Minerals Engineering 19 (2006) 56–61

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Treatment of pyritic matrix gold–silver refractory

ores by ozonization–cyanidation
E. Elorza-Rodrı́guez a, F. Nava-Alonso a,*
, J. Jara b, C. Lara-Valenzuela c

a
CINVESTAV Unidad Saltillo, Carretera Saltillo-Monterrey km 13, Fraccionamiento Molinos del Rey,
25900 Ramos Arizpe, Coahuila, México
b
Air Liquide Canada, 1250 Rene Levesque Blvd. West, Montreal, Que., Canada H3B-5E6
c
Servicios Industriales Peñoles, Prof. Antonio Coello 310 Norte Col. Obrera, Monterrey NL, 64010 México

Received 20 January 2005; accepted 8 June 2005

Available online 27 July 2005

Abstract

Most of the gold and silver produced worldwide are extracted by the cyanidation process. The recovery of the precious metals
involves two distinct operations: the oxidative dissolution of gold and silver by an alkaline cyanide solution, and the reductive pre-
cipitation of metals from the solution. From the cyanidation point of view, gold and silver ores can be classified as free milling, and
refractory ores. The term ‘‘refractory ore’’ defines those materials that when submitted to a conventional cyanidation process, show
low recoveries (<80%) or high consumption of reactants [Weir, D., Berezowsky, M., 1984. Gold Extraction from Refractory Con-
centrates, Sherrit Research Centre, Alberta, Canada, pp. 1–26; Haque, K.E., 1992. The Role of Oxygen in Cyanide Leaching of
Gold Ore, CIM Bulletin 85963, pp. 31–38]. These refractory ores are usually pretreated by some oxidizing process after which gold
and silver can be recovered by standard cyanidation process. Since ozone gas (O3) is a strong oxidizing, it may be regarded as a
promising alternative in the treatment of refractory ores.
The present work summarizes the results obtained when two pyritic refractory ores from Mexican sites (samples A and B), were
pretreated with an oxygen/ozone stream in acid media before cyanidation. Two contacting methods were studied: the indirect
method (contacting the ore three times with ozone saturated water), and the direct method (direct addition of ozone to the mineral
slurry). Sample A did not show any difference in recoveries with indirect pretreatment, while the direct pretreatment reduced the
cyanidation time for maximal gold and silver recovery from 40 to 24 h. Sample B, only tested with indirect contact method,
increased the gold recovery from 53% to 88% and the silver recovery from 26% to 78%.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Cyanidation; Ozone oxidation; Refractory ores

1. Introduction association and complexity, but also on the behavior

Most of the gold and silver produced in Mexico
comes from the treatment of sulphide ores of base met-
als: lead, copper and zinc. Due to their low concentra-
tion, the dissolution of gold and silver in cyanide
solutions not only depends on their mineralogical
*
Corresponding author. Tel.: +52 844 438 9600; fax: +52 844 438
9610.
E-mail address: fabiola.nava@cinvestav.edu.mx (F. Nava-Alonso).
of the associated sulphides. The depletion of easily
leachable secondary deposits and the high price of gold,
have forced the mining industry to process low grade
ores as well as primary deposits. In primary deposits,
the association of gold with the main host minerals such
as pyrite, arsenopyrite and pyrrhotite, can be at atomic
level, thus a large quantity of the metal cannot be effi-
ciently extracted. Typically a gold–silver refractory
ore, where precious metals are found intimately associ-
ated with sulphides, requires an oxidizing pretreatment

0892-6875/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.06.003
 E. Elorza-Rodrı́guez et al. / Minerals Engineering 19 (2006) 56–61 57

before cyanidation (Weir and Berezowsky, 1984). The
main available pretreatments are: roasting, oxidation
at high and low pressure, chemical oxidation and bacte-
rial oxidation. These pretreatments often imply environ-
mental problems, excessive capital requirements,
excessive operation time, high operating and mainte-
nance costs or highly trained operating personnel. These
disadvantages, coupled with the depletion of easily
leachable ores, are forcing the mineral industry to ex-
plore new options to treat the refractory gold and silver
ores.
Ozone has been used in the hydrometallurgy of gold
to eliminate the cyanide contained in the effluent (Car-
rillo et al., 1999; Ruiz and Nava, 2001). Its high oxidiz-
ing power (2.0 V) makes it thermodynamically able to
oxidize all metals, sulphides and arsenides (Roca et al.,
2000; Viñals et al., 2001). Previous works with sulphide
ores containing gold and silver propose the use of ozone
as pretreatment to cyanidation in order to increase the
recovery of precious metals (Antwerp and Lincoln,
1987; Carrillo et al., 2001). In this work the use of ozone
is studied as oxidative pretreatment for gold and silver
refractory ores with the aim of modifying the pyritic ma-
trix to allow the precious metals to be leached by
cyanide.
2. Materials and methods
The samples used in this work were flotation tailings
of two industrial operations of base metal sulfides. Both
are of pyritic matrix (sample A 68% of pyrite, sample B
38% pyrite). In sample A, 60% of gold is free and finely
grained (6–20 lm) and the rest is associated with pyrite
and quartz. Silver is present as silver sulfides (pyrargirite
and freibergite). In sample B 14% of gold is free measur-
ing an average of 8 lm and the remaining gold is associ-
ated with pyrite, sphalerite and quartz. In sample B silver
is in the form of the sulfides freibergite and pyrargirite.
Table 1 presents the chemical composition of the ores.
All solutions were prepared with distilled water and
analytical grade reagents. The resulting solutions of
the tests were analyzed for Ag, Pb, Cu, Zn and Fe by
atomic absorption in a Perkin Elmer spectrometer
model 2380. The solid residues were sampled and ana-
lyzed for gold and silver by fire assay and for Pb, Cu,
Zn and Fe by atomic absorption. Free cyanide analysis
was performed in solutions with volumetric titration and
specific ion electrode.
The experimental set up can be seen in Fig. 1. The
ozone was produced from extra dry pure oxygen with
a Pacific Ozone Technology (L22) generator. A bubble
column was used for saturating water with ozone. This
column was in acrylic, 0.057 m diameter, 2 m height
and provided at the bottom with a stainless steel cylin-
drical sparger (0.025 m diameter, 0.065 m height and
5 lm of pore diameter). The contact between the min-
eral sample and the ozonizated water (or the direct
ozonization of the mineral pulp) was carried out in an
acrylic reactor (0.15 m diameter, 0.22 m height) pro-
vided with a Lightnin mechanical stirrer and a stainless
steel cylindrical sparger similar to that located in the col-
umn. The reactor had three baffles and a stainless steel
hermetic covering on which the electrodes were located.
On line measurements were taken of pH (Orion 720 A),
redox potential (Orion 520 A), dissolved oxygen (Orion
835), dissolved ozone (ATI A15/64) and ozone concen-
tration in gas (BMT 963). Signals were acquired with
a board DAS 1601 and processed with the TestPoint
Software.

Table 1
Refractory ores used in this work (tailings of two metal sulphide
flotation plants in Mexico)
Sample A Sample B
Specific gravity 4.3 3.5
Size (d80) lm 120 45
Au (g/ton) 1.67 0.85
Ag (g/ton) 49 153
Pb (%) 0.30 0.54
Cu (%) 0.18 0.78
Zn (%) 1.08 3.21
Fe (%) 34.4 18.11
Au species Native, free and Native, free, associated
associated to to pyrite and occluded
pyrite and quartz in quartz and sphalerite
Ag species Pyrargyrite Pyrargyrite and freibergite
and freibergite
Fig. 1. Experimental set up for ozone pretreatment tests.
58 E. Elorza-Rodrı́guez et al. / Minerals Engineering 19 (2006) 56–61

Oxygen plays an important role in cyanidation. If the While stirring at 800 rpm, 3 L/min of oxygen/ozone
amount of oxygen present in the cyanidation pulp is mixture (50 g O3/Nm3) was fed to the reactor for
low, the gold and silver dissolution rate will decrease, 15 min. After sampling for chemical analysis and dis-
or even stop (Haque, 1992). The great amount of sul- carding the rest of the solution, the solid content was ad-
fides present in the samples, and its high reactivity, sug- justed with distilled water and a standard cyanidation
gest that the dissolved oxygen present in the mineral was performed. Data of chemical analysis as well as
pulps of samples A and B is too low to assure the pre- pH, redox potential, dissolved oxygen and dissolved
cious metal dissolution. In order to verify the oxygen ozone were recorded.
availability for the cyanidation process, the oxygen de-
mand of each mineral sample was measured.
The oxygen demand of samples A and B was mea- 3. Results and discussion
sured by placing 10 g of mineral in a 250 ml water-jack-
eted glass reactor filled with distilled water. The reactor 3.1. Oxygen demand of minerals
was hermetically closed with a rubber stopper provided
with an oxygen probe and magnetically stirred at con- The oxygen demand for both samples is shown in
stant temperature (25 °C) for 2 h. The dissolved oxygen Fig. 2. When sample A is in contact with distilled water
concentration was continuously measured and regis- (7 mg/L initial dissolved oxygen), the mineral shows an
tered by means of a computer. The oxygen demand of oxygen demand of 44 g O2/ton/h. When the water is
each mineral sample was computed with the data col- bubbled with oxygen before the addition of mineral
lected, the volume of distilled water and the weight of (25 mg/L initial dissolved oxygen), the demand raises
mineral. to 123 g O2/ton/h. When mineral B is placed in contact
For contacting the ozone with the mineral two meth- with distilled water (7 mg/L initial dissolved oxygen),
ods were tested: the indirect pretreatment, where the the resulting oxygen demand is 152 g O2/ton/h. Such
mineral was washed several times with ozone saturated high values suggest that increasing the dissolved oxygen
water; and the direct pretreatment, where the ozone will favor the recovery of precious metals.
was added directly to the mineral pulp. In the indirect Since precious metals must be oxidized to form solu-
pretreatment, 2.5 L of distilled water were saturated ble cyanide complexes, the dissolution rate of gold and
with ozone by bubbling 3 L/min of an oxygen/ozone silver is directly related to the concentration of dissolved
mixture (94 g O3/Nm3) for 5 min. Once the saturation oxygen in the solution. Some tests were carried out in
was achieved, the water was transferred to the reactor order to determine the effect of bubbling oxygen and
containing 300 g of mineral. The slurry was stirred for oxygen/ozone on to the mineral slurry before cyanida-
1 min at 800 rpm, the solids decanted and the solution tion. A 6 h standard cyanidation was performed for
drained off for chemical analysis. Two more contacts mineral sample A. Two pretreatments were performed
were carried out with the same procedure and, after consisting in bubbling oxygen or oxygen/ozone for
draining the solution, the solid content of the remaining 15 min to the mineral pulp. Table 2 shows the gold
slurry was adjusted by adding distilled water and a stan- and silver recoveries for mineral sample A under the fol-
dard cyanidation process was performed: 0.1% sodium lowing conditions: (a) standard cyanidation (2.5 L
cyanide, 25% w/w solids and pH 11 adjusted with lime. water, 0.10% NaCN, 25% ww solids, pH of 11 and
For the direct pretreatment, 300 g of mineral sample 6 h), (b) feeding 3 L/min oxygen for 15 min to the min-
and 2.5 L of distilled water were placed into the reactor. eral slurry before cyanidation and (c) feeding 3 L/min
Cumulative O 2 consumed (g / ton)

100 30
Cumulative O 2 consumed (g / ton)

Sample A [O2 ]o = 25 mg / L Sample B

80 25
[O2 ]o = 7 mg / L
123 g O2 / ton / h 20
60
15
40 152 g O2 / ton / h
10
[O2 ]o = 7 mg / L
20
44 g O2 / ton / h 5

0 0
0 0.5 1 1.5 0 0.05 0.1 0.15 0.2
Time (h) Time (h)

Fig. 2. Oxygen demand of mineral samples A and B (27 °C).

 E. Elorza-Rodrı́guez et al. / Minerals Engineering 19 (2006) 56–61 59

Table 2 treatment, metals that usually consume cyanide. The

Gold and silver recoveries for sample A
Cyanidation O2-cyanidation
Ag (%) 8.9 19.2
Au (%) 70.0 70.0
(a) Six hours standard cyanidation, (b) 15 min oxygen bubbling and
6 h standard cyanidation and (c) 15 min oxygen/ozone bubbling and
6 h standard cyanidation.
ozone/oxygen (55 g O3/Nm3) for 15 min to the slurry be-
fore cyanidation.
From this table is clear that the oxygen by itself does
not increase the recoveries of the precious metals in the
same magnitude as ozone addition. In this mineral sam-
ple, silver extraction was improved by oxygen addition,
but the ozone oxidation step did give better results for
both gold and silver.
3.2. Indirect pretreatment with ozone
The samples were submitted to a pretreatment with
ozone by contacting three times the mineral with ozone
saturated water, as mentioned in methodology, and then
to a standard cyanidation. Table 3 presents the metal
recoveries for these tests. As can be seen, the indirect
ozone pretreatment of the mineral before cyanidation
did not cause any change in the recovery of gold and sil-
ver in sample A, but the cyanide consumption decreases
from 1.94 kg NaCN/ton to 1.06. This fact is due to de
dissolution of copper, zinc and iron sulphides in the pre-
metal recoveries for sample B are improved with the pre-
O3-cyanidation treatment with ozone as can be seen in Table 3 and
29.6 Fig. 3.
76.0 Even though both samples are from mining dis-
tricts located within the same volcanic belt of metal
sulfides, the mineralogy of the species is different, and
also is the oxygen demand for the samples. The oxida-
tion of the metal sulfides and the high oxygen concentra-
tion in the initial stage of cyanidation explain the
improved recoveries obtained in sample B.
3.3. Direct pretreatment with ozone
Contacting the mineral three times with ozone satu-
rated water implies intensive use of equipment and labor
work. In order to simplify the procedure, ozone was
added directly to the mineral slurry, and then, submitted
to a conventional cyanidation. At this point, one of the
mines closed and it was impossible to obtain more sam-
ple of mineral B. Direct pretreatment was performed
only to sample A.
Ozone was fed for 15 min to the mineral sample in
water distilled as mentioned in methodology, and a stan-
dard cyanidation was performed. Results are shown in
Fig. 4, where can be observed that with the ozone pre-
treatment the silver dissolution rate is increased: 6 h of
cyanidation can produce the same silver recovery that
40 h of standard cyanidation. The gold dissolution rate
appears to be less sensitive to this pretreatment. In this

Table 3
Metal recoveries and cyanide consumption for the different tests with standard cyanidation and indirect ozone pretreatment and standard
cyanidation
Time (h) Mineral sample A Mineral sample B
Standard cyanidation O3-cyanidation Standard cyanidation O3-cyanidation
Au (%) Ag (%) CN (g/t) Au (%) Ag (%) CN (g/t) Au (%) Ag (%) CN (g/t) Au (%) Ag% CN (g/t)
24 71.4 19.2 – – – – 35.1 17.8 3.9 52.9 40.0 4.57
48 71.4 35.8 1.9 71.4 34.6 1.06 52.9 26.0 6.0 88.2 78.3 6.99
72 71.4 44.1 – – – – 61.2 51.9 7.1 – – –

100 100
Au (Cyanidation) Ag (Cyanidation) A Au (Cyanidation) B
Au (O3-Cyanidation) Ag (O3-Cyanidation) Ag (Cyanidation)
Au and Ag Recovery (%)

Au and Ag Recovery (%)

80 80 Au (O3-Cyanidation)
Ag (O3-Cyanidation)

60 60

40 40

20 20

0 0
0 20 40 60 80 0 20 40 60 80
Cyanidation Time (h) Cyanidation Time (h)

Fig. 3. Gold and silver recoveries of minerals A and B when treated by standard cyanidation and indirect ozone pretreatment and cyanidation.
Pretreatment conditions: 2.5 L water, 3 L/min gas, 94 g O3/Nm3. Cyanidation conditions: 0.10% NaCN, 300 g solids, 25% w/w and pH = 11.
60 E. Elorza-Rodrı́guez et al. / Minerals Engineering 19 (2006) 56–61

100
Au (Cyanidation ) Ag (Cyan idation)
Au (O 3-Cyanidation) Ag (O3 -Cyanida tion)
Au and Ag Recovery (%)

80

60

40

20

0
0 20 40 60 80
Cyanidation Time (h)

Fig. 4. Gold and silver recoveries of mineral A when treated by direct
ozone addition and cyanidation. Pretreatment conditions: 12% solids
w/w, 15 min gas addition, 3 L/min, 50 g O3/Nm3. Cyanidation
conditions: 0.10% NaCN, 300 g solids, 25% w/w solids and pH = 11.
mineral (sample A), even with an extended cyanidation
time, the recovery of gold and silver did not exceed that
obtained with conventional cyanidation, suggesting that
in this ore the ozone can not reach the included gold and
silver.
Silver in both samples is mainly in the form of pyrar-
gyrite (Ag3SbS3). In order to study the effect of ozone on
the sulfide mineral, a highly pure sample of pyrargyrite
(550 kg Ag/t, from Zacatecas Mexico) was submitted
to the same ozone pretreatment and observed in the
Scanning Electron Microscope equipped with Energy
Dispersion X-Ray Spectrometry microanalysis probe
(EDS). Fig. 5 shows an ozonated pyrargyrite particle
and Fig. 6 the elemental analysis in (a) the oxidized
Fig. 5. Photomicrograph of pyrargyrite superficially oxidized with
ozone (12% solids w/w, 20 min ozone addition 1 L/min, 50 g O3/Nm3).
surface and (b) the non-oxidized matrix of the silver
sulfide.
This analysis is not quantitative but demonstrates
that sulfur and silver in the surface decrease due to the
ozone oxidation and suggests the dissolution of the sil-
ver and the formation of sulfate ion.
4. Conclusions
Refractory gold and silver ores require an oxidative
pretreatment in order to recover the precious metals.
The main available pretreatments are not always practi-
cal due to environmental problems or excessive costs.
Ozone pretreatment can be regarded as a promising
alternative for treating refractory ores.

Fig. 6. Chemical analysis of the pyrargyrite in (a) the ozone oxidized surface and (b) the non-oxidized centre. Scanning electron microscope with
EDS microprobe.
 E. Elorza-Rodrı́guez et al. / Minerals Engineering 19 (2006) 56–61
Ozone pretreatment was tested with two Mexican
refractory ores of pyritic matrix. In both cases, silver
was in the form of pyrargyrite and freibergite. Gold in
sample A was native, free and associated to pyrite and
quartz. In sample B, gold was native, free, associated
to pyrite and occluded in quartz and sphalerite. Both
minerals presented high oxygen demand (44 g O2/ton/h
for sample A and 152 for sample B).
In order to establish the significance of the oxygen ef-
fect in the cyanidation of the samples, a standard cyan-
idation without pretreatment was performed for mineral
sample A, and the gold and silver recoveries obtained
were compared with those obtained when oxygen and
ozone pretreatment were performed before cyanidation.
Results showed that the oxygen pretreatment in-
creases the silver recovery in sample A from 8.9% to
19.2% while the gold recovery remains constant. The
addition of ozone/oxygen mixture to the mineral slurry
before cyanidation increases the recoveries from 8.9% to
29.6% for the silver and from 70% to 76% for gold. It
can be concluded that the ozone effect in increasing
the precious metals recoveries is not due to the oxygen
added with the ozone.
For contacting the ore with the ozone gas, two meth-
ods were studied: indirect method (contacting the ore
three times with ozone saturated water) and the direct
method (direct addition of ozone to the mineral slurry).
The indirect pretreatment with ozone did not show any
significant change in gold and silver recoveries for sam-
ple A, but increases the gold recovery in cyanidation for
sample B from 53% to 88% and the silver recovery from
26% to 78%. Direct pretreatment with ozone of sample
A increased the dissolution rate of gold and silver in
cyanidation: a pretreatment of 15 min plus a cyanida-
tion of 6 h give the same metal recoveries than 40 h of
standard cyanidation. Sample B was not tested with di-
rect pretreatment.
Depending on the size and mineralogy of the gold
and silver species, a pretreatment with ozone can be con-
sidered as a promising option for treating refractory
gold and silver ores. The pretreatment with ozone does
61
not involve environmental problems (SO2 production
in roasting), high costs (processes at high temperature
or pressure), nor extended treatment time (bioleaching).
An economical evaluation is needed for each refractory
mineral.
Acknowledgements
The authors thank CONACYT and PEÑOLES for
the financial support received for this research project
and M.C. González Anaya for his technical assistance.
E. Elorza-Rodrı́guez thanks the Cosupera program of
the Guanajuato University for the financial support
through the PhD scholarship granted.
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