was initiated at McClelland Laboratories
in Sparks, Nevada. In due course, further extensive
work was conducted on Tarkwa ore and other samples
from West Africa at the Tarkwa Mine Laboratory; at the
SGS-Lakefield Laboratory (SGS) in Johannesburg, South
Africa; at Kappes, Cassiday & Associates (KCA) in Reno,
Nevada; and at the Advanced Mineral Technology Labo-
ratory (AMTEL) in London, Ontario, Canada. The test
work involved extensive programs geared to providing
flowsheets and plant design parameters for engineering
purposes. Results reported here represent a focused se-
lection from a large body of data to illustrate specific ore
leaching characteristics. The Tarkwa project culminated
in a 4.2 Mt/a (4.6 million stpy) mill that was eventually
expansion to 12 Mt/a (13 million stpy).
The subject of this paper was prompted by some curious
metallurgical behavior that was observed in the course of
the test work.
Gold ore leaching kinetics
Metallurgical extraction reactions involving low-grade
comminuted ores typically exhibit highly nonlinear kinet-
ics. The reaction is normally very rapid to begin with, but the
rate tails off markedly as high extractions are approached.
This behavior is largely caused by progressive changes in
the rate-controlling step (Brittan, 1975). The initial reaction
may be governed by chemical reactions at the surfaces
of exposed gold particles, or diffusion through boundary
layers if pulp agitation is not adequately vigorous.
Chemical equilibrium effects do not normally restrict
gold leaching. The Elsner equation governing the gold
leaching reaction (Marsden and House, 2006) is essen-
tially irreversible, so that even though gold builds up in
the solution as the reaction proceeds, it would not inhibit
the leaching of additional gold.

Paper number MMP-08-011. Original manuscript submitted March 2008. Revised manuscript accepted for publication May
2008. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept.
prior to Feb. 28, 2009. Copyright 2008, Society for Mining, Metallurgy, and Exploration, Inc.

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Figure 1 — Dilution effect on leach extraction kinetics
(Tarkwa ore, Tarkwa Laboratory).
Unless caused by large gold particles, the long tail on the
extraction curve is usually a reflection of the slow diffusion of
cyanide and oxygen reagents, and/or of gold-cyanide complex,
through pores in ore particles (Brittan, 1975). The reagents
will be diffusing to the surfaces of residual partially occluded
gold particles, and the gold-cyanide complex product will be
diffusing away from the surfaces via the interstices to the bulk
solution. For plant design purposes, it is generally this long
tail on the leach curve that dictates the cyanidation residence
time, and therefore the tank capacity, required to achieve the
desired extraction.
The observations made in the course of studying the two
West African ores suggest that effects other than classical
chemical and mass transport phenomena may, in certain cases,
contribute to the form of the gold leach curve.
Laboratory leaching procedures
A few words on test work procedures are appropriate at this
point. The standard milled-ore kinetic leach test conducted by
many laboratories involves taking small intermediate solution
samples from the leach reactor (usually a rolling bottle or a
stirred vessel) to follow the course of the gold extraction. The
gold concentration in the intermediate solution samples is
measured, and pH and cyanide concentration (sometime dis-
solved oxygen as well) usually checked. Makeup solution is
added back to the leach vessel, along with reagents as may be
needed to compensate for evaporation and sample volumes so
as to maintain the original solution volume and the specified
leaching conditions. The gold in solution is implicitly assumed
to represent all the gold that has leached from the ore.
At the end of the test, the pregnant solution is sampled for
gold and reagent concentrations, and the filtered solids are
typically washed before drying and splitting out an aliquot
(or aliquots) for fire assay. Any gold that may be washed from
the solids over and above pregnant solution entrained values
would not be accounted for.
In the case of a column leach test carried out on crushed (and
perhaps agglomerated) ore, pregnant leach solution leaving the
bottom of the column may typically be passed through a bed
of activated carbon to remove the gold in solution before being
returned to the top of the column. The solution grade would
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mmp_117_122.indd 118
normally be monitored on a daily basis while the extraction rate
is reasonably rapid, with appropriate adjustments to maintain
the cyanide strength and the pH.
With extended leach times, column extraction rates drop and
the rate of extraction per pass may be low enough to compromise
accurate measurement of the incremental gold in solution at a
daily frequency. Under these circumstances, the solution leaving
the bottom of the column may be returned directly to the top
of the column, bypassing the activated carbon. Allowing the
gold in solution to build up over several days or a week before
monitoring reduces the labor requirement, while accumulating
sufficient soluble gold to assist analytical accuracy.
Initial test work observations
Initial column cyanide leach testing of crushed and agglomer-
ated Tarkwa ore was carried out at McClelland Laboratories
for heap leach design purposes. It was observed that the low-
porosity ore appeared to be leaching particularly slowly. It was
also noted that when the columns were switched from daily
solution monitoring and circulation through carbon to weekly
circulation without carbon, there was a marked drop in the gold
extraction rate. Once cyanide starvation had been eliminated
as a possible cause, it was apparent that the slowdown was
commensurate with the build-up of gold in solution during
the weekly circulation periods.
Bottle roll cyanidation tests on crushed ore were used as
a means to supplement the column testing. It was similarly
observed that these tests also required excessively long leach
times.
In these tests, gold would be building up in solution as the test
progressed. Could this increase in concentration in the solution
be responsible for inhibition of further gold extraction from
the solid phase? Because, as noted above, the cyanide leach
reaction itself is non-reversible, another reversible equilibrium
reaction of some sort appeared to be in play.
If in fact some equilibrium was being established between
gold in solution and gold in solids, it might be expected that
running tests at different dilutions would influence the extraction
curve. For example, a bottle roll test conducted with a higher
liquid:solids ratio would yield lower soluble gold concentra-
tions in solution. If the hypothesis were correct, the law of
mass action would dictate that this should reduce the kinetics
of the reverse reaction and thus speed up the overall extraction
kinetics. Accordingly, the Tarkwa Laboratory was requested to
run kinetic bottle roll tests on a sample at three dilutions: 1:1,
2:1 and 3:1 (liquid:solids). The results are given in Fig. 1.
Figure 1 shows that the rate of gold extraction does in fact
increase with dilution such that longer times are required to
reach the same gold extraction with less dilute pulps, particu-
larly at higher extractions.
Further observations at SGS-Lakefield
A second test program was initiated at SGS-Lakefield in 2002
to provide design data for the Tarkwa mill option. Bottle roll
and stirred leach testing of milled Tarkwa ore samples were
carried out. It was observed that a sample that required 72
hours to reach 97% extraction in a kinetic leach test (i.e., with
build-up of gold in solution and intermediate solution sampling)
required only 24 hours in a bottle roll carbon-in-leach (CIL)
test. These data are shown in Fig. 2.
In this case, the activated carbon in the CIL test would
adsorb the gold in solution, thereby keeping the concentration
to a low level. Once again, this scenario appeared to promote
much higher rates of extraction.
As mentioned above, the leaching of gold from ores is
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 not just a simple matter of free gold particles in contact with
cyanide and dissolved oxygen. Other steps are involved, such
as diffusion of reagents through boundary layers around ore
particles and within pores and interstices in the particles to
the surface of the gold, along with similar diffusion of reac-
tion products away from the surface to the bulk solution. It
is generally these solid-phase diffusion steps associated with
partially occluded gold particles that determine the ultimate
leaching time required for commercial CIL or CIP plant opera-
tion (Brittan, 1975).
To explain the test work observations, it was speculated
at the time that perhaps the gold was actually leaching at the
particle surface but that the gold-cyanide complex product was
inhibited from finding its way to the bulk solution by the gold
already in solution. If this were the case, it could well be that
the gold concentration in the solution was not a good measure
of the potential extraction kinetics, as suggested by Fig. 2.
There should also be residual solubilized gold remaining in the Figure 2 — Leach vs. CIL extraction kinetics (Tarkwa ore,
solids. Some indication of such gold hold-up in ore had already SGS Laboratory).
been noted during a heap drilling campaign at Tarkwa — it
was found that substantial pockets of rinseable water-soluble
gold existed in apparently spent areas of the heaps. Similarly,
bottle roll tests on clay fractions of ore samples showed periods
when the gold concentration in solution actually dropped as
time passed.
As noted above, typical kinetic leach test procedures con-
ducted by metallurgical laboratories allow for solids residue
washing ahead of drying and sampling of leach residues for fire
assay. The gold in residue washings is not normally measured.
Given the unusual behavior experienced with the Tarkwa ores,
a revised laboratory test work procedure was specified in which
solids residues were to be washed twice with specified aliquots
of water and the gold in the washings accounted for as part of
a total material balance for the test. Thus, the mass of gold in
every product and sample would be accounted for. Figure 3
is an example of the results.
Figure 3 shows that the solid phase is holding up a signifi-
cant portion of soluble gold, an amount greater than would
be accounted for by simple entrainment. This gold would not
appear in the solution samples that are normally taken in the
course of a kinetic cyanidation test. This gold rinses out easily Figure 3 — Solution vs. washed solids leaching kinetics
and, therefore, should be considered as part of the gold that (Tarkwa ore, SGS Laboratory).
has been extracted.1 As was seen, it is preferentially captured
by activated charcoal in a CIL test.
It should also be noted that if the soluble gold in the final
residue is not accounted for, the back-calculated head grade
of the sample will be lowered accordingly.
The results generally seemed more commensurate with
“Preg-borrowing” weak, reversible adsorption of the complex onto gangue par-
One possible hypothesis to explain the observations could be ticles, with Tarkwa ores having certain gangue constituents
that the gold-cyanide complex in solution reduces the driving that might promote the adsorption. The term “preg-borrowing”
force for diffusion of complex out of the ore particles into was coined to describe the phenomenon. As opposed to preg-
the bulk solution. If this were the case, however, one would robbing, where the gold is strongly adsorbed, the adsorption
expect to have experienced this manifestation of gold leaching experienced in this case was reversible.
behavior with many ores, particularly given the widespread Thus, removing the gold from solution (as in CIL) creates
kinetic testing of gold ores in the industry over the last century a desorption driving force to keep the gold from adsorbing
and more. on to gangue. Similarly, operating at greater dilution (higher
liquid:solids ratio) will reduce the tendency to adsorb because
1 It is necessary here to distinguish between gold that has the solution concentration of the gold-cyanide complex is lower.
already been solubilized and additional gold that could leach The fact that the gold is easily washed from the residue solids
out of test residue solids during the washing stage. Vacuum indicates that the adsorption bonds are indeed weak.
filtration and washing of residues introduces a dose of fresh The ability of activated carbon to accelerate the apparent
oxygen that, with residual cyanide in the filter cake, could lead kinetics is an indication that chemical control or depletion of
to further leaching if oxygen starvation had been a problem cyanide and oxygen reagents were not issues in these tests.
in the test. Certainly, over all the test work programs, there was a large

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Figure 4 — Solution vs. washed solids vs. CIL leach kinetics
(Tarkwa ore, AMTEL Laboratory).
Figure 5 — Whole ore leaching kinetics (West African ore,
KCA Laboratory).
body of test work conducted (not reported here) to establish
and maintain appropriate cyanide and oxygen concentrations
during leaching.
An attempt was made to determine which of the gangue
species could be responsible for the weak adsorption of the
gold. Clays, for example, are recognized adsorbers of gold. A
sample of the Tarkwa ore tested by SGS was sent to AMTEL
in Canada for examination. The mineralogical composition of
this sample is given in Table 1.
Surface microanalysis of the clay fraction showed no evi-
dence for preg-borrowing. However, it should be noted that any
quest to uncover the responsible gangue component in just a
few tests with limited sample is a tall order because the weak
nature of the adsorption bond means that any sample preparation
technique involving washing or drying of the cyanided solids
militates against the adsorbed species remaining intact.
In any event, AMTEL carried out their own independent
leach tests on the sample and found behavior similar to that
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mmp_117_122.indd 120
Table 1 — Mineralogical composition of Tarkwa
sample.
Mineral Concentration, %
Quartz 86.1
K-feldspar 0
Na/Ca Plagioclase 0
Calcite 0
Dolomite 0
Pyrite 0
Kaolinite 0.9
Muscovite (2M1, 3T) 9.8
Chlorite 0
Paragonite 3.2
Total: 100
reported by McClelland Laboratories and SGS, as shown in
Fig. 4.
In Fig. 4, the gold extraction based solely on solution
samples is both lower and slower than that determined from
washed solids. A single CIL test at a 24-hour residence time
once again duplicated the extraction achieved by washing of
the solids.
Second ore from West Africa
In 2005, Gold Fields began an investigation of another ore
deposit in West Africa. Oxide ores in this deposit typically
contained major quartz with some muscovite and minor go-
ethite and kaolinite. Primary ores contained major quartz and
plagioclase, along with ankerite and muscovite and minor
tourmaline and sulfides.
Metallurgical testing for this project was initially carried out
by Kappes, Cassiday & Associates and involved both column
leach tests on crushed ore and bottle roll tests on milled ore
samples. The ores from this deposit displayed the same charac-
teristics as had been observed with the Tarkwa material, but in
this case the results were exacerbated by a very strong nugget
effect — the ore samples contained visible gold particles.
The same apparent slow leaching kinetics was observed
when whole ore was subjected to kinetic leach tests, as illus-
trated in Fig. 5. Here it can be seen that the ore still appears
to be leaching at a significant rate after 48 hours.
When the same tests were repeated on gravity tails after a
gravity concentrate had been removed, much faster kinetics
was in evidence, as shown in Fig. 6. The gold in gravity tails
appears to have leached fully after only 24 hours.
The leach solution gold concentrations would, of course,
be lower for gravity tails with reduced leach feed grades
than they would for whole ore. In keeping with the behav-
ior of the Tarkwa ores, it could be speculated that this was
responsible for the faster kinetics of the other West African
ore gravity tails. The difference in rates, however, appeared
too dramatic for this to be the primary cause. At the same
time, ores with large free gold particles often exhibit slow
leaching behavior.
As further tests would show for the West African ore, large
gold particles were not the sole contributing factor. Additional
samples for this prospect were tested at McClelland Labora-
tories. Relevant results are shown in Fig. 7.
From Fig. 7 it can be seen that CIL leaching of whole ore is
a lot faster than cyanidation in the absence of activated carbon.
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 Figure 6 — Gravity tails leaching kinetics (West African ore,
KCA Laboratory).
Figure 7 — Whole ore vs. CIL vs. gravity tails leaching (West
African ore, McClelland Laboratories).
If the cyanidation extraction rate were being determined only by
the leaching of large particles, it would not be possible to speed
up the kinetics merely by having the gold in solution adsorb
on to activated carbon. Consequently, some preg-borrowing
appears to be at play in this case as well. Figure 7 also shows
that with a gravity concentrate removed, the gravity tails leach
readily. The ultimate extraction in 36 hours for the whole ore
CIL case, and the gravity-with-tails-cyanidation case, are es-
sentially the same. Whole-ore cyanidation, on the other hand,
requires 72 hours to reach the same extraction.
pH investigation
Early on in these test work programs, it was anticipated that
pH could have an influence on leaching kinetics, because pH
effects are known in gold ore cyanidation (Marsden and House,
2006) and have been observed in the analysis and optimiza-
tion of gold plant operations (see, for example, Brittan and
Taschereau, 2005). One effect of increasing pH is to raise the
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mmp_117_122.indd 121
Figure 8 — Effect of pH on leaching kinetics (Tarkwa ore,
McClelland Laboratories).
Figure 9 — Effect of pH and alkaline reagent on initial leach-
ing kinetics (West African ore, McClelland Laboratories).
viscosity of the pulp, which might tend to inhibit mass transfer
if pulp agitation is not adequately vigorous.
To determine whether pH may have an influence on this
phenomenon, conventional cyanide leach kinetic tests at two
different pH levels were conducted in the original 2002 Mc-
Clelland Laboratory investigation on a Tarkwa sample. The
results are given in Fig. 8.
Figure 8 shows somewhat faster kinetics at lower pH, but with
the same ultimate extraction being attained after 24 hours.
A recent paper by Davidson and Sole (2007) has also ques-
tioned whether the calcium ion associated with the lime used
for pH control may not in fact have adverse consequences for
gold cyanidation chemistry. With this in mind, a test was car-
ried out at McClelland Laboratories in 2007 on a gravity tails
sample of the West African ore in which caustic soda was used
for pH control. For comparison, two pH levels were tested with
lime as the base. The results are shown in Fig. 9.
The results again accord with a tendency for faster initial
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 extraction kinetics at lower pH and, perhaps, with caustic used
for pH adjustment in place of lime.
Interpretation of the kinetic results in Figs. 8 and 9 is not
unequivocal, however, in establishing a definite chemical role
for lime or the calcium ion. As noted above, lime can have a
negative influence on pulp viscosity, thereby affecting rates of
mass transfer. In addition, any testing of pH has to be rigorously
conducted to ensure that extraneous effects such as cyanide
depletion (at lower pH) and competing reactions (Marsden and
House, 2006) do not influence the results. Extensive testing under
well-controlled conditions of sample homogeneity, temperature,
agitation and reagent concentrations would have to be carried
out in combination with viscosity measurement to address these
issues. This is beyond the scope of the present exercise.
Discussion and conclusions
The kinetic effects observed in the case of the two West African
ores may well represent extreme cases of what could be a fairly
general phenomenon. For most ores that one encounters, it is
conceivable that the quantity of solubilized gold held up by
gangue adsorption in the solids is relatively small so that the
preg-borrowing effect would not be noticeable. Cases have,
however, been reported in kinetic cyanidation testing where
the gold concentration in solution reaches a peak and then
declines with time. This could well accompany a drop in pulp
temperature, such as with leach tests left to run overnight. In
this instance, any equilibrium between gold in solution and gold
adsorbed on solids would be pushed slightly in the direction of
more adsorption as the temperature drops, leading to a small
depletion in solution concentration.
The two West African ores studied may well have gangue
components that promote a much higher degree of gold complex
adsorption than most run-of-the-mill ores one encounters.
The exact mechanism of the “preg-borrowing” phenomenon
cannot be determined unequivocally from the limited data
August 2008 • Vol. 25 No. 3 122
mmp_117_122.indd 122
available in the studies reported here, but certainly has many
of the characteristics of a reversible adsorption phenomenon.
The “preg-borrowing” label is, therefore, appropriate.
In practical terms, “preg-borrowing,” because of its revers-
ible character, should not be problematic for plant operation.
Nevertheless, for the plants designed by Gold Fields where ores
have exhibited this behavior, preg-borrowing has constituted
one reason for selecting CIL as the process of choice rather
than leach-CIP.
The phenomenon could well have implications for the pro-
cedures used in the testing of gold ores and the interpretation
of test work results:
• Kinetic testing with results based solely on solution
samples and final washed residue assays may yield mis-
leading results. This could affect, inter alia, the design
residence time specified for plant operation.
• If a significant proportion of solubilized gold is held
up in the solids and is not accounted for, this will lead
to an underestimation of ore head grade. This can have
repercussions not only for metallurgical processing, but
also for ore reserve estimation and project valuation.
• Any wet chemical leach assay method employed for grade
estimation purposes should be thoroughly investigated
using the total gold mass-balance concept.
References
Brittan, M.I., 1975, “Variable activation energy model for leaching kinetics,”
International Journal of Mineral Processing, Vol. 2, pp. 321-331.
Brittan, M.I., and Taschereau, C.A., 2005, “Improving cash flow at Gold Fields’
Damang Mill, Ghana with the aid of diagnostic process analysis,” Mining
Engineering, December 2005, pp. 41-47.
Davidson, R.J., and Sole, M.J., 2007, “The major role played by calcium in gold
plant circuits,” Journal of the South African Institute of Mining and Metal-
lurgy, Vol. 107, pp. 463-468.
Marsden, J.O., and House, C.I., 2006, The Chemistry of Gold Extraction, 2nd
Edition, Society for Mining, Metallurgy, and Exploration, Inc. (SME).
MINERALS & METALLURGICAL PROCESSING
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