Applied Clay Science 29 (2005) 187 198

www.elsevier.com/locate/clay

Acid leaching of malachite in synthetic mixtures of clay and

zeolite-rich gangue. An experimental approach to improve the
understanding of problems in heap leaching operations
Ursula Kelm*, Sonia Helle
Instituto de Geologa Economica Aplicada, Universidad de Concepcion, Casilla 160-C, Concepcion, Chile
Received 26 June 2003; received in revised form 7 September 2004; accepted 21 December 2004
Available online 25 January 2005

Abstract

Column leaching experiments with sulphuric acid have been carried out on synthetic rock aggregate, thus relating leachate
composition to one specific gangue or ore phase. Rock aggregates were prepared using quartz (57%) and short term reactive
gangue (42%, SAZ and SWY montmorillonites, KGA-1 and KGA kaolinites, NAU-Nontronite and IMT illite from the CMS
repository, and from Chile a bentonite rock, a mordenite and a laumontite-rich rock) and malachite (1%). Short leaching
experiments (approximately 4 h) and 4 weeks post-leaching repose resulted in partial dissolution of the smectite gangues and
minor dissolution of illite. Kaolinites caused temporary clogging of the columns. Mordenite proved to be relatively stable, while
laumontite with a lower Si/Al ratio dissolved. Precipitation of alunogen, meta-alunogen, coquimbite and goldichite was
observed, with the sulphate species depending on the cations released from the gangue. Cu-retention in residue reached a
maximum of 20% for smectite gangue (bentonite rock); Cu recovery was improved by water elution. Column leaching
experiments for single (short term) reactive gangues represent a realistic option to translate knowledge available from single
mineral dissolution experiments to the reality of metallurgical extraction, although strict guidelines are needed for test set up,
timing of sampling and analytical procedures.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Heap leaching; Smectite; Zeolite; Malachite; Gangue; Chile

1. Introduction amounts to 20% of Chiles refined copper production

Heap leaching followed by solvent extraction and
electro-winning (Lix-Sx-Ew) of exotic copper ore
* Corresponding author.
E-mail addresses: ukelm@udec.cl (U. Kelm)8 shelle@udec.cl
(S. Helle).
0169-1317/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2004.12.004
(Cochilco, 2001) with a rising projection for this
extraction procedure in the case of low grade copper
ore. Despite solution mining being an interdisciplinary
activity (Bartlett, 1992) which takes into account a
wide range of parameters, such as leachate and rock
chemistry, solution and air flow, void space, rock
porosity, solution loss and metal recovery technology,
188 U. Kelm, S. Helle / Applied Clay Science 29 (2005) 187198
there is still a surprising lack of understanding
concerning the interaction of potentially short term
(leach cycle) reactive gangue, ore extraction, solution
composition and neo-formation of sulphate hydrate
minerals. This is particularly marked for clays and
zeolites; these mineral groups are often mis-mapped,
overlooked or ill-preserved in thin sections and some-
times at the limit of detection for routine X-ray
diffraction (XRD) whole rock scans. As a result, bill-
definedQ problems with gangue are frequent scapegoats
for unexpected drops in copper extraction, even with
apparently well-adjusted metallurgical parameters.
Bulk chemical studies of rocks and leachates are
routinely carried out for a priori heterogeneous mine
tailings and their drainage, acid mine drainage and
heap leaching environments (e.g. Dold and Fontbote,
2001; Catalan and Li, 2000), which allow the overall
assessment of temporary acidity, fluid composition
and eventual environmental impact, but it is impos-
sible to evaluate ore-gangue interaction under con-
trolled conditions. Furthermore, the pH environment
of tailing empoundments is generally N1, while the
actual leaching process is carried out at more acid
conditions. Jambor et al. (2000) have reviewed the
formation of metal-sulphate-hydrates resulting from
sulphide oxidation; a similar focus has been taken by
evaluations of temporary acidity in tailings (Hutch-
inson and Ellison, 1992; Moore, 2000). Independent
from any mining application, phyllosilicate dissolu-
tion during weathering has been reviewed (e.g. Nagy,
1995), without pursuing further the possible precip-
itation from solution of secondary minerals other than
phyllosilicates, suggestingbased on early dissolution
experimentsthat the octahedral sheet may dissolve
more easily than the tetrahedral layer. Studies of
dissolution sites and rates at low pH (2.5) have been
carried out on chlorite (Brandt et al., 2003), hectorite
(Bosbach et al., 2000) and hectorite and nontronite
(Bickmore et al., 2001) using atomic force micro-
scopy to monitor the response to proton attack. In all
cases edge surfaces were found to be the most reactive
sites. Gomer et al. (1991) studied potential copper
retention by cation exchange in selected Clay Miner-
als Society Source Clays using shake flask tests and
found the Cu-retention to be lowest for the highest
acid concentration (pH 1).
This study intends to bridge the gap between the
metallurgical whole ore approach in heads and tailings
and the individual dissolution studies, which are
unfortunately too often ignored by the mining
industry. Column leaching of synthetic rock aggre-
gates is carried out monitoring dissolution of gangue
minerals and precipitation of new mineral phases. The
use of synthetic aggregates of well characterized
starting composition allows to establish a direct
relationship between the cation input and the leach
solution and the gangue and ore phase. This would be
impossible for a natural multiphase ore and gangue
rock. Scenarios studied are bworst caseQ with a high
proportion of potentially reactive gangue and low ore
concentrations. The analytical techniques are those
routinely used in the Chilean mining industry. Few
standardized procedures existeven within individual
mining companiesregarding leach test parameters
and the analytical routines that follow. For this study a
4-week post leaching repose of residues was applied
before proceeding with solid characterizations.
2. Selection of minerals for rock aggregates
The artificial rock aggregates (M series) consisted
of 57% quartz (N83b60 Tyler mesh), 42% reactive
gangue and 1% ore phase (both b200 Tyler mesh). A
non-mineralized blank set (BL series) was prepared
replacing the 1% malachite by quartz. Microscopic
analyses carried out on ore and gangue of Mina Sur
and its northward extension, Codelco, Chuquicamata,
Chile, served as reference for the proportions of
quartz and reactive gangue. There, copper is being
extracted since the 1920s from conglomerates
mineralized by chrysocolla, Cu-pitch and Cu-wad
in submersed and heap leaching operations. A low
mineralization of 1% ore mineral phase has been
selected, because any gangue interference in Cu-
extraction becomes attenuated at low ore grade
(b0.6% Cu), whereas it may pass unnoticed at
grades N1% Cu. In Chile the most frequently
extracted exotic copper ore phases are chrysocolla
and its black Mn-rich equivalent Cu-pitch, atacamite,
malachite and minor brochantite and antlerite
(Chaves, 2000; Munchmeyer, 1996; Fam, 1979). As
this study focuses on the potential interaction of ore
and gangue during percolation leaching, extreme rock
aggregate compositions were chosen in terms of
mineral reactivity due to charge deficiencies per
 U. Kelm, S. Helle / Applied Clay Science 29 (2005) 187198 189

Table 1
Short term reactive gangue phases used in synthetic rock aggregates, total CEC at pH 7, (pH 1.5) and BET determined on b200 mesh Tyler
fraction
Reactive Gangue Mineralogy DRX Total CEC BET
(cmol/kg) (m2/g)
SAZ-1 Montmorillonite (CMS Source Clay) 98% smectite, traces of quartza 118 (103) 147
SWY Montmorillonite (CMS Source Clay) 75% smectite, 8% quartz, 17% feldspar and othersa 90 (112) 117
NAU-1 Nontronite (CMS Speciality Clay) N80% smectite, 1015% illite and quartza 71 (73) 97
Bentonite Rock (BENT R) Chile N80% smectite, traces of Fe-oxides, vitreous matter 62 (67) 180
KGA-1 Kaolinite (CMS Source Clay) 96% kaolinite, 3% anatase, 1% other tracesa 12 (1.2) 141
KGA-2 Kaolinite (CMS Source clay) 96% kaolinite, 3% anatase, 1% other tracesa 0.6 (0.7) 180
IMT-1 Illite (CMS Speciality Clay) Illite, b10% quartz and chlorite 18 (7.1) 97
Mordenite (MORD) Chile N90% mordenite, traces of clinoptilolite, quartz, 132 (118) 126
plagioclase and smectite
Laumotite Rock (LAUM R) Chile laumontite, quartz, plagioclase, chlorite, calcite 32 (91) 118
(4.6% CO3 equivalent), epidote trace
a
Chipera and Bish (2001).

formula unit, expandability, cation exchange capacity, responsible for drops in Cu-recovery. These rather
potentially high specific surface area, as well as narrow zones are difficult to avoid in large scale
possible tendency for de-lamination. Thus preference mining operations. Vein quartz commercialized for
was given to phyllosilicate and zeolite gangue, mill cleaning has been used as short-term inert
although acid reactivity is experimentally docu- gangue. Aldrich reagent 207896 was chosen for
mented for amphiboles and pyroxenes (Brantley and malachite ore phase.
Chen, 1995) and has been inferred in mine column
tests (CODELCO Norte, personal information). It
should be taken into consideration that in particular 3. Preparation of rock aggregates and leaching
phyllosilicate rich gangue types (e.g. argillic alter- experiments
ation or advanced argillic alteration) also present
additional problems of geomechanical stability, lead- The following steps were strictly followed for the
ing to increased fines during comminution. High preparation of the artificial rock aggregates (Fig. 1).
purity and homogeneity of the material and the Quartz was crushed, rough milled (W capsules)
relevance to Chilean exotic copper deposits influ- and the N83b60 Tyler mesh size fraction was
enced the selection of gangue phases. The SAZ-1 and
SWY-2 montmorillonites, the KGA-1 and KGA-2 (all
CMS Source Clays) and the NAU-Nontronite and
IMT specials claysfrom the CMS repositorywere
chosen (Table 1). These clay minerals were comple-
mented by a bentonite rock (BENT R) and a Na
exchanged mordenite (MORD) concentrate from the
7th administrative Region, Chile, both well removed
from any copper mineralization. In addition, a
laumontitecalcite bearing meta-andesite (LAUM
R) was included. This material has been extracted
from a fracture zone within a propylitic alteration of
the Combarbala district (4th administrative region,
Chile, Kelm et al., 2001). This comparatively
impure zeolite gangue has been included, as zeolite
enriched fracture zones have been considered Fig. 1. SEM photograph of artificial rock aggregate (BENT R BL).
190 U. Kelm, S. Helle / Applied Clay Science 29 (2005) 187198
separated; all gangue phases were homogenized,
crushed and milled and the b200 Tyler mesh fraction
retained; the CMS source clays and the malachite
were received milled ready for use; respective
percentages of starting rock compositions were
weighed (Table 1), homogenized and filled into
PVC support rings and placed in a 40 tons/cm2 press;
60 g were prepared for each aggregate type. Once the
PVC rings had been removed by hand, the rock disks
were crushed by dropping them, inside a steel
container filled with steel bearing balls, five times in
a fitted tube, from a height of one meter. For kaolin
gangues one drop was enough to break the material.
Quartz blanks were not crushed due to the lack of a
binding mineral phase.
Columns (4.4 cm wide, 6.5 cm high, Fig. 2) with
a fused quartz glass bottom were filled with 40 g of
artificial rock chips (ranging from 10 to b42 Tyler
mesh size ) homogenized prior to filling . Care was
taken to obtain an even surface of the rock material
Fig. 2. Experimental set up (1A: SAZ aggregate, 2A SWY
aggregate). Note the volume increase from original filling level of
column (bar mark) and formation of cavities in column centre.
using only slow filling and gentle tapping on the
column walls to accommodate the material. A
perforated glass diffuser was placed on top of each
column to ensure an even distribution of the acid
during leaching. Leaching was carried out with 50
ml 15% H2SO4 pro analisi. Column and leachate
surfaces were protected from evaporation by covers
of parafilm. Initially 10 ml of acid were added to
inundate the diffuser; the remainder was added very
slowly during 1 h. A visual record was kept of
volume changes, clogging, liquid recovery etc.
Aliquots of 20 ml were taken from recovered
solutions for analyses, once free dripping stopped
for all samples. This happened after 4 h, except for
the laumontite rock, in which case samples were
collected after 10 days.
4. Chemical and mineralogical analyses
Starting materials and residues were characterized
for major elements by X-ray fluorescence spectrom-
etry (XRF). Leachates were analyzed by ICP-MS
and ICP-OES. All ICP work and XRF analyses of
residues was contracted out to Actlabs, Canada. XRF
major element analyses of the starting mixtures were
carried out at Concepcion University using a Rigaku
3700 equipment. The cation exchange capacities
(CEC) of the starting materials and residues were
determined using ammonium acetate at pH 7. In
addition, cation exchange with potassium chloride
for the starting materials was carried out at pH 1.5.
Di-ethylene-triamino penta acetic acid exchange was
used to determine CEC of Cu and Zn. Total and
soluble copper were determined by atomic absorp-
tion spectroscopy (AAS) following dissolution by
HNO3+H2SO4+HCl (hot) and H2SO4 (20% cold),
respectively. All AAS determinations were obtained
on a Hitachi 8100 model. The apparent specific
surface area (BET, Table 1) of the starting materials
was determined by nitrogen adsorption at 21 8C after
degassing the samples for 12 h at 70 8C. The
mineralogy of the starting aggregates and residues
was analyzed by XRD (Rigaku Dmax-C) using Ni-
filtered CuKa radiation and the following conditions:
40 kV, 20 mA, 18 2h/min continuous scan speed. A
JEOL 5300 scanning electron microscope was used
to visualize aggregate textures.
 U. Kelm, S. Helle / Applied Clay Science 29 (2005) 187198 191

5. Results and discussion ways formed in the columns, concomitant with an

enhanced rate of leachate recovery. A characteristic
5.1. Observations during leaching feature of the KGA-1 and KGA-2 kaolinite gangues is
the accumulation of acid on top of the column due to
Similar phenomena were observed during leaching the formation of a temporary physical barrier caused
for the M and BL series. Smectite gangues (SAZ, by the de-lamination of kaolinite.
SWY, NAU, BENT R) increased their volume up to For all samples, except LAUM R, percolation of
75% upon saturation with acid solution. For similar leachate ceased after approximately 4 h, when aliquots
gangue types maximum volume differences of 20% for leachate analyses were taken. The LAUM R-BL
were observed, which must be attributed to a variable sample only permitted recovery of 10 ml after 10
packing density of the rock chips. Visible porosity days, whereas 20 ml were collected for the mineral-
between chips was lost for expandable and non- ized counter-samples. For both LAUM R samples no
expandable gangue once the columns saturated with leachate was recovered for the first 7 days.
acid. This is due to the semi-consolidated consistency
of the aggregates. Drainage of the leachate occurred 5.2. Cation exchange capacity, total copper content
by fractures opening in the aggregates. Upon acid and specific surface area
saturation, all smectite gangues developed first air and
later acid-filled cavities in the central part of the The cation exchange capacity (CEC) was deter-
column (Fig. 2). This air and liquid entrapment is due mined for all starting materials (Table 1) at pH 7.
to the rapid top and bottom sealing capacity of this Despite repeated analyses no systematic decrease in
gangue type. Cavities disappeared once fluid path- CEC was observed for the acid pH as reported by

250

200

150

cmol/kg

100

Calc CEC
50 Total CEC
Zn
Cu
K
0
Na
Saz-Smectite BL
Swy-Smectite BL
Nau Nontronite BL
Bentonite R-BL

Mg
Kga-1 Kaolin-BL
KGA-2 Kaolin-BL
Imt-Illite-BL
Mordenite BL
Laumontite R
Quartz-BL

Saz-Smectite M

Ca
Swy Smectite M
Nau Nontronite M
Bentonite R M
Kga-1 Kaolin M
Kga-2 Kaolin M
Imt Illite-M
Mordenite M
Laumontite R M
Quartz M

Fig. 3. CEC of BL and M Series. Calculated CEC is based on proportional CEC of starting materials (CEC for quartz is 0.26 cmol/kg).
192 U. Kelm, S. Helle / Applied Clay Science 29 (2005) 187198

0.6
Gomer et al. (1991). In order to best adjust analytical
proceedings to the reality of those practiced in mining 0.5
operations, CEC was determined in the first place
0.4
without prior elution of samples (Fig. 3), determining

% Cu
the exchangeable cations plus any dissolved, adsorbed 0.3
or entrapped in gels at pH 7. For LAUM-R the
0.2
increase in Ca-CEC at pH 1.5 is due the decom-
position of calcite (Table 1). Cu retention monitored 0.1
by CEC in residues corresponds to up to 20% of the
0
total CEC. However, eluting residues with distilled SAZ SWY NAU BENT R KGA-1 KGA-2 IMT MORD LAUM
water releases an important proportion of the cations M-Residue M-Head
retained in the samples (Fig. 4). This contribution of
Fig. 5. Total Cu (M-Series) for artificial rock aggregates with
residual cations to the CEC measurement can also be
reactive gangue and residues.
demonstrated when comparing the total CEC of the
residue to the calculated CEC based on the starting copper since it is present in easy leached malachite
materials (Fig. 3). and copper is completely released into the aggregate.
One percent malachite mineralization in the M Best copper recovery (Fig. 5) was achieved for
series corresponds to a total copper content of 0.5% kaolinite and illite gangues, recovery decreased in
(Fig. 5); the 0.4% determined for LAUM R gangue gangue types with high cation exchange capacity and
may be due to a primary mixing problem. The clear mineral dissolution (see below). The maximum
concentration of total copper is equal to soluble copper retained in residues (0.2%) is observed in

70

60

50

40
cmol/kg
30

20

10 eluted Mg
Mg
0 eluted Cu
Cu
SAZ-M
SWY-M
NAU-M
BENT-M
KGA-1-M
KGA-2-M

eluted Na
IMT-M
MORD-M
LAUM R-M
QUARTZ-M

Na
SAZ-BL
SWY-BL
NAU-BL
BENT-BL
KGA-1-BL
KGA-2-BL
IMT-BL
MORD-BL
LAUM R-BL
QUARTZ-BL

Fig. 4. CEC and additional cation recovery for Na, Mg and Cu (cmol/kg) by water rinsing.
 U. Kelm, S. Helle / Applied Clay Science 29 (2005) 187198 193

sample BENT R, where remainders of vitreous particular for material received milled (e.g. kaolinites)
material and iron oxides (XRD amorphous or below and account for the similarity in BET surface areas of
limit of detection) are present. expandable and non-expandable gangues.
The specific surface area of all gangues (Table 1)
varies between 97 and 180 m2/g; for malachite ore 5.3. Leachate and residue composition
165 m2/g were measured. Brantley and Chen (1995)
report 1020% errors associated with BET determi- Except for the ore-linked Cu and Pb (see below)
nations on duplicate samples. This difference may no systematic variation between M and BL series has
increase when different degassing or heating routines been observed for leachate and residue compositions
are considered. The specific surface areas of minerals (Figs. 6 and 7). Sulphur levels in the leachate
with external and internal surface areas measured for fluctuate between 12888 (LAUM R-M) and 15609
this study (smectites, zeolites) are comparable with (SWY-BL) mg/L. The lower S-concentration of
minerals having only external surfaces. This is due to sample LAUM-R BL is attributed to the precipitation
the fact that samples were not degassed at high of alunogen/meta-alunogen in the rock aggregate.
temperatures thus analyzing preferentially external This is corroborated by the lower Al-concentration of
surfaces. Furthermore, it should be taken into consid- LAUM R-BL leachate compared to LAUM-R-M and
eration that the b200 Tyler mesh fraction may the 7 days stagnation until leachate dripping com-
comprise a wide range of grain size distributions in menced. The concentration of Si in the leachate

16000.0

14000.0

12000.0

10000.0

mg/L 8000.0

S
6000.0 P
Mn
4000.0 Mg
Na
2000.0 Ca
K
0.0 Fe
Saz- Smectite-BL
Saz-Smectite-M

Al
Swy-Smectite-BL
Swy-Smectite-M
Nau-Nontronite-BL
Nau-Nontronite-M
BentoniteR-BL
BentoniteR-M
Kga-1 Kaolin-BL
Kga-1 Kaolin-M
Kga-2 Kaolin-BL

Si
Kga-2 Kaolin-M
Imt-Illite-BL
Imt-Illite-M
Mordenite-BL
Mordenite-M
LaumontiteR-BL
LaumontiteR-M
Quartz-BL
Quartz-M

Fig. 6. Major element composition of leachates, M and BL series.

194 U. Kelm, S. Helle / Applied Clay Science 29 (2005) 187198

Fig. 7. Major element composition of starting aggregates (heads) and residues exemplified for BL series. A table of head and residue
compositions can be obtained from the authors.

reflects the dissolution of the respective gangue
phases. Highest dissolution is observed for LAUM
R gangues due to the dissolution of laumontite and
chlorite phases (Fig. 8). Dissolution rate is also high
for IMT, NAU and BENT R gangues as is indicated
by the reduction of XRD intensity of these minerals
on the XRD charts (Fig. 8). The SAZ and SWY
smectites (Fig. 2) display a slightly higher dissolu-
tion rate (4758 mg/L) than kaolinite (3035 mg/L).
No compositional difference is observed, probably

20000
AB,
AN
A A, M A
LAUM R

M M
MORD

IMT
A
CPS

KGA-2
A, MA
KGA-1
A
BENT R

C NAU
C
SWY
A
SAZ
0
3 13 23 33 43 53 63
2 theta

Fig. 8. Comparative head-residue XRD charts for M-series gangues. Diffractograms of different gangue types are offset by 2000 counts per
second (CPS). For reasons of scale only some key features are marked on graph. Black: head, Grey: residue. A: Alunogen, C: Coquimbite, AB;
Plagioclase (albite), AN: Anhydrite, MA: Meta-alunogen.
 U. Kelm, S. Helle / Applied Clay Science 29 (2005) 187198 195

due to the short duration of the leaching experiment. substitution of Pb in the carbonate lattice; but no
The presence of Na in the leachates reflects the discrete cerussite was detected by XRD.
composition of the exchangeable sites: gangues with Although a direct comparison of ICP-OES results
SWY-smectite and mordenite yield abundant Na, (leachates) and XRF results (residues and starting
while leachates from SAZ and NAU smectites are materials) is not plausible due to the different
poor in Na. analytical approaches, the observations made for
Similarly the abundance of K, Ca and Mg in the the leachates are reflected in the changes of major
leachate is a function of their availability in exchange element composition of the head-residue pairs for
sites. The concentration of MnO in the starting each gangue. Depletions of 1022% are found for
aggregates is close to the detection limit of XRF in SiO2 (Fig. 7) followed by Al2O3 and Fe2O3, both
the starting aggregates and has not been assigned to lowered by 15% in the residues relative to the
any XRD detectable mineral phases. The ease of heads. BENT R, KGA-1, KGA-2 and LAUM R
release of Mn indicates that it is possibly adsorbed on gangues show an increased Na2O content in the
hydroxides which are easily dissolved an acid medium residue samples, never exceeding 0.27% for the
(Taylor, 1987). Al in leachates is released from the phyllosilicates (SWY) and 0.81% for LAUM-R. This
dissolution of the octahedral sheet of phyllosilicates difference is considered to be due to the use of two
(Nagy, 1995 and literature cited therein); the solubility different XRF equipments and slightly divergent
of this element may be increased by presence of calibrations at very low Na2O levels (residues were
vitreous or amorphous matter (BENT R). In the case analyzed in Canada and heads in Chile).
of mordenite de-aluminization is observed, but with- Ti has been monitored due to its abundance in
out noticeable destruction of the crystal lattice. This is several gangue phases (Mermut and Faz Cano, 2001).
not the case for laumontite due to the lower Si content The concentration of Ti in leachates is not in
of the crystal framework (Tschernich, 1992). Leaching accordance with the presence of up to 1.11% for the
of Fe is highest for NAU, BENT-R and LAUM-R kaolinite gangues. Although the use of different
gangues, reflecting the presence of Fe in the octahe- methods of analyses (XRF for solids, ICP-OES for
dral sheet and the presence of Fe-oxides (not detected leachates) is unsuitable for direct comparison, the
by XRD, but implied by colour of the material) for the concentration of Ti detected in leachates is low for
latter two gangue types. Pb concentrations in the kaolinite gangue due to the low acid solubility of
leachates for the M series were found to be anatase (Taylor, 1987). Ti can be more successfully
consistently higher than for the BL series (Fig. 9). It solubilized when only adsorbed or present in remain-
is possible that the malachite ore contains minor ing vitreous (amorphous) matter (BENT R).

10000000
9000000
8000000
7000000
6000000
ug/L 5000000
4000000 Cu
3000000
Pb
2000000
1000000
0
SAZ-M
SWY-M
NAU-M
BENT-M
KGA-1-M
KGA-2-M
IMT-M
LAUM R-M
MORD-M
QUARTZ-M
SAZ-BL
SWY-BL
NAU-BL
BENT-BL
KGA-1-BL
KGA-2-BL
IMT-BL
MORD-BL
LAUM R-BL
QUARTZ-BL

Fig. 9. Cu and Pb (Ag/L) in leachates.

196 U. Kelm, S. Helle / Applied Clay Science 29 (2005) 187198
5.4. Mineralogical changes
Column residues were analyzed by XRD 4 weeks
after leaching, a period within the blife cycleQ of an ore
loading for many short term heap leaching operations;
changes are depicted in Fig. 8. The reduction in
intensity of the basal reflection of smectites (air dried
and ethylene glycol saturated) is most marked for the
SAZ, BENT R and NAU samples in which smectite
almost disappears. These samples also retain most
copper (Fig. 5), suggesting mineral dissolution and
subsequent formation of gels a possible mechanism to
impede a more complete leaching of copper. In IMT
samples the 001 illite reflection has a very reduced
intensity in the residue, but no shift in the basal peak
position to lower 2 theta angles was observed. The
intensities of the basal reflections of the KGA-1 highly
crystalline kaolinite (Moll, 2001) are clearly reduced in
the residues, this effect is less obvious for the low
crystallinity KGA-2 kaolinite, suggesting an important
contribution of the basal gibbsite surfaces to mineral
dissolution (Nagy, 1995) for the highly crystalline
kaolinite. Neoformed mineral phases are sulphate salts,
such as alunogen and metalunogen, present in SAZ,
SWY, KGA-1 and KGA-2 gangues. Coquimbite and
traces of goldichite appear in NAU and IMT gangues
and reflect the mobilization of Fe and K from
nontronite and illite. The above mentioned sulphate
salts are abundant metastable phases in tailings
(Jambor et al., 2000). No Cu salts have been identified
in samples retaining Cu in the residues, possibly due to
the low grade of original Cu-mineralization, or any
secondary Cu species formed will remain below the
limit of detection of XRD. For laumontite leachates
(collected after 10 days), a precipitation of alunogen/
meta-alunogen in the leachate was observed. This
gangue type also has the highest Al concentrations in
the leachates (Fig. 6). Considering that most heaps are
leached for weeks or even months, this precipitation
indicates the potential for rapid temporary self-clog-
ging within heaps. This phenomenon has been
observed by Meruane (1999).
5.5. Implications of the experimental results for heap
leaching operations
The preceding results permit to draw initial parallels
to observations in heap leaching operations. Mina Sur,
CODELCO Norte, Chile, is taken as a reference for
several of the outlined problems. The presence of
gangue with advanced argillic alteration which com-
bines kaolinite and smectite has a high potential for
low copper extraction, (1) due to the retention of Cu in
exchange or surface absorption sites and (2) potential
physical clogging of fluid pathways. This combined
problem may be easily overlooked as smectite abun-
dance is often below the detection limit of routine (fast)
XRD scans. At Mina Sur, copper recovery may drop to
40% when kaolinite (b15%) and smectite (b5%)
combine in gangue, whereas good extractions range
from 70% to N90%.
The precipitation of alunogen and other sulphates
with trivalent cations within 4 weeks of leaching
indicates the potential for permeability reduction in
the heaps; this may be enhanced in superficial parts
for arid climates (Dold and Fontbote, 2001). Sul-
phate precipitation can be important, even in absence
of sulphides (Meruane, 1999). Fe and Al in the
leachate depend directly on their presence in the
short term leachable phases; here single mineral
dissolution of weathering studies predict their avail-
ability, although most of that information has been
obtained at pHN2.
The presence of even small proportions of zeolitic
gangue combined with calcite (often associated with
fracture zones of propylitic alteration) can lead to a
noticeable drop in copper recovery by additional acid
consumption, sulphate precipitation and Cu-exchange.
Often these fracture zones cannot be avoided during
mining.
6. Conclusions
Leaching of synthetic rock aggregates with sul-
phuric acid (15%) demonstrates the effect of single
phase, short-term (leach cycle) reactive gangue on
copper recovery. Leaching tests using laboratory
parameters and analytical methods similar to those
in the exotic copper mining industry represent a valid
option to translate/apply existing information on
single mineral dissolution to metallurgical whole rock
approaches. However, the elaboration of strict guide-
lines for experimental routine in particular repose
times and timing of sampling are required. Smectite
rich gangues (montmorillonites, nontronite, bentonite
 U. Kelm, S. Helle / Applied Clay Science 29 (2005) 187198
rock) are partially dissolved, and in the case of
nontronite CEC is reduced. Kaolinite rich gangues
are responsible for clogging of the leaching columns
due to de-lamination. Mordenite was acid resistant,
while more Al-rich dissolved. Zeolites combined
with carbonate constitute a frequent fracture-zone
mineral assemblage which may result in increased
acid consumption and low leachate recovery. Copper
retention in residue is highest for smectite and
zeolite phases, but the copper can be partially
recovered by water elution. Gangue dissolution is
directly reflected in leachate composition and inver-
sely in residue composition. Within 4 weeks of
leaching, precipitation of Al, Fe (and K) sulphate
hydrates occurred, demonstrating their potential for
reduction of permeability.
Acknowledgements
The financial support of CONICYT (Chilean
Science Foundation, Fondecyt project 1010823) is
acknowledged. The authors thank Mr Andres
Reghezza, Director of Extractive Metallurgy,
CODELCO Norte, Chuquicamata, and his staff for
comments and suggestions on test routines and
discussion of the problems observed in leaching
operations. The enthusiastic help of laboratory staff
at the GEA Institute is appreciated. The authors also
wish to thank Dr George Christidis and an anonymous
reviewer for their helpful comments.
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