Mineralium Deposita (2005)
DOI 10.1007/s00126-005-0017-7
A RT I C L E
Adrian J. Hartley Clive M. Rice
Controls on supergene enrichment of porphyry copper deposits in the
Central Andes: A review and discussion
Received: 28 February 2004 / Accepted: 27 July 2005

Springer-Verlag 2005
Abstract The Central Andes host some of the worlds
largest porphyry copper deposits. The economic viabil-
ity of these deposits is dependent on the size and quality
of their supergene enrichment blanket. Published models
that have strongly inuenced exploration policy suggest
that supergene enrichment ceased at 14 Ma due to an
increase in aridity. Here we discuss these models using
published geochronological, geomorphological and
geological data. Geochronological data indicate that
supergene oxidation and enrichment has been active
between 17 and 27S across the forearc of northern Chile
and southern Peru from 44 to 6 Ma, and on the Bolivian
Altiplano and Eastern Cordillera of Argentina from
11 Ma to present. There is evidence for cessation at 20,
14 and 6 Ma. However, a major problem is that as more
geochronological data become available the age ranges
and periods of enrichment increase. This suggests that
the full spectrum of enrichment ages may not have been
sampled. The relationship between supergene enrich-
ment and the age of regional pediplain surface devel-
opment is not well constrained. Only in two areas have
surfaces related to enrichment been directly dated
(southern Peru and south of 26S in Chile) and suggest
formation post 14 Ma. Sedimentological data indicate
that a uctuating arid/semi-arid climate prevailed across
the Atacama Desert until between 4 and 3 Ma, climatic
conditions that are thought to be favourable for super-
gene enrichment. The balance between uplift, erosion,
burial and sucient water supply to promote enrich-
ment is complex. This suggests that a simple model for
controlling supergene enrichment is unlikely to be widely
applicable in northern Chile. General models that in-
volve climatic desiccation at 14 Ma related to rain-
shadow development and/or the presence of an ancestral
Editorial handling: A. Boyce
A. J. Hartley (&) C. M. Rice
Department of Geology and Petroleum Geology,
University of Aberdeen, Aberdeen, AB24 3UE, UK
E-mail: a.hartley@abdn.ac.uk
E-mail: c.m.rice@abdn.ac.uk
cold-upwelling Humboldt Current are not supported by
the available geological evidence. The integration of
disparate sedimentological, geomorphological and
supergene age data will be required to fully understand
the controls on and distribution of supergene oxidation
and enrichment in the Central Andes.
Introduction
The Central Andes, and in particular northern Chile,
host some of the worlds largest porphyry copper
deposits (e.g. Chuquicamata and La Escondida; Figs. 1
and 2). The economic viability of these deposits is
commonly dependent on the size and quality of the
supergene enrichment blanket (Sillitoe and McKee
1996). Understanding the controls on the development
of the supergene blanket could therefore have a signi-
cant impact on the perceived economic viability of po-
tential deposits and future exploration policy. Published
models (e.g. Alpers and Brimhall 1988; Sillitoe and
McKee 1996) demonstrate that supergene enrichment of
porphyry copper deposits in the Central Andes ceased at
14 Ma due to an increase in aridity. This climate-driven
model has signicant economic implications. It implies
that exploration for major cumulative enrichment
blankets should not be carried out beneath thick se-
quences of pediment gravels of Oligocene to Middle
Miocene age unless their accumulation can be shown to
be late in the documented history of supergene activity
(Sillitoe and McKee 1996). It also implies that major
post 14 Ma enrichment blankets will not be developed.
Recent work suggests that the evidence for a shift to
hyperaridity at 14 Ma in the Atacama Desert of north-
ern Chile and southern Peru is not supported by sedi-
mentological and geomorphological data (Hartley and
Chong 2002; Hartley 2003). Here we summarise and
discuss the published evidence for the timing of super-
gene enrichment in the Central Andes and its relation-
ship to the Neogene climate change deduced from
sedimentological and geomorphological evidence. In
addition we consider the implications of these observa-
tions for the discovery of supergene-enriched porphyry
copper deposits in northern Chile and southern Peru.
Formation and dating of supergene enrichment
Supergene enrichment is an economically important
weathering process that concentrates some metals (e.g.
Cu and Ag) within the weathering prole while others
are lost. It may produce ore or signicantly upgrade
existing ore bodies. The oxidation and acid leaching of
sulphide deposits may produce spectacularly rich con-
centrations of Cu and Ag towards the base of the
prole. Enrichment is a function of uplift, climate,
initial rock composition (especially pyrite) and struc-
ture (Anderson 1982; Chavez 2000). Assuming the last
two factors are satised, for supergene enrichment to
take place a balance is required between: (1) tectoni-
cally induced uplift that depresses the water table and
thereby exposes underlying sulphides to the eects of
oxidative weathering but does not result in excessive
erosion (2) at least moderate precipitation (>100 mm/
years, Clark et al. 1990) to provide the groundwater
required for leaching, oxidation and precipitation and
to maintain a low water table and (3) a lack of burial
by subsequent sediments as, an appreciable thickness
of gravels and ignimbrites (up to 50 m) will result in
location of the palaeowater table within the gravels
rather than the subjacent mineralised bedrock, a situ-
ation that precludes oxidative weathering of sulphides
and release of the copper required for enrichment
(Sillitoe and McKee 1996).
Alunite and jarosite are relatively common alteration
products in supergene proles developed over sulphide-
rich rocks where acidic conditions prevail (Anderson
1982). They have been used to date, by KAr/ArAr
techniques, the timing of oxidation in a variety of ore
deposits including porphyry coppers and AuAg
deposits of various types (e.g. Arehart et al. 1992; Silli-
toe and McKee 1996; Darke et al. 1997). In addition,
recent ArAr dating of copper wad minerals such as
birnessite and cryptomelane has allowed exotic copper
deposit formation to be constrained, extending our
knowledge of the timing of supergene enrichment (Mote
et al. 2001). The dates derived from these minerals
provide a time constraint on when sucient ground-
water (i.e. >100 mm/years) was available for their pre-
cipitation and by implication the secondary minerals of
economic interestthe youngest date indicating the last
time sucient moisture was available for precipitation.
The causes of a fall in the water table may be tectoni-
cally, climatically or burial related, or a combination of
these mechanisms. These sulphates may also form dur-
ing hypogene mineralisation as a component of ad-
vanced argillic alteration in the epithermal environment.
Their appearance and textural relations together with
the application of stable isotope studies may be used to
distinguish the two settings (Rye et al. 1992; Sillitoe and
McKee 1996).
Distribution of supergene oxidation and enrichment
in the Central Andes
Copper-, gold- and silver-bearing sulphide ore deposits
with well developed supergene oxidation zones and in
many cases supergene enrichment blankets occur
throughout the Central Andes in Chile, Peru, Bolivia
and Argentina (Figs. 1 and 2). The ore deposits com-
prise arc parallel belts of porphyry copper deposits in
Peru, Chile and Argentina and polymetallic vein
deposits in Peru, Bolivia and Argentina. The belts of
porphyry coppers progressively young from early Cre-
taceous in the west to late Miocene in the east. The most
extensive and most economically important belts are
those of Paleocene and late Eocene to early Oligocene
age (Sillitoe 1990). The polymetallic veins contain
important hypogene concentrations of Sn, Ag and Au
(Turneaure 1971; Ludington et al. 1992). Both types of
deposit show supergene oxidation but well developed
enrichment blankets are only known over the porphyry
coppers.
Supergene oxidation and enrichment has occurred at
a number of deposits/prospects located in the following
morphotectonic regimes in Chile, Peru, Bolivia and
Argentina (Figs. 1 and 3). From west to east these in-
clude the following. (1) The Coastal Cordillera which is
up to 3 km high (average 1 km) and 50 km wide and is
posed of the remnants of the Jurassic arc (granodiorite
and andesite) now cut by a series of active extensional
faults. (2) The Central Depression which has an aver-
age elevation of 1,000 m in the west and rises to
2,000 m in the east. It is 25100 km wide and separated
from the Coastal Cordillera by the 900-km-long, north-
trending extensional Atacama fault zone. Up to
1,100 m of Oligocene to Holocene strata are preserved
within the Central Depression (Fig. 4). The eastern
basin margin comprises a series of compressional and/
or strike-slip faults. (3) The Precordillera which is up to
4,300 m high and 1070 km wide and consists of re-
verse-fault and strike-slip-fault-bounded blocks of Tri-
assic-Eocene strata. It includes the Calama basin,
which represents an eastward extension of the Central
Depression with which it shares a similar sedimentary
and tectonic history (May et al. 1999, 2005). The Pre-
cordillera contains the majority of early Oligocene
porphyry copper deposits in northern Chile which were
originally intruded following the demise of the Late
Cretaceous to Eocene volcanic arc. Major faults in the
Precordillera such as the strike-slip Argomedo-West
Fissure fault system signicantly inuenced the devel-
opment and distribution of these porphyry copper
deposits. (4) The Preandean Depression is up to
100 km wide and has an average elevation of 2,300 m.
It is bounded by reverse faults along the eastern and
western margins and includes basins such as the Salar
Fig. 1 a Regional map of the
Central Andes showing the
main morphotectonic
provinces. Supergene
enrichment in deposits in
Bolivia: KK Korri Kollo, E
Escala, southern Peru: C, Q
Cuajone and Quellaveco, and
northwest Argentina: AR Agua
Rica. Dashed box outlines the
area shown in Fig. 2. b Map
showing present day climatic
zones of western South America
de Atacama. (5) The High Andes or Western Cordillera
comprises the largely Miocene to Holocene volcanic arc
which is 50100 km wide. (6) The Altiplano/Puna is
bounded to the west by the volcanic arc. It comprises a
150-km-wide plateau that stretches throughout the
Central Andes and has an average elevation of 3,700 m
(Fig. 1). (7) The Eastern Cordillera forms the eastern
margin of the Altiplano and developed as a result of
compressional deformation in the late Oligocene al-
though the majority of shortening took place in the
middle and late Miocene (Jordan and Alonso 1987).
Minor deformation of the Altiplano continued into the
Quaternary. (8) The Subandean Ranges form the
eastern edge of the Andean orogen and comprise a late
Miocene to Quaternary thin-skinned thrust belt
(Jordan and Alonso 1987).
All of the morphotectonic regimes outlined above
have had separate tectonic, and in some cases, climatic
histories from at least the Oligocene onwards (see
Hartley et al. 2000; Hartley 2003; Houston and Hartley
2003 for details). Any model that accounts for supergene
enrichment must incorporate these dierences.
Age of supergene oxidation and enrichment
in the Central Andes
Gustafson and Hunt (1975) were the rst authors to date
supergene enrichment in northern Chile. They reported
alunite dates of 36.10.6 and 36.02.5 Ma from El
Salvador using the K/Ar technique. Subsequently Alpers
and Brimhall (1988) reported four K/Ar dates ranging
from 18.00.7 to 14 .7 0.6 Ma from La Escondida.
Sillitoe and McKee (1996) in a comprehensive study of
supergene enrichment of porphyry coppers from north-
ern Chile reported K/Ar dates from 13 deposits/pros-
pects (summarised in Figs. 2 and 3), ranging from
34.31.1 to 14.10.6 Ma. Subsequent work has been
undertaken by Marsh et al. (1997) who reported three
supergene alunite ages from Potrerillos near El Salvador
ranging from 120.5 to 9.10.5 Ma and one jarosite
age of 6.340.50 Ma. Mote et al. (2001) reported ten
supergene alunite Ar/Ar dates ranging from 19.440.3
to 12.890.03 Ma and jarosite ages ranging from 10 to
20 Ma from El Salvador. They also reported copper wad
dates from associated exotic deposits of 35.350.80 to
11.050.12 Ma. Bouzari and Clark (2002) undertook a
study on 15 samples of supergene alunite group minerals
from Cerro Colorado reporting ages ranging from
35.30.7 to 14.62.5 Ma. They also documented
supergene ages from the Spence deposit which range
from 440.54 to 20.92.2 Ma. The majority of the
deposits sampled are located in the Precordillera, the
remainder are found in the other morphotectonic zones
including the Coastal Cordillera, Central Depression
and Western Cordillera (Figs. 2 and 3).
In southern Peru the upper age of supergene miner-
alisation was constrained by Clark et al. (1990) to
13.10.4 Ma at Cuajone and 9.50.5 Ma at Quellav-
eco by the dating of volcanics directly overlying the
supergene blanket. Long et al. (1992) and Columba and
Cunningham (1993) reported supergene alunite ages
(4.70.2 and 5.30.2 Ma, respectively) from the Korri
Kollo gold mine located on the Altiplano of SW Bolivia.
Further supergene mineralisation dates from the Boliv-
ian Altiplano were reported by Darke (1996) and Darke
et al. (1997) ranging from 3.70.2 to 11.90.5 Ma for
Kori Kollo, 1.30.2 to 10.61.2 Ma for the Escala

gold mine and 5.00.2 Ma for the Esperanza gold
mine. Landtwing et al. (2002) dated the age of intrusion
of the porphyry CuMoAu deposit at Agua Rica on
the eastern ank of the Eastern Cordillera in northwest
Argentina to between 8 and 5 Ma. Subsequent super-
gene enrichment is considered to have taken place from
4 Ma to the present day.
b
Fig. 2 Regional map of northern Chile, southern Peru and
southwestern Bolivia showing porphyry copper deposits and
morphotectonic provinces with dated supergene enrichment pro-
les. Letters are keyed to the deposits/prospects documented in
Fig. 4. The two deposits in southern Peru correspond to Cuajone
13, and Quellaveco 9. Inca de Oro is not shown on the map. AFZ
Atacama fault zone; for other abbreviations, see Fig. 3. Ages are
from radiometric determinations of the end of alunite/jarosite
formation in supergene enrichment proles above porphyry copper
deposits. a Cerro Colorado (Sillitoe and McKee 1996; Bouzari and
Clark 2002), b Collahuasi, c Puntillas, d Chuquicamata, e MM, f
Mani, g Sierra Gorda, h Telegrafo, i Lomas Bayas (all Sillitoe and
McKee 1996), j Escondida (Alpers and Brimhall 1988), k Angelina
(Sillitoe and McKee 1996), l El Salvador (Gustafson and Hunt
1975; Sillitoe and McKee 1996; Mote et al. 2001), m La Coipa (Can
Can) (Sillitoe and McKee 1996), n Potrerillos (Marsh et al. 1997), o
Spence (Bouzari and Clark 2002), Korri Kollo Darke et al. (1997),
Columba and Cunningham (1993), Long et al. (1992), Escala
Darke (1996), Agua Rica Landtwing et al (2002)
Supergene oxidation, enrichment and geomorphology
The intimate relationship between geomorphology and
supergene enrichment has long been recognised in the
Central Andes. Sergestrom (1963) for example, noted
the correspondence between an extensive surface trace-
able throughout the Central Depression of northern
Chile and southern Peru and supergene enrichment of
major porphyry copper deposits. In fact pediment and
pediplain recognition in relation to supergene enrich-
ment became a key exploration strategy in the 1960s and
1970s (e.g. Sillitoe et al. 1968).
Hollingworth (1964) was one of the rst workers to
describe the surfaces from a geomorphological perspec-
tive and termed a locally developed surface a pediment,
and a regionally extensive surface a pediplain. Both
these surface types can be developed on gravels or
weathered bedrock. Subsequent geomorphological
studies identied a number of uplifted and dissected
pediments and pediplains that were not just restricted to
the Central Depression but could also be identied in the
Coastal Cordillera and Precordillera of northern Chile
and southern Peru (e.g. Clark et al. 1967a, b, 1990;
Galli-Oliver 1967; Hollingworth and Rutland 1968; Sil-
litoe et al. 1968; Mortimer 1973, 1980; Mortimer et al.
1974; Mortimer and Saric 1972, 1975; Tosdal et al. 1984;
Naranjo and Pasko 1985). In addition to the work in
the forearc region, a number of regional pediplains have
also been recognised on the Altiplano (e.g. Walker 1949;
Servant et al. 1989; Gubbels et al. 1993).
The age of pediplain development in relation to
supergene enrichment has only been determined in two
areas of the Andean forearc. In the southern part of the
Atacama Desert between 26 and 29S three signicant
erosional surfaces were identied by Sillitoe et al. (1968).
The two older surfaces were associated with supergene
enrichment and had formed by 11.60.5 Ma (Mortimer
1973; Alpers and Brimhall 1988). The youngest surface
termed the Atacama pediplain formed before
9.40.25 Ma and was associated with the destruction
and erosion of earlier formed copper enrichment proles
 6000 6000
Altiplano
Precordillera
4000 Eastern
Coastal Western
Cordillera Cordillera Cordillera
Central
2000 Depression

0
QUAT Escala
2
L Agua Rica
PLIO.

4
E n Korri Kollo
6
L 8

10
Escala
MIOCENE

12 p
M 14 b

16 g m j d
18 l
h
E 20

22 a
c i f e a - Cerro Colorado (Sillitoe and McKee 1996; Bouzari and Clark 2002),
24 b - Collahuasi (Sillitoe and McKee 1996)
c - Puntillas (Sillitoe and McKee 1996)
L 26 d - Chuquicamata (Sillitoe and McKee 1996)
OLIGOCENE

e - MM (Sillitoe and McKee 1996)

28 n f - Mani (Sillitoe and McKee 1996)
30 g - Sierra Gorda (Sillitoe and McKee 1996)
h - Telegrafo (Sillitoe and McKee 1996)
32
o i - Lomas Bayas (Sillitoe and McKee 1996)
E k j - Escondida (Alpers and Brimhall 1988)
34 k - Angelina (Sillitoe and McKee 1996)
l - El Salvador (Gustafson and Hunt 1975; Sillitoe and McKee 1996;
36 Mote et al. 2001)
L m - La Coipa (Can Can) (Sillitoe and McKee 1996)
EOCENE

38 l n - Potrerillos (Marsh et al. 1997)

o - Spence (Bouzari and Clark 2002)
40
M p - Inca de Oro (Sillitoe and McKee 1996)
42 Korri Kollo - Darke et al. (1997), Columba and Cunningham (1993),
Long et al (1992)
44 Escala - Darke (1996)
Agua Rica - Landtwing et al (2002)
46

Fig. 3 Chronostratigraphy of supergene alunite, jarosite and Fig. 2 plus p Inca de Oro (Sillitoe and McKee 1996). Thick lines
birnessite/cryptomelane dates from the Central Andes related to show areas where dates with overlapping error bars have been
morphotectonic province. A schematic elevation prole at approx- dened for each deposit. Thin lines show the error bars. Dashed
imately 22S is shown at the top. Letters correspond to those in lines link dierent phases of enrichment at the same deposit

(Sillitoe et al. 1968; Mortimer 1973; Alpers and Brimhall
1988). Recent cosmogenic radionuclide analyses of
boulders from the Atacama pediplain developed at the
top of the Atacama gravels yielded an age of 8.29 Ma
for the surface (Owen et al. 2003). An additional K/Ar
date on biotite from an ash deposit associated with a
younger surface yielded an age of 4.2 Ma (Owen et al.
2003).
In southern Peru, Tosdal et al. (1984) and Clark et al.
(1990) were able to constrain pediplain development in
relation to supergene enrichment. They identied a
regionally extensive surface of the lower Miocene age
succeeded by a phase of multiple pediment development
between 15 and 8 Ma. Both these periods were marked
by signicant supergene enrichment, although variations
in uplift, erosion and deposition during the multiple
pediment stage resulted in diering enrichment proles
for each studied deposit. Pedimentation ceased in the
Pliocene and was largely replaced by a valley incision
and terrace stage up to the present day.
Elsewhere, a regional pediplain surface at 19 30S in
the Precordillera was dated by Mortimer et al. (1974) to
between 8.80.5 and 9.10.6 Ma. Mortimer and Saric
(1972) working in the Coastal Cordillera between 19 and
21S identied a regional planated bedrock surface
known as the Tarapaca pediplain considered to be
equivalent to the Choja pediplain described from the
Precordillera at 20S by Galli-Oliver (1967). Based on
the age of overlying dated volcanic strata this surface is
considered to be Oligocene in age (Mortimer et al.
1974). Naranjo and Pasko (1985) used regional map-
ping and the ages published by Mortimer et al. (1974) to
Fig. 4 Chronostratigraphy of
the MioceneHolocene deposits
of Central Depression (CD),
Calama basin (CB), and
Preandean Depression
including Salar de Atacama
(SA) and Cordillera de Sal
(CS), for section location, see
Fig. 2. Radiometric dates are
from biotite separates in
volcanic ashes using the KAr
method (Naranjo 1987), and the
ArAr method (Saez et al.
1999; May et al. 1999, 2005). N
Naranjo (1987), S Saez et al.
(1999); all remaining dates from
May et al. (1999, 2005). Errors
on all radiometric dates are
<0.5 million years. Numbers in
the boxes refer to the thickness
of strata in metres

suggest that pediplain development across northern
Chile occurred during the late Miocene and had ceased
by 9 Ma.
Sillitoe and McKee (1996) in summarising previous
work suggested that the composite pediplain of northern
Chile was established by 14 Ma and that the landscape
as far east as the Precordillera has become largely fos-
silised since that time with the exception of erosion
associated with externally sourced rivers. They believe
that supergene oxidation and enrichment takes place
before and during development of the composite pedi-
plain. In some places supergene proles are completely
or partially concealed beneath piedmont gravels and/or
ignimbrite ows that accumulated before and during the
pedimentation event (Sillitoe and McKee 1996). The
origin of the planation surfaces remains under discus-
sion. Hollingworth (1964) considered them to have
formed in response to episodes of rapid uplift of the
Western Cordillera. Whereas, Galli-Oliver (1967)
thought they formed during phases of increased aridity.
Subsequent workers have been divided between these
two theories since.
What is clear from the above is that the relationship
between supergene enrichment and the age and inter-
pretation of pediments and pediplains in northern Chile
and southern Peru is not well constrained. Although
Sillitoe and McKee suggest that the composite pediplain
of northern Chile was established by 14 Ma, there is no
strong evidence to support this. In both cases where the
age and relationship of surfaces and supergene enrich-
ment are constrained, enrichment occurred in southern
Peru before 9.50.5 Ma (Clark et al. 1990) and south of
26S at 11.60.5 Ma (Mortimer 1973; Alpers and
Brimhall 1988) or possibly before 8.29 Ma (Owen et al.
2003). The only other place where a regional pediment
surface has been dated is in the Precordillera at 19 30S
(Mortimer et al. 1974) where formation prior to
9.10.6 Ma was established. As such there is no strong
evidence to suggest that there was a 14 Ma cut-o for
supergene enrichment associated with pediplain surfaces
and that supergene enrichment may have persisted up to
9 Ma and beyond in some areas. However, given that
the age of pediplain development is only locally well
constrained, the regional signicance of these dates is yet
to be established. In particular, given the range of ele-
vations and number of pediments and pediplains present
in northern Chile, pediplain correlations based upon
similar geomorphic criteria are unlikely to be robust.
Until reliable radiometric age dates constrained by ro-
bust geomorphic studies are available across northern
Chile, the generation and regional extent of pediplains
and their relationship to supergene enrichment proles
will remain only partially understood. In addition the
relationship between supergene oxidation/enrichment
and pediplain development on the Altiplano is yet to be
determined.
Supergene enrichment and sedimentological evidence
for climate change
Alpers and Brimhall (1988) and Sillitoe and McKee
(1996) suggested that hyperaridity in the Andean forearc
became established at 14 Ma and that this climatic re-
gime has persisted to the present day. An implication of
this interpretation is that there has been little or no
erosion/sedimentation since 14 Ma, consequently pre
14 Ma supergene enrichment proles and pediplain
surfaces have remained largely intact. Recent studies of
post-Eocene basin-ll successions in the forearc do not
support a change to hyperaridity at 14 Ma. The evidence
for this has been presented previously (e.g. Hartley and
Chong 2002; Hartley 2003) and is summarised here.
Sedimentological studies of Oligocene to early Plio-
cene age deposits from the Andean forearc (the Central
Depression, Calama Basin and the Salar de Atacama,
Fig. 4) allow constraints to be placed on the climatic
regime that prevailed during this time period. From 34
to 6 Ma alluvial fans anked basin margins with evap-
oritic mud ats in basin centres (e.g. Flint 1985; Saez
et al. 1999; May et al. 1999, 2005). From 6 to between 4
and 3 Ma in the Central Depression perennial, diato-
mite-bearing lakes were developed in the basin centre fed
by permanent uvial systems derived from the Pre-
cordillera and by runo from anking alluvial fans (Saez However, subsequent work at El Salvador and Potrer-
et al. 1999). At the same time in the eastern part of the
Central Depression extensive calcretes, diatomites,
perennial uvial deposits and marginal lacustrine lime-
stones were deposited (May et al. 1999). In the Salar de
Atacama from 5 to 2 Ma perennial uvial and lacustrine
sedimentation prevailed (Naranjo et al. 1994). These
sedimentary rocks are considered to have been deposited
under a predominantly semi-arid climate with occasional
uctuations between periods of increased aridity and
increased humidity. A change in climate and the estab-
lishment of the present day hyperaridity occurred be-
tween 4 and 3 Ma as indicated by cessation of uvio-
lacustrine and alluvial-fan sedimentation (Hartley and
Chong 2002). Increased desiccation is indicated by post
3 Ma evaporite precipitation in topographic lows above
Pliocene strata and development of a saline crust
throughout the PeruChile Desert (Chong 1988). The
extreme eastern and southern margins of the Atacama
uctuated between arid and hyperarid conditions during
the Pleistocene as documented by evidence for higher
water table levels (e.g. Betancourt et al. 2000; Latorre
et al. 2002; Rech et al. 2002; Grosjean et al. 2003).
The Cenozoic sedimentary record from the present
day Atacama Desert indicates that sedimentation under
a uctuating arid/semi-arid climate was continuous from
the Oligocene to Early Pliocene, with a change to hy-
peraridity between 4 and 3 Ma (Fig. 4). These observa-
tions do not support a switch to hyperaridity at 14 Ma
as suggested previously. They indicate the possibility
that sucient moisture in the form of precipitation or
groundwater may have been present to promote super-
gene enrichment in the forearc from 14 to 43 Ma.
A further important observation is that the sedi-
mentary succession in the Central Depression and Ca-
lama Basin is derived directly from supergene-enriched
porphyry copper deposits. For example, alluvial fan
gravels sourced from the Chuquicamata and MM area
internger with the 35 Ma limestones that form part of
the Calama basin-ll succession (May et al. 2005).
Discussion
Sillitoe and McKee (1996), building on the work of
Alpers and Brimhall (1988), concluded from their study
of supergene enrichment proles in northern Chile that
there was no obvious relationship between the geological
features of deposits/prospects, their morphotectonic
position, present latitude, present elevation and super-
gene chronology. As there was no evidence to suggest
otherwise, these authors concluded that enrichment did
not proceed beyond 14 Ma due to a forearc wide des-
iccation event which has persisted to the present day.
Further, they suggested that this climate change re-
corded a shift to hyperaridity driven by uplift of the
Andes to create an orographic barrier with an associated
rainshadow in northern Chile and southern Peru.
illos (Marsh et al. 1997; Mote et al. 2001) clearly indi-
cates that supergene activity has continued beyond
14 Ma and in one case up to 6 Ma. Although it should
be noted that El Salvador and Potrerillos are located on
the edge of the hyperarid part of the Atacama, and may
therefore have had a dierent hydrological history
compared to the more northerly deposits.
Another important aspect of the supergene enrich-
ment dates obtained from northern Chile is that a sig-
nicant proportion of the dated deposits have yielded
ages that indicate enrichment had ceased before 14 Ma.
In addition, Clark et al. (1990) reported that enrichment
may have persisted in the Peruvian Precordillera up to
9.50.5 Ma, although it should be noted that the pre-
cise upper age limit on enrichment could not be con-
strained, but it is considered likely to have persisted into
the late Miocene. Clearly the causes of the cessation of
enrichment cannot be ascribed to one simple climatic
desiccation event at 14 Ma. Other important factors
such as the tectonically induced uplift, variations in local
climatic conditions and/or burial by sedimentary and
volcanic rocks, and variations in the geology of indi-
vidual mineral deposits (e.g. hypogene mineralisation,
alteration and structure) need to be assessed for each
deposit/prospect before the controls on supergene
enrichment can be correctly determined.
In southwest Bolivia and northwest Argentina the
persistence of supergene oxidation throughout the Late
Miocene to the present day suggests that a greater
amount of moisture was present in this area relative to
the forearc region of southern Peru and northern Chile.
At present, the Altiplano receives precipitation of over
200 mm/years (Garreaud et al. 2003) and during glacial
times the climate was signicantly wetter than today
(Grosjean 1994). Consequently it is likely that sucient
moisture was available on the Altiplano for supergene
oxidation to continue throughout the late Miocene to
Pleistocene and possibly even to the present day. A
similar scenario is envisaged for Agua Rica in northwest
Argentina where supergene oxidation and enrichment
commenced almost immediately after porphyry intru-
sion and continues today. The present day arid/semi-
arid climatic regime in this area is similar to that of the
Altiplano at Korri Kollo and Escala. There is only a
weak copper enrichment blanket at the former deposit
which can be attributed to the copper decient nature of
Korri Kollo and other polymetallic mineral deposits.
These deposits might be expected to display silver
enrichment blankets but the oxidised silver ores were
mined out during the Colonial period and few records
were kept (Turneaure 1960).
The data presented in Figs. 2 and 3 illustrate that
supergene oxidation and enrichment has been active
between 17 and 27S across the forearc of northern Chile
and southern Peru from 44 to 6 Ma, and on the Alti-
plano and Eastern Cordillera from 11 Ma to the present
day. There is no record of post 6 Ma supergene
enrichment in northern Chile. From these data, together
with those derived from sedimentological and geomor-
phological studies, the evidence for a forearc wide cli-
matic desiccation at 14 Ma is dicult to support. In
short, these data suggest a need to reassess our under-
standing of the controls on supergene enrichment in the
Central Andes.
One of the main problems in correctly assessing the
controls on supergene enrichment is accurately con-
straining the timing and longevity of enrichment. This is
illustrated by the fact that in a number of deposits follow
up work after the original publication has considerably
extended the time span recorded for the supergene
phase, rather than simply conrming the original data.
For example, the initial study at El Salvador by Gus-
tafson and Hunt (1975) suggested a 36 Ma age for
supergene enrichment. Subsequently, Sillitoe and
McKee (1996) reported a 14 Ma date and since then
Mote et al. (2001) extended the enrichment period to
10 Ma and were able to show that rather than enrich-
ment occurring in separate phases it was largely con-
tinuous between 26 and 11 Ma. A 14 Ma supergene
enrichment age was reported from Cerro Colorado by
Sillitoe and McKee (1996), and subsequently extended
back a further 21 million year to 35 Ma by Bouzari and
Clark (2002). The signicance of these observations is
that as more data become available, the age ranges and
periods of enrichment increase. This suggests that the
full spectrum of enrichment ages in the Central Andes is
not likely to have been sampled at the moment. This can
be illustrated by the fact that only the upper 200 m of an
approximately 1,000 m thick zone of oxidation (Os-
sandon et al. 2001) has been sampled at Chuquicamata.
Notwithstanding the above comments, a notable
feature of the data presented in Fig. 3 is the apparent
presence of two time periods when supergene enrich-
ment ceased: (1) 2021 Ma (Puntillas, Spence, Lomas
Bayas, Telegrafo, Mani and MM) and (2) 1415 Ma
(Sierra Gorda, La Coipa, Escondida, Chuquicamata,
Collahuasi and Cerro Colorado, Inca de Oro). Deposits
where enrichment ceased between 21 and 20 Ma are
restricted to the Precordillera between 22 and 23S (plus
Puntillas in the Coastal Cordillera). In contrast deposits
where enrichment ceased around 1514 Ma cover a
much wider geographical area between 20 and 26S.
This could indicate a local control for the 2120 Ma
event (e.g. a local fault/uplift controlled phase of pedi-
plain development) and a more regional control for the
1514 Ma event. However, care should be taken with
this broad approach to interpretation, because deposits
that are immediately adjacent to each other and that
have virtually identical geological settings such as Chu-
quicamata and MM have dierent time periods for
cessation of enrichment, 15 and 20 Ma, respectively.
Further, it is possible that with additional work the time
span of enrichment in these deposits may expand, par-
ticularly as many of them display evidence for at least
two or more phases of leaching and enrichment.
Deposits that have been subject to extensive study show
evidence for continuous enrichment through the 20 Ma
(El Salvador, Cerro Colorado) and 14 Ma (El Salvador,
Potrerillos) time periods, which could indicate a local
control (e.g. proximity to a long-lived fault) on super-
gene oxidation and enrichment.
The inuence of climate on supergene enrichment in
the Central Andes has yet to be fully evaluated. Clearly
the model for the cessation of supergene enrichment due
to the onset of hyperaridity at 14 Ma cannot be sus-
tained. However, the paucity of post 14 Ma dates from
northern Chile does suggest that 14 Ma was a signicant
time period for supergene development and like-wise the
shuto of enrichment at 20 Ma as well. It is notable that
14 15 Ma was a period of cooling in the southern
Hemisphere with increases in aridity recorded in the
Atacama, Namib and Sahara (Hartley and Chong 2002).
A similar cooling event was recorded at 9 Ma and may
be reected in the surfaces dated at 9 Ma by volcanic
strata and cosmogenic radionuclide techniques. Conse-
quently it is possible that supergene enrichment may
have ceased at 14 and ?9 Ma as a result of these phases
of increased aridity that are not related to the formation
of the Andean rainshadow.
Given the variety of variables that are involved in
developing a thick (and high quality) supergene enrich-
ment blanket, the fact that dierent deposits do show
the same age for the end of enrichment does point to a
regional control, because it is unlikely that dierent
deposits will have been subject to the same post-intru-
sion tectonic, erosional or depositional history. How-
ever, the range of ages for cessation of supergene
enrichment shown in Fig. 3 does suggest that climate is
not the only control, for example it is unlikely that even
local climatic eects could result in hyperaridity aect-
ing one deposit and not an adjacent one.
The balance between uplift, erosion, burial and suf-
cient water supply to promote enrichment is complex.
This suggests that a simple model for controlling
supergene enrichment is unlikely to be widely applicable
in northern Chile. In detail each deposit has specic
characteristics which need to be taken into account when
developing models for controls on enrichment. General
models that involve climatic desiccation related to
rainshadow development and/or the presence of an
ancestral cold-upwelling Humboldt Current (e.g. Alpers
and Brimhall 1988; Sillitoe and McKee 1996; Bouzari
and Clark 2002) are not supported by the available
radiometric dates for supergene enrichment, sedimen-
tological and geomorphological data.
Implications for exploration
We have demonstrated that there are insucient con-
straints on the timing and duration of supergene
enrichment, and consequently we cannot with con-
dence identify the specic controls on the enrichment
process in the Central Andes. In particular, the evidence
for a switch to hyperaridity at 14 Ma is unconvincing.
Therefore it is unsafe to assume that post 14 Ma
enrichment has not occurred. Indeed there is evidence
from the sedimentary successions that ank the super-
gene-enriched deposits, that considerable pluvial activity
occurred under a semi-arid climate during the late
Miocene and Pliocene along the Precordillera and west
ank of the Western Cordillera (Saez et al. 1999; Hartley
and Chong 2002). This climatic regime would be su-
cient to promote supergene enrichment as indicated by
deposits on the Altiplano, Eastern Cordillera and Cen-
tral Chile and suggests that sucient groundwater was
available during the Late Miocene to Pliocene to pro-
mote supergene enrichment. The dates of 116 Ma from
Marsh et al. (1997) and Mote et al. (2001) indicate that
this process has indeed occurred in the southern part of
the Atacama Desert. It is likely therefore that post
14 Ma supergene dates will be reported from the Ata-
cama north of 26S and that post 14 Ma enrichment
proles will be associated with post 14 Ma gravels (e.g.
Cameron et al. 2002). In addition it would be expected
that exotic deposits will have formed throughout this
period up to the present day, particularly as active
groundwater recharge is occurring at the present day.
Indeed, the formation of exotic deposits may be fa-
voured over supergene blanket enrichment by the pre-
dominance of lateral rather than vertical (percolation
and leaching) groundwater ow, particularly during the
last 4 million years
Exploration in recent years has focussed on super-
gene-enriched deposits buried beneath piedmont gravels.
Geochemical anomalies have been used to locate buried
deposits (Cameron et al. 2002). A further exploration
tool could involve integrating sedimentological and
geomorphological data with dates from supergene pro-
les. For example, recent age dates from the Calama
Basin located adjacent to ve major porphyry copper
deposits (Fig. 2) have shown the development of at least
three and maybe more phases of alluvial gravel deposi-
tion during the last 10 million years (May et al. 1999,
2005; Fig. 3). A number of unconformities can also be
recognised within the Calama basin-ll succession which
may be tentatively correlated with pediplain surfaces
that can be mapped into the adjacent highlands. Could
these surfaces represent horizons at which supergene
enrichment or exotic copper deposits have been depos-
ited?
Conclusions
This review of the available geochronological, geomor-
phological and geological data has aimed to constrain
the controls on supergene oxidation and enrichment of
porphyry copper deposits in the Central Andes. The
following conclusions can be drawn:
(1) Geochronological data indicate that supergene oxi-
dation and enrichment has been active between 17
and 27S across the forearc of northern Chile and
southern Peru from 44 to 6 Ma, and on the Alti-
plano of Bolivia and Eastern Cordillera of Argen-
tina from 11 Ma to the present day. There is no
record of post 6 Ma supergene enrichment in
northern Chile. However, a major problem is that as
more geochronological data become available the
age ranges and periods of enrichment increase. This
suggests that the full spectrum of enrichment ages
has not been sampled.
(2) Geomorphological studies of pediplain surfaces
have been used to constrain the timing of supergene
enrichment. However, the age of these surfaces in
relation to supergene enrichment proles has only
been constrained in two areas (southern Peru and
south of 26S in northern Chile), and their age and
regional signicance elsewhere is poorly known.
(3) Sedimentological data indicate that sedimentation in
basins anking major porphyry copper deposits has
been continuous throughout much of the Tertiary to
between 3 and 4 Ma. Deposition took place under
an arid/semi-arid climate.
The above data do not support a simple 14 Ma ces-
sation of oxidation and enrichment in the Central Andes
as suggested by previous workers. Instead there is evi-
dence for cessation at various times both before, notably
at 20 Ma, at 14 Ma and beyond at 6 Ma. However, it
must be emphasised that the full picture of the timing
and duration of enrichment is only just emerging as
more radiometric ages are reported.
Given these uncertainties it is clearly unwise to re-
strict exploration programmes by assuming that post
14 Ma enrichment has not occurred. It is likely that the
picture will become more rather than less complex, as
regional and local controls on enrichment become better
understood. The integration of disparate sedimentolog-
ical, geomorphological and supergene age data will be
required to fully understand the controls on and distri-
bution of supergene oxidation and enrichment in the
Central Andes.
Acknowledgements This paper is based upon numerous eld sea-
sons in northern Chile supported in part by the British Council, the
Universidad Catolica del Norte and the Timothy Jeerson Re-
search Fund of the Geological Society, London. We would espe-
cially like to thank Anne Mather (Plymouth) for her insight into
the geomorphological development of northern Chile and Guil-
lermo Chong (Universidad Catolica del Norte) for his continued
support, input and knowledge of the geology of northern Chile.
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