DTD 5

ARTICLE IN PRESS

Hydrometallurgy xx (2005) xxx – xxx

www.elsevier.com/locate/hydromet

Experimental leaching of atacamite, chrysocolla and malachite:

Relationship between copper retention and cation
exchange capacity
Sonia Helle*, Ursula Kelm
Instituto de Geologı́a Económica Aplicada, Universidad de Concepción, Casilla 160-C, Concepción, Chile
Received 30 January 2004; received in revised form 16 December 2004; accepted 5 March 2005

Abstract

Copper retention due to chemical and physical interaction with reactive gangue has been studied during sulphuric acid
leaching of atacamite, chrysocolla and malachite, using a synthetic rock (57% quartz, 42% reactive gangue and 1% ore).
Smectite- and mordenite-rich gangues represent the highest copper retention whereas the lowest is found for kaolinites and illite.
During leaching, smectites show the largest change (increase) in volume; no volume change occurred for kaolinites, zeolite and
illite. Kaolinite-rich gangue forms barriers due to de-lamination demonstrated by acid accumulation at the top of the columns.
The X-ray diffraction patterns of smectite, illite and kaolinite in the residues demonstrate the diminution or complete loss of
basal crystal faces accompanied by the neo-formation of alunogen, meta-alunogen, coquimbite and goldichite. These new
phases contribute to a temporary reduction of permeability. For all the synthetic rocks assayed, the copper retention is directly
proportional to cation exchange capacity (CEC) of the starting materials, and corroborated by the CEC of Cu of the residues
determined without water elution prior to analysis.
This test used represents a predictive tool to evaluate the potential Cu retention and gangues with elevated CEC.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Acid leaching; Copper ores; Reactive gangue

1. Introduction H2Si2O5(OH)4d nH2O, Bideaux and Nichols, 1995)

Oxidised copper ores, consisting mainly of silicates
(chrysocolla, a mineraloid with cited formula (Cu,Al)2
* Corresponding author. Tel.: +56 41 204867.
E-mail addresses: shelle@udec.cl (S. Helle), ukelm@udec.cl
(U. Kelm).
0304-386X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2005.03.005
carbonates (malachite, Cu2(CO3)(OH)2) and chlorates
(atacamite, Cu2Cl(OH)3), are generally treated by
leaching of the crushed ore with sulphuric acid to
produce impure solutions of copper sulphate. Copper
recovery is a function of the whole rock mineralogy,
particle size distribution, porosity and permeability
amongst others. Solvent extraction of copper takes
place from a solution with complex ionic charge due

HYDROM-02405; No of Pages 7
 ARTICLE IN PRESS
2 S. Helle, U. Kelm / Hydrometallurgy xx (2005) xxx–xxx
to the element input not only from ore minerals but
also from the acid dissolution of gangue phases. Sol-
vent extraction of copper by organic solutions thus
takes place in a solution with a complex ionic charge,
as a result of the mineralogical and chemical changes
that occur in almost all the minerals submitted to the
leaching process.
The extraction of copper from low grade oxide
ores is considered to be an economical operation if
the efficiency of the extractive operations borders
95%. This process is continuously being developed
to improve the removal of copper from a wide
variety of ores; in many cases the ore is a micro-
scopically inseparable mixture of reactive gangue
minerals such as smectites (Mu+v+z+[(Alx Fey Mgz )2.00
(Si4.00 (u+v)Fev Alu )O10(OH)2], Elzeo and Murray,
1994), white micas (K2(Al, Fe)2(Mg, Fe)2(Si8)O20
(OH)4, Newman, 1987), chlorites and zeolites. It
can also be present as microcrystalline Cu phases
or copper retained already in cation exchange sites
prior to mining and processing. Gangue reactivity
produces mainly acid consumption, loss of perme-
ability, copper exchange and absorption and, finally,
copper retention in the pad. To monitor these para-
meters a wide range of studies have been developed
to predict times of acid pre-treatment, selective
chemical extraction, leachate recovery, acid con-
sumption and evolution of permeability, copper ad-
sorption and release of Si, Al, Ca, Mg and Na from
some zeolites (Bartlett, 1992; Hutchinson and Elli-
son, 1992; Fonseca et al., 1992; Zänker et al., 2002).
In recent years, many publications have addressed
acid mine drainage or the release and retention of
elements in different types of rocks, sediments and
minerals (Dinelli and Tateo, 2002; Doula et al.,
2002; White and Brantley, 1995, and literature
cited therein).
It is therefore considered important to establish an
analytical predictive link between the metallurgical
whole ore/rock approach and single phase mineralog-
ical studies, as this will permit one to observe and
understand mineralogical changes in residues and
copper retention by potentially reactive gangue phases
under acid conditions in a short-term experimental
setup.
This experimental study intends to semi-quantify
the interaction between atacamite, malachite and
chrysocolla with potentially reactive gangue using a
non-traditional chemical and mineralogical character-
ization in a short and severe acid leaching test. These
ore minerals, atacamite, chrysocolla and malachite,
were selected for their importance for Chilean copper
deposits and availability of pure materials.
The criteria for selection of the gangue were the
reactivity due to charge deficiencies per formula unit,
expandability, the cation adsorption and exchange
capacities (CEC), the possibility of physical barrier
formation, relevance for Chilean exotic copper-ore
deposits, and on an experimental level, purity, homo-
geneity and availability of the materials.
2. Methods
2.1. Experimental setup
The short-term leach tests were carried out with a
strong solution of sulphuric acid (265 g/L) at ambient
temperature (18 to 21 8C) in small columns (Fig. 1)
using a synthetic rock composed of 57% quartz, 1%
ore phase, and 42% reactive gangue. Synthetic rock
compositions used in this study represent extreme
scenarios to demonstrate the interaction of ore and
phyllosilicate or zeolite gangue without the need for
concentrations steps, as would be required for the
routine X-ray diffraction (XRD) control for phyllosi-
licates. A blank series of 58% quartz and 42% reac-
tive gangue acted as non-mineralized control for each
gangue type. A pure quartz sample (99% quartz and
1% ore mineral) was used to monitor complete ore
dissolution during leaching and the contribution of Si
from quartz to the leachate.
The mixtures were compressed to the consistency
of a semi-consolidated sediment at 40 ton/cm2.
Quartz was added as binertQ as permeabilizer to
avoid the formation of instant hydraulic barriers for
smectite type gangues. Details of the preparation of
artificial mineralized rock and leaching setup have
been published elsewhere (Kelm and Helle, 2003).
The high sulphuric acid concentration of 265 g/L
permits one to obtain information about the removal
of ions from the gangue silicates within a very short
period of time compared to bottle leachings using
mine acid concentrations. Ore minerals were obtained
from Chuquicamata Mine, CODELCO NORTE
(chrysocolla), Aldrich chemicals (malachite) and
 ARTICLE IN PRESS

S. Helle, U. Kelm / Hydrometallurgy xx (2005) xxx–xxx 3

SAZ SWY KGA-1 KGA-2 BL

Fig. 1. Experimental laboratory columns. Smectites (SAZ and SWY) kaolinites (KGA-1 and KGA-2) and BL (blank). Line on glass marks
original filling level of columns. Note the volume increase for SAZ and SWY smectite.

purpose synthesized (atacamite/para-atacamite). A
summary of the mineralogy, cation exchange capac-
ity (CEC) and specific surface area (BET) of the
reactive gangue phases can be found in Table 1.
Further details of provenance and their character-
ization can be found in Kelm and Helle (2003),
Chipera and Bish (2001), and Clay Mineral Society
of America Webpage (2004). At ambient tempera-
ture, all materials have a high specific external
surface area (BET after degassing at 70 8C) for
b 200 Tyler mesh size, and their CEC range from
0.6 to 132 cmol/kg. This provides ideal conditions
to study the copper retention with respect to cation
exchange capacity.
The mixtures (40 g of ore and gangue) were placed
in columns (4.4 cm diameter, 6.5 cm height) and the
leaching process was carried out with 50 mL H2SO4
(265 g/L). After approximately 4 h, an aliquot of 20
mL of the leachate was taken for the analyses. Full
details on the experimental procedure are given in
Kelm and Helle (2003).
2.2. Determination of cation exchange capacity, cop-
per contents and mineralogical analyses
Cation exchange capacities (CEC) of the starting
materials and residues were carried out by ammonium
acetate (Ca, Mg, Na and K) and di-ethylene-triamino

Table 1
Reactive gangue, mineralogy (XRD), cation exchange capacity (CEC) and specific surface area (BET) of the b200 Tyler mesh fraction
Reactive gangue Mineralogy by XRD CEC BET
(cmol/kg) (m2/g)
MORD mordenite (Chile) N95% mordenite, trace clinoptilolite 132 126
SAZ-1 montmorillonite (CMS Source clay) 98% smectite, trace quartz 118 147
SWY-1 montmorillonite (CMS Source clay) 75% smectites, 8% quartz, 17% feldspar and others 90 117
NAU-1 nontronite (CMS Special Clay) N80% smectite, 10–15% illite and quartz 71 97
BENT R bentonite rock (Chile) N90% smectite, trace Fe-oxides, vitreous matter 62 180
Imt-1 illite (CMS Special Clay) illite, b10% quartz and chlorite 18 97
KGA-1 kaolin (CMS Source clay) 96% kaolinite, 3% anatase, 1% quartz 12 141
KGA-2 kaolin (CMS Source clay) 96% kaolinite, 3% anatase, 1% other traces 0.6 180
CMS: Clay Mineral Society of America.
 ARTICLE IN PRESS
4 S. Helle, U. Kelm / Hydrometallurgy xx (2005) xxx–xxx
pentaacetic acid (Cu and Zn) exchanges and analyzed
by AAS (Hitachi Z-8100). Total and soluble copper
were determined by AAS following attacks by
HNO3 + H2SO4 + HCl (hot) and H2SO4 (20% cold),
respectively. The presence of crystalline phases was
detected by X-ray diffraction (XRD, Rigaku Dmax-
C) using Ni-filtered Cu radiation at scanning speeds
of 1 8/min.
3. Results and discussion
During the leaching experiments smectite-rich
gangue increased up to 75% in volume with for-
mation of air–then acid–filled cavities due to the
rapid sealing effect of overlying smectite in the
column. No volume change occurred for illite
and mordenite (Ca,Na2,K2)Al2Si10O24d 7(H2O); for
kaolinite (Al2Si2O5(OH)4) mixtures acid puddles
formed on top of the columns. Fluid recovery
was b 60% for expandable phases and reached up
to 80% for non-expandable mixtures.
Mineralogical changes in the residues were most no-
torious for the smectite group gangues. Nontronite ((M0.97
(Si7,57Al0.01Fe0.42)[Al0.52Fe3.32Mg0.7O20](OH)4), pre-
liminary formula CMS webpage, 2004), SAZ montmo-
rillonite((Ca 0.39Na0.36K0.02)(Al2.71Mg1.11Fe0.12Mn0.01
Ti0.03)[Si8.00O20](OH4)) and the Chilean Bentonite
lost most of their basal 001 reflections on the
XRD charts (Fig. 2). Only the SWY montmorillonite
9000
counts/second
0
3 9
Fig. 2. XRD patterns of heads (dark line) and residues (pale line) of smectites BENT-R, NAU, SWY and SAZ. Quartz (Q), coquimbite (coq),
alunogen (alun) and smectites (arrows). Broad arrow marks basal (001) smectite reflections.
( ( Ca 0.12 Na 0.32 K0.05 )[ Al 3.01 Fe 3+
0.41Mn 0.1Mg 0.54Ti 0.2 ]
[Si7.98Al0.02O20](OH)4)) appeared to withstand short-
term sulphuric acid leaching. This is considered to be
due to the comparatively lower interlayer charge (CMS
Webpage, 2004) for this montmorillonite. Reduction of
basal reflections also has been found for illite and
kaolinite gangues. Mordenite XRD traces did not
change after leaching, although major element analyses
of head and residues show a dealuminization (Kelm
and Helle, 2003). Amongst natural zeolites, mordenite
has one of the highest Si/Al ratios and thus improved
acid resistance (Tschernich, 1992). Neoformed species
are alunogen (Al2(SO4)3d 17H2O), meta-alunogen
(Al2(SO4)3d 12H2O); for nontronite gangues coquim-
bite (Fe23+(SO4)3d 9(H2O)) formed and traces of gold-
ichite (K,Fe3+(SO4)2d 4(H2O)) were detected in the
3+ 2+
case of illite (Mg0.09Ca0.06K1.37 )[ Al2.69 Fe0.76 Fe0.06
Mg0.43Ti0.06][Si6.77Al11.23O20](OH)4, CMS website,
2004). The formation of the latter two minerals is due
to the increased availability of Fe and K, respectively,
in the gangues. The described mineralogical changes of
each gangue type were repeated for the three mineral-
ized and the blank series.
Total copper in the head and residue of the
mineralized series shows similar efficiency of the
leaching process for the three mineral species inter-
acting with all the gangues studied (Fig. 3). This is
not surprising, as all three ore phases are easily acid
soluble and not occluded in this experimental de-
sign. The highest copper retention is present in three
15 21 27
° 2 theta
 ARTICLE IN PRESS

S. Helle, U. Kelm / Hydrometallurgy xx (2005) xxx–xxx 5

%Cu(t) A Residue %Cu(t) A Head %Cu(t) C Residue

%Cu(t) C Head %Cu(t) M Residue %Cu(t) M Head

0,600

0,500

0,400
% total Cu

0,300

0,200

0,100

0,000

KGA-1 Kaolinite

KGA-2 Kaolinite
SAZ Smectite

SWY Smectite

BENT Rock

NAU Nontronite

IMT Illite

MORD

Quartz
Fig. 3. Total copper in the head and residues of malachite (M), atacamite (A) and chysocolla (C) series.

smectite group gangues (SAZ, NAU, BENT R) and the complete dissolution of the ore phases during
mordenite. Lowest copper retention is found indis- the short-term leaching experiments.
tinctly for the high and low crystalline kaolinites The preferential copper retention in most of the
(KGA-1, KGA-2) and illite (Fig. 4). The 99% smectite gangues could be due to: (1) adsorption of
quartz and 1% copper mineral blank demonstrates Cu on montmorillonite and nontronite surface sites and

Atacamite Series Chrysocolla Series Malachite Series

45

40

35
Cu retention (%)

30

25

20

15

10

0
KGA-1 Kaolinite

KGA-2 Kaolinite
SAZ Smectite

SWY Smectite

BENT Rock

NAU Nontronite

IMT Illite

MORD

Quartz

Fig. 4. Copper retention (%) in the residues of malachite, atacamite and chysocolla series.
 ARTICLE IN PRESS
6 S. Helle, U. Kelm / Hydrometallurgy xx (2005) xxx–xxx
BL Series
120
100
80
cmol/kg
60
40
20
0
SAZ Smectite
Smectite R
BENT Rock R
SWY
R
Fig. 5. Total CEC of the residues of blank (BL), malachite (M), atacamite (A) and chysocolla (C) series. CEC head calculated from CEC of
starting materials.
in the remaining cation exchange positions, (2) reten-
tion of Cu as suspended gel or in water within the
residues. This second option could be favored if abun-
dant cations are made available by the silicate gangue,
as happened in three of the smectite species. The more
acid stable SWY montmorillonite retains comparative-
ly less copper, but at the same time maintains its crystal
structure, suggesting as for the acid resistant mordenite,
Cu retention in charge compensation positions.
These phenomena repeat for all three ores studied,
irrespective of the total Cu of 0.5% for atacamite and
malachite and 0.25% for chrysocolla (Fig. 3).
There is a good correlation between the total ex-
change capacity of the residues (considering remnant
cation proportion) (Fig. 5) and the total CEC of the
starting materials (Table 1). Finally, comparing Figs. 4
and 5 it is possible to say that the CEC is directly related
to copper retention of the ores and reactive gangues
studied.
Therefore this study shows that the parameter of
cation exchange capacity, when applied as a straight-
forward interchange procedure without water elution of
the residue to wash out remaining solution or gels, does
not permit one to pinpoint the location of the retained
copper; however, it reflects well the overall capability
of a gangue to retain copper in the residue, the principal
concern in mineral processing. A single step exchange
is easy to implement in many mining laboratories on
site. Applications of CEC to natural mineralized ore
can be a very efficient predictive tool for potential
copper retention.
M-Series A Series C Series CEC Head
Nontronite R
Kaolinite R
Kaolinite R
IMT Illite R
MORD R
Quartz R
KGA-1
KGA-2
NAU
4. Conclusions
The highest copper retention is found for smectites
and mordenite gangue; the lowest is observed for kao-
linite, illite and quartz. The use of CEC without prior
elution of the residue with water provides a measure for
the overall Cu retention which may either be due to
cation exchange capacity, surface adsorption or, in the
case of an expandable phase, retention of solution or gel
in the residue. Together with the XRD analysis focused
on the possible presence of clay mineral phases, the
CEC represents a powerful predictive tool for Cu re-
tention by clay mineral and zeolite phases. Both meth-
ods are easy to implement on a production site. As a
complement to traditional mineralogical characteriza-
tion, the combination of CEC and XRD analyses incor-
porates a robust knowledge of gangue–solution
interaction during leaching and the potential loss of
copper and its retention in minerals with elevated CEC.
Acknowledgements
This research was made possible by the FONDE-
CYT Grant 1010823 bThe interaction of oxide zone
copper minerals and gangue during leaching: a geo-
metallurgical and experimental perspectiveQ. Staff at
the GEA Institute is thanked for their help with the
analytical work. The helpful comments and sugges-
tions of two anonymous reviewers are very much
appreciated.
 ARTICLE IN PRESS
S. Helle, U. Kelm / Hydrometallurgy xx (2005) xxx–xxx
References
Bartlett, R.W., 1992. Solution mining. Leaching and Fluid Recovery
of Materials. Gordon and Breach Science Publishers, Philadel-
phia, USA.
Bideaux, A., Nichols, B., 1995. Handbook of Mineralogy, Part 1.
Mineral Data Publishing, Tucson, AZ. 446 pp.
Chipera, S.J., Bish, L., 2001. Baseline studies of the clay minerals
society clays: powder X-ray diffraction analyses. Clays and
Clay Minerals 49 (5), 398.
Clay Mineral Society (CMS) of America, 2004. http://www.clays.
org/sourceclays/SourceClaysData.html.
Dinelli, E., Tateo, F., 2002. Different types of fine-grained sedi-
ments associated with acid mine drainage in the Libiola Fe–Cu
mine area (Ligurian Apennines, Italy). Applied Geochemistry
17, 1081.
Doula, M., Ioannou, A., Dimirkou, A., 2002. Copper adsorption and
Si, Al, Ca, Mg and Na release from clinoptilolite. Journal of
Colloid and Interface Science 245, 237.
Elzeo, J., Murray, H.H., 1994. Bentonite. In: Carr, D.D. (Ed.),
Industrial Minerals and Rocks, 6th edition. Society for Mining,
Metallurgy, and Exploration Inc., Littleton, CO, p. 233.
Fonseca, C., Cardoso, C., Martins, E., Vairinho, M., 1992. Selective
chemical extraction of Cu from selected mineral and soil sam-
7
ples: enhancement of Cu geochemical anomalies in Southern
Portugal. Journal of Geochemical Exploration 43, 249.
Hutchinson, P.G., Ellison, R.D. (Eds.), 1992. Mine Waste Manage-
ment. Lewis Publishers, Boca Raton, USA.
Kelm, U., Helle, S., 2003. An experimental study of malachite,
atacamite and chrysocolla interaction with reactive gangue dur-
ing sulphuric acid leaching. In: Riveros, P., Dixon, D., Drei-
singer, D., Menacho (Eds.), Copper 2003, IIMCH-MET SOC
Canada, Santiago, Chile, vol. VI, p. 117.
Newman, A.C.D., 1987. Chemistry of clays and clay minerals.
Mineralogical Society Monograph, vol. 6. Longman Scientific
& Technical, Harlow, Great Britain. 480 pp.
Tschernich, R.W., 1992. Zeolites of the World. Geoscience Press
Inc., Phoenix, AZ, USA.
White, A.F., Brantley, S.L. (Eds.), 1995. Chemical weathering
rates of silicate minerals, Reviews in Mineralogy, vol. 31.
MSA, p. 583.
Zänker, H., Moll, H., Richter, W., Brendler, V., Hennig, Ch., Reich,
T., Kluge, A., Hüttig, G., 2002. The colloid chemistry of acid
rock drainage solution from an abandoned Zn–Pb–Ag mine.
Applied Geochemistry 17, 633.