Miner Deposita (2014) 49:235–259
DOI 10.1007/s00126-013-0485-0
ARTICLE
Alteration patterns and structural controls of the El Espino
IOCG mining district, Chile
G. P. Lopez & M. W. Hitzman & E. P. Nelson
Received: 8 February 2012 / Accepted: 19 August 2013 / Published online: 14 September 2013
# Springer-Verlag Berlin Heidelberg 2013
Abstract The El Espino IOCG mining district is character-
ized by several mineralized bodies the largest of which is the
El Espino deposit, which has an estimated geologic resource
of 123 Mt at 0.66 % Cu and 0.24 g/t Au. Mineralized bodies
are distributed in a 7×10 km2 area throughout a 1,000-m
vertical section. They range from single veins to stockworks
and breccias to manto-type deposits. The ore bodies are hosted
primarily by volcanic, volcaniclastic, and sedimentary rocks
of the Early Cretaceous Arqueros and Quebrada Marquesa
formations, with a few mineralized zones within Late Creta-
ceous dioritic intrusions. The fault and vein architecture shows
that El Espino IOCG system was localized within a dilatation-
al jog along a major transtensional dextral fault system. Sodic
alteration (albite) is the most extensive style of alteration in the
district, and it is bounded by major NS–NNE trending faults.
Sodic–calcic (epidote–albite) alteration occurs at deep to me-
dium elevations (1,000–500 m) and grades inward into calcic
alteration. Calcic alteration surrounds dioritic intrusions of the
Llahuin plutonic suite. Significant iron oxides are associated
with later calcic alteration associations (actinolite–epidote–
hematite). The upper portions of the alteration system
(0–500 m) display hydrolytic alteration associations with
abundant hematite. Hydrolytic veins are feeders to zones of
manto-type alteration and mineralization within favorable
volcano-sedimentary lithologies that formed El Espino
deposit. Sulfides are largely confined to calcic and hydrolytic
alteration associations. Hydrothermal fluids responsible for
hematite and sulfide mineralization had salinities between 32
Editorial handling: R. P. Xavier
G. P. Lopez (*) : M. W. Hitzman : E. P. Nelson
Department of Geology and Geological Engineering,
Colorado School of Mines, Golden, CO 80401, USA
e-mail: gplopezo@gmail.com
and 34 wt% NaCleq and temperature of approximately 425 °C
at an estimated depth of 3–4 km. Geochronological U–Pb and
40
Ar/39Ar data indicate that hydrothermal alteration was coe-
val with magmatic intrusive activity. One particular dioritic
intrusion (88.5 Ma) preceded the calcic stage (88.4 Ma),
which was accompanied by iron oxide copper and gold min-
eralization. Hydrolytic alteration, related to economic iron
oxide copper and gold mineralization, came immediately after
at 87.9 Ma.
Introduction
Iron oxide copper gold (IOCG) deposits are magnetite- and/or
hematite-rich hydrothermal systems with economic copper
and gold. Their classification and genesis are still contentious
(Haynes 2000; Hitzman 2000; Barton and Johnson 2000;
Sillitoe 2003; Williams et al. 2005; Pollard 2006; Chiaradia
et al. 2006; Groves et al. 2010). Andean-type IOCG deposits,
which are the youngest major province of the IOCG class,
formed in an extensional to transtensional tectonic regime
within the Jurassic–Cretaceous magmatic arc along the con-
vergent margin of the Central Andes—from southern Peru to
north central Chile (Sillitoe 2003). Andean IOCG deposits
display variable morphologies and alteration styles and have a
variety of relationships to possible causative intrusive rocks.
The El Espino deposit located at 31°23′ S in the Coastal Range
of Northern Chile is one of the southernmost known IOCG
systems in Chile (Fig. 1). Currently, the El Espino deposit has
a measured and indicated total resource of 145 Mt at 0.55 %
Cu and 0.22 g/t Au (Explorator Resources 2011). The El
Espino deposit is located at the west margin of a much larger
mining district (El Espino mining district) that contains a
number of small vein, stockwork, manto, and irregularly
shaped iron oxide-bearing copper–gold deposits within a
mixed sequence of Mesozoic volcanic and sedimentary rocks
236
Fig. 1 Location of El Espino deposit in relation of other Chilean IOCG
deposits. Two NS trending belts of ore deposits overlap along the Chilean
Iron Belt: magnetite–apatite deposits and IOCG deposits
cut by intermediate composition intrusions. The El Espino
mining district has a vertical relief of approximately 1,000 m
allowing investigation of alteration and mineralization styles
through a significant vertical section. This paper presents
information on lateral and vertical zonation of alteration and
mineralization in the district, the structural setting of the
mineralization, the relative ages of igneous and hydrothermal
events, and the chemistry of the hydrothermal fluids inferred
from petrographic and isotopic investigations.
Miner Deposita (2014) 49:235–259
Methods and materials
Project goals were achieved through a combination of detailed
field mapping and laboratory studies. Geological, structural,
and alteration mapping were done throughout the 70-km2
study area at 1:20,000 scale during 2004 and 2005. Additional
information was gathered from mapping pits and underground
adits and from logging of drill core from the El Espino
deposit (Fig. 2). Field mapping and logging concentrated
on establishing the time–space relationships and structural
and stratigraphic controls of alteration and mineralization.
Samples collected during the fieldwork were examined
petrographically at Colorado School of Mines using trans-
mitted and reflected light microscopy and with scanning
electron microscopy (SEM) and a PGT Spirit analyzing
system attached to the SEM for X-ray energy dispersive
spectrometry. Detailed petrography was conducted on
samples for fluid inclusion analyses using the methodol-
ogy of Goldstein and Reynolds (1994) at Colorado School
of Mines.
Major and trace element geochemical analysis were
performed on relatively unaltered samples of volcanic rocks
(7) and intrusive (13) rocks, together with hydrothermally
altered and mineralized samples from throughout the district
to investigate chemical changes associated with hydrothermal
alteration. The samples were crushed and pulverized at ALS
Chemex, La Serena, Chile, and then were sent to ALS
Chemex, Vancouver, Canada, for geochemical analyses.
Whole rock analysis involved lithium metaborate/lithium
tetraborate (LiBO2/Li2B4O7) fusion and analysis by inductive-
ly coupled plasma (ICP) atomic emission spectroscopy. Trace
element analysis was conducted by a combination of ICP
mass spectrometry and ICP atomic absorption spectroscopy
after four acid near total digestions.
Fluid inclusions were analyzed on three double-sided
polished thick sections (50 μm) from the Espino and Romero
areas at Colorado School of Mines and Fluidinc, Denver. The
analyses were performed using a US Geological Survey-style
gas-flow heating/freezing stage mounted on an Olympus mi-
croscope equipped with a 40× objective (N.A.=0.55) and 10×
oculars. The heating and freezing stages were calibrated at
374.1 and 0.0 °C using synthetic pure H2O fluid inclusions
and at −56.6 °C using synthetic CO2 fluid inclusions. Thermal
cycling was used to bracket the liquid–vapor homogenization
temperatures (T h) and melting temperatures (T m) of the fluid
inclusion assemblages.
Sulfur isotope analysis was performed by G. Lopez at
Colorado School of Mines on pyrite (13), chalcopyrite (22),
and gypsum (1) separates derived from micro drilling of core
and rock samples across the district. Approximately 25–
100 μg (weight dependent on the mineral analyzed) of sample
were combusted in a Eurovector 3000 elemental analyzer at
Colorado School of Mines, yielding sulfur dioxide that was
Miner Deposita (2014) 49:235–259
Fig. 2 Geological framework and location of Espino district. Regional map is simplified from the 1:1,000,000 scale Chilean Geological Survey map
(Servicio Nacional de Geología y Minería, 2002). Rectangle shows location of Fig. 3
delivered to a Isoprime mass spectrometer using continuous-
flow techniques, with helium as the carrier gas. Repeat anal-
yses of a lab working standard (Colorado School of Mines
Barium Sulfate) yield a precision of 0.2 ‰. The isotopic data
are reported using the δ notation in units of per mile, relative
to the Cañón Diablo Troilite standard.
Tectonic and geological setting
The segment between 27° and 33° S in Chile is characterized
by a Mesozoic–Cenozoic magmatic arc built mostly over a
Late Paleozoic to Triassic accrecionary prism and arc along a
subducting margin. The Mesozoic Andean evolution was
characterized by a Jurassic–Early Cretaceous magmatic arc
accompanied by a sedimentary back-arc basin and an aborted
marginal basin followed by a Late Cretaceous magmatic arc
with a fold and thrust belt to the east (Fig. 2). The Jurassic–
Early Cretaceous magmatic arc comprised coeval inner and
237
outer arcs developed in the present Coastal Cordillera and in
the Chile–Argentina border, respectively (Mpodozis and
Ramos 1990). The El Espino deposit is located at the eastern
margin of this inner magmatic arc.
The Early Cretaceous times were marked by an extensional
regime, marine transgression, decreased plutonism in the Coast-
al Cordillera, and extensive subaerial volcanism—with marine
intercalations—associated with intra-arc rifting (Åberg et al.
1984; Vergara et al. 1995). The volcanic rocks are high-K,
calc-alkaline to shoshonitic basaltic andesite to andesite. Stron-
tium and neodymium isotopic studies suggest that the volcanic
rocks and coeval intrusive rocks were derived from depleted
mafic magmas and metasomatized subducted sediments with
inclusion of partially melted Jurassic plutonic rocks (Morata
and Aguirre 2003). These rocks underwent high subsidence and
low-grade burial metamorphism concurrent with extension-
related plutonism (Levi and Aguirre 1981; Parada et al. 2005).
At approximately 100 Ma, the tectonic regime shifted from
extensional to compressional between 32 and 33° lat. S,
238
resulting in crustal shortening, basin closures, eastward mi-
gration of magmatism, and uplift (Arancibia 2004; Parada
et al. 2005). The change from extensional to compressional
tectonics has been attributed by Arancibia (2004) to higher
spreading rates in both the southeast Pacific and the south
Atlantic (Wilson 1992). Mid-Cretaceous uplift of the Coastal
Range in this portion of Chile has been documented by apatite
fission track data from Jurassic and Early Cretaceous plutonic
rocks that cooled to approximately 80–125 °C by 110–90 Ma
(Gana and Zentilli 2000; Parada et al. 1999).
The Early Cretaceous Arqueros and Quebrada Marquesa
formations were deposited in the Coastal Range region between
30° and 32° S. The Neocomian Arqueros Formation consists of
lava, volcanic breccia, tuff, and agglomerate with lenticular
intercalations of conglomerate, sandstone, and locally thin fos-
siliferous limestone. It has an estimated thickness of 3,500–
4,000 m and is interpreted to have formed near a continental
margin with associated volcanic activity and recurrent marine
transgressions (Aguirre and Egert 1965). The Barremian to
Albian Quebrada Marquesa Formation consists of mixed
volcanic and sedimentary rocks (Aguirre and Egert 1965). The
formation was subdivided in two members: the lower Espino
Member and the upper Quelen Member (Rivano and Sepulveda
1991). The Espino Member consists of limestone, siltstone,
sandstone, and conglomerate with local gypsum lenses. Vertical
and lateral facies variations of the Espino Member made it
difficult to define a representative stratigraphic column. The
Espino member is interpreted to have been deposited in
relatively small marine to transitional basins with sea level
variations (Rivano and Sepulveda 1991). The Quelen Member,
with estimated thickness of 1,200 m, consists of red colored
volcaniclastic and sedimentary rocks including lava, pyroclastic
breccia, and volcanically derived sandstone and conglomerate.
The Quelen member represents deposition in a continental
environment accompanied by intense volcanism.
The Early Cretaceous Espino and Quelen members in the
El Espino district are covered by the Late Cretaceous Sala-
manca Formation (initially defined as the Viñita Formation by
Aguirre and Egert 1965, but later included into Salamanca
Formation by Rivano and Sepulveda 1991). The Salamanca
Formation is preserved from the Coastal Range up to the Main
Cordillera and ranges in thickness from approximately 3,500–
4,000 m. The formation is subdivided into two units: lower
Santa Virginia Member and upper Rio Manque Member
(Rivano and Sepulveda 1991). The Santa Virginia Member
consists of conglomerate and red, hematitic sandstone with
minor siltstone and lacustrine limestone intercalations. These
sedimentary rocks are interpreted to have been deposited as
alluvial fans and debris flows with finer-grained sediments
deposited in the basin center. The overlying Rio Manque
Member consists of tuff and volcanic breccia; it represents
deposition during a period of intense and explosive latest
Cretaceous volcanism (Rivano and Sepulveda 1991).
Miner Deposita (2014) 49:235–259
Cretaceous intrusions are exposed over an area of approx-
imately 3,000 km2 along the Coastal Range between 31° and
32° S (Fig. 2). This area contains three large plutonic bodies
(Fig. 3) and a number of smaller bodies of similar composition
(Rivano and Sepulveda 1991). The plutons include diorite,
tonalite, amphibole and pyroxene granodiorite, and amphibole
monzodiorite. Potassium–argon geochronology available in-
dicates that the Quilatapia–El Durazno pluton (Fig. 3) ranges
in age from 134 to 108 Ma, whereas the Illapel–Caimanes
pluton (Fig. 3) ages range from 130 to 86 Ma and young to the
east (Rivano and Sepulveda 1991).
El Espino district geology
The El Espino mining district contains the Cretaceous volcano-
sedimentary Arqueros, Quebrada Marquesa, and Salamanca
formations. Only the upper portion of the Arqueros Formation
and the basal portion of the Salamanca Formation are exposed
in the area (Fig. 3).
These formations are intruded by a series of Late Cretaceous
intermediate stocks of granodioritic to dioritic composition
(Llahuin pluton in the north-central area and Illapel–Caimanes
pluton to the south; Fig. 3).
Stratigraphy
The Arqueros Formation in the El Espino district has a min-
imum thickness of 1,500 m and consists of gray-greenish
andesitic lava, andesitic breccia, and andesitic lapilli tuff with
lenses up to 100 m thick of andesitic conglomerate, sandstone,
siltstone, and limestone (Fig. 4). The unit displays a high
degree of lateral facies variability.
The Quebrada Marquesa Formation (Figs. 3 and 4) dis-
plays a conformable contact with the underlying Arqueros
Formation in the southern portion of the El Espino district
but is in fault contact with the Arqueros Formation in the
north. The Quebrada Marquesa Formation consists of a mixed
sequence of volcanic and sedimentary rocks.
The Espino Member of the Quebrada Marquesa Formation
is composed of continental to marginal marine volcaniclastic
and sedimentary rocks. The marine sedimentary rocks of
Espino member were deposited in a relatively small, structur-
ally controlled basin that is approximately 13 km long in a
north–south direction and approximately 5 km wide. The base
of the Espino Member consists of a 5–10 m thick, well-
stratified red andesitic conglomerate that grades upward into
red graywacke beds, then siltstone, and finally limestone. This
basal unit is overlain by two additional, normally graded
sequences each with a base of sandstone that grades upward
to siltstone, limestone, and local gypsum beds. Graywacke is
dominantly gray in color and is composed of feldspar, quartz,
and lithic clasts of andesite. Sandstone is yellow to pink and
Miner Deposita (2014) 49:235–259
Fig. 3 Geological map of El Espino mining district, showing the location of the three mineralized areas that were examined in detail: Espino, Romero,
and Llahuin
fine to coarse grained. There is complete gradation from
volcanic-derived arkosic graywacke to feldspathic sandstone.
Siltstone beds range from dark gray to yellow with the former
being locally organic rich with relatively abundant diagenetic
pyrite. Limestone is thick bedded and commonly contains
chert nodules. The largest gypsum bed in the district is
100 m thick and has been mined over a strike length of
800 m (San Enrique mine). In the central portion of the
district, the sedimentary rocks within these sequences
are intercalated with volcanic lavas, pyroclastic beds, and
volcaniclastic sedimentary rocks. Volcanic and pyroclastic
rocks include gray to green colored porphyritic lava flows
239
with pyroxene and hornblende phenocrysts, lapilli tuff, and
breccia. Major element chemistry of volcanic rocks indi-
cates these rocks are medium- to high-K basaltic andesite
to andesite (Fig. 5). The uppermost sequence in the Espino
Member consists of inversely graded sandstone beds, with
subsidiary limestone and siltstone. Sandstone is yellow to
gray and fine to medium grained. Limestone beds are a few
meters thick and commonly contain chert nodules. The
thickness of the Espino Member is estimated to be approxi-
mately 900–1,000 m in the southern portion of the district and
approximately 600 m in the northwest where it is truncated by
the Llahuin pluton.
240 Miner Deposita (2014) 49:235–259

Fig. 4 Cretaceous stratigraphy in

the El Espino mining district
showing the stratigraphic
intervals of the Espino, Romero,
and Llahuin areas

The Quelen Member of the Quebrada Marquesa Formation

is characterized by several centimeter thick medium- to
coarse-grained sandstone base that grades upward to a region-
ally extensive coarse conglomerate with clasts of well-
rounded porphyritic andesite, andesitic breccia, and phaneritic
dioritic intrusive rocks. The conglomerate is overlain by a
thick greenish lapilli tuff of the Late Cretaceous Salamanca
Formation.
The Late Cretaceous Salamanca Formation (Figs. 3 and 4)
is in fault contact with the Quebrada Marquesa Formation in
the El Espino mining district, although a few outcrops at
higher elevations show an erosional unconformity between
red conglomeratic sandstone of the Quelen Member and
Fig. 5 Plot of SiO2 vs. K2O (Tatsumi and Eggins 1995) showing
lapilli tuff of the Santa Virginia member of Salamanca chemical compositions of volcanic rocks in the Arqueros and
Formation. In the study area, the Salamanca Formation Quebrada formations. Rocks are classified as medium- to high-potassium
contains a basal unit that comprises volcanic breccia and andesite and basaltic andesite
Miner Deposita (2014) 49:235–259
locally gray thin-bedded siltstone. Higher in the sequence,
this formation contains red to gray polymictic conglomerate
and red sandstone.
Intrusive rocks
Approximately 30 % of the El Espino mining district is
underlain by intrusive rocks (Fig. 2). The northern portion of
the study area exposes the large, multiphase Llahuin pluton.
The central portion of the area exposes a number of isolated
diorite plutons, and the southern portion of the area exposes
the large multiphase Illapel–Caimanes pluton (Fig. 3).
The Llahuin pluton (or Llahuin plutonic suite) comprises at
least nine individual intrusions, which are distinguished by
texture and mineralogy, and geographical location. Few
intrusive contacts between intrusions were observed due
to soil, debris, and/or vegetation cover, so some textural
and mineralogical variations observed in the district might
be due to zonation within a single stock. Some of the dioritic
intrusions have caused local contact metamorphism of adjacent
volcano-sedimentary rocks. Biotite-pyroxene hornfels occurs
adjacent to sills in drill cores in the El Espino deposit. Locally
andesitic breccias in the Llahuin area display a meter-wide
metamorphic aureole composed of fine-grained recrystallized
quartz with lesser magnetite and epidote adjacent to a quartz
monzonite intrusion.
Three intrusions present in the El Espino deposit area
include a hornblende-bearing porphyritic dioritic stock and
sills; an hornblende-bearing, fine-grained monzodiorite; and
an equigranular, fine-grained hornblende and pyroxene-
bearing diorite. A sharp contact was observed between the
amphibole-bearing monzodiorite and the hornblende and
pyroxene-bearing diorite. A medium- to coarse-grained,
equigranular quartz-dioritic to tonalitic intrusion is exposed
at higher elevations north of the El Espino deposit. East of
the El Espino deposit at low to medium elevations, a
hornblende and pyroxene-bearing microdiorite, NS-strike
gray dioritic dikes, and a NS-trending tabular body of leuco-
monzodiorite are present. Dikes display a sharp contact with
the leuco-monzodiorite. Northeast of the El Espino deposit an
equigranular, medium-grained, olivine and pyroxene-bearing
gabbro diorite, an equigranular medium-grained quartz mon-
zonite, and a monzodiorite occur in topographically high
areas. The monzodiorite unit displays a transitional contact
between a dark gray idiomorphic medium-grained unit and a
pink xenomorphic finer-grained unit.
U–Pb geochronology on zircons from a weakly altered
diorite from the Llahuin pluton at the El Espino deposit
yielded an age of 88.5±1.7 Ma. A quartz diorite from the
Llahuin area in the northern portion of the district yielded an
age of 88.1±1.1 Ma. More detailed descriptions of samples
analyzed, and age results are reported in Lopez (2012).
241
Structure
A fault architecture model of the El Espino mining district was
developed by mapping topographic lineaments on Landsat
and Aster imagery that were then field checked during geo-
logical mapping (Fig. 6). Fault orientation data from outcrop
show two principal strike sets: NNW–NS, and NE (Fig. 7).
Fault dips are mostly >45° (Fig. 7d). Fault cores are mostly
about 0.5–1 m thick, but ranging up to 20 m thick and consist
of matrix-supported breccia, gouge, and locally a penetrative
fracture cleavage. Damage zones of fractured and locally
folded rocks can be up to 150 m thick. Analysis of slickenline
rake (Fig. 7d) shows that, although the majority of faults are
strike-slip faults, oblique-slip and dip-slip fault also are pres-
ent. Multiple slickenlines on some major faults indicate a
protracted faulting history. This is supported by the presence
of hydrothermal alteration (specular hematite) and copper
mines along NNW-strike faults that were probably active
previously during basin formation.
The Quebrada Marquesa formation has a general NS trend
and is bounded to the west by the Espino–Illapel fault that
extends for ∼20 km from near the city of Illapel to the El
Espino area. Although the fault trends generally N to NNE,
about 8 km south of the area this structure changes trend to
NNW and becomes a set of right-stepping en echelon fault
segments along the west boundary of the basin (Fig. 3). With-
in the basin, strata generally have low homoclinal dip to the
NE, but are broadly folded in the southern portion. Boudinage
in limestone and fine-grained sandstone units of the El Espino
member suggests bedding-parallel extension during diagenet-
ic compaction or during subsequent folding. Folds have EW
trend in the east and NE trend in the west (Fig. 6). Near the
southern edge of the basin, a broad open NE plunging anti-
cline is present and strata dip to the E and SE. In addition, dips
are locally steep where strata are drag folded within about
10 m of some major faults. A π-analysis, which modeled the
average axis of rotation of bedding in the Quebrada Marquesa
Formation (in this case caused by fault-block rotation), sug-
gests that the eastern margin of the basin may be bounded by a
NNW-strike fault (∼350°) (Fig. 7a). A fault with this approx-
imate strike, although not the basin margin fault, is present
east of the Romero area (Fig. 6).
The Quebrada Marquesa strata are also cut by a set of NE-
strike, left-stepping en echelon faults (Fig. 3). Most mineral-
ized veins in the district, including those in the El Espino,
Romero, and Llahuin areas, strike NS to ENE, and many are
related to these NE-strike faults (Fig. 7). Veins are defined
here as fractures with infill of more of 5 cm width, and veins
that display a fault plane or fault zone with gouge and/or
breccia are termed fault-veins. Several types of veins were
identified based on their ore and/or gangue mineralogy in the
district and include iron oxide sulfide (with or without-quartz)
veins, quartz sulfide veins, and calcite- and/or barite sulfide veins.
242 Miner Deposita (2014) 49:235–259

Fig. 6 Structural map of El

Espino mining district showing
faults in blue, lineaments in
black, folds in black, and veins in
red. Blue triangles indicate
inverse fault, dots indicate normal
faults, and blue arrows indicate
sense of movement along faults.
The district is bounded on the
west and east by major fault zones

Iron oxide sulfide veins are the most common followed by quartz
sulfide veins. Iron oxide sulfide veins range from 5 to 2 m in
width, whereas quartz sulfide veins range from 5 cm to 1 m.
In the El Espino deposit area, iron oxide and quartz sulfide
veins occur in the Espino Member and intrusive units
of Llahuin pluton. Orientations are variable but average
∼240°/75° (right-hand rule); quartz sulfide veins have a wider
dispersion in orientation than iron oxide sulfide veins (Fig. 8).
Veins frequently terminate at contacts with overlying limestone
units where the calcareous rock above is mostly silicified and
the rock beneath shows stratabound metal disseminations, in-
dicating that locally iron oxide and sulfide mineralization was
focused immediately beneath these contacts. The wall rocks
surrounding iron oxide sulfide veins are commonly altered to
Miner Deposita (2014) 49:235–259 243

calcic and hydrolytic associations depending on their structural
level. The true width of the alteration zones range from 20 cm
to 5 m. Wall rocks surrounding quartz sulfide veins are altered
to hydrolytic to argillic associations with widths ranging from
20 cm to 1 m.
In the Llahuin area iron oxide and quartz sulfide veins
occur in the Quelen Member of Quebrada Marquesa Forma-
tion. Veins have an average strike of ∼020°; quartz sulfide
veins have an average dip of ∼55° (towards the east), while
iron oxide sulfide veins are steeper with average dip of
∼90° (Fig. 8). Barite sulfide veins occur in the Arqueros
Formation and in the Espino Member of Quebrada Marquesa
Formation. They are distal to the El Espino deposit area and
have scattered orientations.
In the Romero area, iron oxide and quartz sulfide veins
occur mostly in the Quelen Member and have strikes ranging
from NNW to NNE and averaging ∼185°. Dips of the veins
average 65° (Fig. 8). Vein density is higher in the Romero area
(up to ∼6/km) than in the Espino area (∼3/km), where
stockworks of specular hematite are a common feature related
to major veins.
Kinematic data indicate that the NNW- and NE-striking
faults in the district had both dextral and sinistral strike-slip
and normal and reverse dip-slip motion (Fig. 7c). Fault-vein
kinematic data display dextral and sinistral strike-slip compo-
nents, but all dip-slip components show normal fault motion
(Fig. 8c, d). The orientations of the instantaneous principal
strain axes were modeled from fault kinematic data using the
Faultkin program (Allmendinger et al. 2001). The results
(Fig. 9) show near vertical shortening and NNW–SSE exten-
sion for the major faults and near vertical shortening and
WNW–ESE extension for the fault veins. Although the results
are only an approximation due to the likelihood of multiple
faulting events, the models suggest that the fault architecture
was established prior to mineralization during NNW–SSE
crustal transtension with a dextral component and that the
fault veins formed during extensional faulting and WNW–
ESE oriented crustal extension.
The overall geometry and kinematics of the faults and veins
suggests the district contains a negative flower structure de-
veloped in a right-stepping jog locally along a major N-strike
dextral fault system. This architecture also controlled the

Fig. 7 Lower hemisphere, equal

area stereonets showing bedding
a b
and fault orientation data. a
Bedding poles in Quebrada
Marquesa Formation excluding
areas of drag folds near exposed 2%

major faults. The average bedding

orientation is ∼000°/20°. Fault 4%
rotation axis (π-axis
perpendicular to best fit great
circle) is nearly horizontal and 6%

trends 350–170°. b Pole density

contours for 66 faults with gouge
width >5 cm. There are three
main fault set orientations:
∼135°/90°, 205°/80°, 350°/70°.
c Major faults orientations shown
as great circles. Slickenlines in
faults are depicted as dots with
arrows showing the relative
motion of the hanging wall. Black
squares labeled 1, 2, and 3 are the c d
instantaneous strain axes
calculated by Faultkin program
(Allmendinger et al. 2001) that
correspond to σ 3, σ 2, and σ 1
principal stress axes, respectively,
if minimal rotational strain is
assumed. d Histograms showing
dip of major faults (top) and the
rake of major fault slickenlines
(bottom)
244 Miner Deposita (2014) 49:235–259

Fig. 8 Lower hemisphere, equal

area stereonets showing vein a b
orientation data. a Poles to veins;
Espino IOCG veins (black
circle), Espino quartz-sulfide and 2%
calcite-quartz-sulfide veins (open
circle), Romero IOCG (black 4%
square), Romero quartz-sulfide
veins (open square), Llahuin 6%

IOCG veins (black triangle),

Llahuin quartz-sulfide veins 8%

(open triangle), and barite-sulfide

veins (star). b Pole density
contours for 44 IOCG veins in the
El Espino mining district; average
IOCG vein orientation is
∼210°/85°. c Major veins
orientations plotted as great
circles with dots indicating
slickenlines and arrows on the c d 6
dots showing relative motion of

Frequency
the hanging wall. Numbers 1–3
4
are the instantaneous strain axes
calculated by Faultkin program
(Allmendinger et al. 2001) that 2
correspond to σ 3, σ 2, and σ 1
principal stress axes, respectively, 0
if minimal rotational strain is 10 20 30 40 50 60 70 80 90
assumed. d Histograms showing Fault-vein dip
4
dip of major fault veins (top) and
the rake of major fault-vein
Frequency
slickenlines (bottom)
2

0
10 20 30 40 50 60 70 80 90
Slickenline rake

localization of later IOCG alteration and mineralization
around the Llahuin pluton (Fig. 10). The Espino vein system
formed mostly as NE-strike extension fractures and normal
faults within the jog, whereas the Romero and Llahuin veins
formed along the eastern N- to NNE-strike basin margin fault
system. The Romero area contains NS-striking dioritic dikes
that locally controlled the location of IOCG fault veins.
Alteration and mineralization
The El Espino mining district displays a variety of different
alteration types and styles (Figs. 11 and 12). The paragenetic
sequence of alteration (Fig. 11) was built based on crosscut-
ting relationships between alteration minerals observed either
in the field or petrographically with the microscope. An early
sodic alteration event affected much of the district. It was
followed by sodic–calcic and potassic alteration events. These
alteration events are associated with iron oxide mineralization.
A later calcic alteration event was synchronous with copper
sulfide mineralization. The district displays a complex series
of late hydrolytic alteration styles that also have associated
copper and gold mineralization.
Structural controls on alteration and mineralization
The distribution of hydrothermally altered and mineralized
zones in the El Espino district indicates a strong structural
control. The NNE-striking Lagarrigue fault forms a fundamen-
tal eastern boundary to the district with altered rocks occurring
to the west but not to the east of this fault. Sodic hydrothermal
alteration appears to have occurred between Lagarrigue and
Illapel–Espino faults. Major alteration zones are distributed
along, or subparallel to, the NNW- to NE-striking faults in the
district. Although the NNW-strike faults may contain iron
oxides and sulfides, these faults rarely contain ore bodies.
Many of the iron oxide and sulfide-bearing veins in the
district have a generally N to NE strike. At the El Espino
deposit steeply dipping sulfide-bearing veins strike NE to
NNE. Similar veins in the Romero area also have an N- to
Miner Deposita (2014) 49:235–259 245

Fig. 9 Lower hemisphere, equal

area stereonets showing fault 3 2
plane solutions for a major faults
and b IOCG fault veins in El
Espino mining district. Labels σ 3, 3
σ 2, and σ 1 correspond to
2
principal stress axes

1
1

NNE strike that extend upward into the Llahuin area. Vein
density is higher at Romero and veins stockworks, commonly
containing abundant specular hematite, are more prominent
here than in other prospects. The width and intensity of
alteration around NE-striking faults and veins are commonly
comparable to, or better developed than, alteration around the
NW striking faults.
The N- to NE-striking fault veins in the district are related
to a transtensional stress regime during the prolonged hydro-
thermal event. The strike of these structures suggests WNW–
ESE extension with an associated dextral component. Calcic
and hydrolytic alteration together with the majority of iron
oxide and sulfide mineralization appear to be synchronous
with this extensional structural event.
The NW-strike Tamara fault (Correa 2003) apparently
postdates both alteration and mineralization. While it locally
contains sericite, it is never mineralized. Instead, the fault
appears to have acted as a conduit for meteoric waters that
resulted in supergene alteration of sulfide-rich zones that it
transects.
Sodic alteration
Sodic alteration affected a large portion of the El Espino
district. It is best developed along a north-striking corridor
from the Caimanes–Illapel pluton to the El Espino deposit.
The style and mineralogy of sodic alteration associations
vary by rock type but generally resulted in the formation of

Fig. 10 Proposed structural

model for El Espino mining
district. a Satellite image
(Landsat 741) with lineament
interpretation. b Fault jog model
showing general orientation and
location of veins (red) in El
Espino (e), Romero (r), and
Llahuin (l) areas. Plutons shown
as pink ellipses: d Llahuin diorite
and equivalents, g dioritic pluton
along southern margin of basin
246
Fig. 11 Paragenetic sequence of alteration minerals. Continuous lines represent a major phase, segmented lines represent a minor phase, and a dotted
line represents a trace mineral
albite (Fig. 13a). Igneous rocks generally display pervasive
alteration with complete replacement of plagioclase by albite
and commonly wholesale destruction of igneous mafic min-
erals by chlorite. Veinlets of massive albite up to 1 cm in width
are common in intrusive rocks. Sedimentary rocks generally
display selective replacement of fine-grained beds by albite or
albite and chlorite, where albite replaces plagioclase and chlo-
rite replaces amphibole and pyroxene. In conglomerate and
volcanic breccias, albite replaces the matrix and/or forms rims
around clasts.
Sodic–calcic alteration
Sodic alteration associations were overprinted by sodic–calcic
alteration associations of albite, epidote, actinolite, titanite,
scapolite, and minor apatite. The area affected by sodic–calcic
alteration is more restricted than that affected by sodic alter-
ation. As with sodic alteration associations, sodic–calcic alter-
ation formed textural and mineralogical differences related to
rock type.
The most common alteration minerals are epidote, actino-
lite, and albite. The most common mineral associations are
epidote–albite, actinolite–albite, epidote–actinolite–chlorite–
albite–(−titanite), and actinolite–scapolite–albite (Fig. 11). Al-
bite partially or totally replaces plagioclase. Epidote partially
Miner Deposita (2014) 49:235–259
replaces the cores of plagioclase, pyroxene, and hornblende
crystals. Actinolite replaces hornblende and pyroxene. Volcanic
rocks display pods of epidote grading outward to albite.
Breccias and conglomerates show clasts replaced by intergrown
epidote and albite, or surrounded by an albite rim. Thin-bedded
siltstone and sandstone are altered to albite and epidote zones
along bedding (Fig. 14b). Some siltstone samples show
irregular, <1-mm-wide epidote veinlets that cut across
albite-altered beds to connect parallel epidote-altered beds.
Intrusions contain epidote veinlets with albite selvages or
pseudo-breccia textures formed due to irregular replacement
of the rock by albite, actinolite, and chlorite. Subhedral dis-
seminated magnetite (1–5 %) is commonly present in sodic–
calcic alteration associations, and it is often partially to totally
martitized. Intense sodic–calcic alteration with scapolite is
restricted to zones within the leucodiorite intrusion located
in the Romero area.
Potassic alteration
Potassic alteration assemblages are present in the El Espino,
Romero, and Llahuin areas. These assemblages are locally
and weakly developed and/or highly affected by subsequent
calcic and hydrolytic alteration. Subsequent alteration of po-
tassic assemblages has commonly resulted in biotite altering
Miner Deposita (2014) 49:235–259 247

Fig. 12 Alteration map of El Espino mining district

Fig. 13 Outcrop photographs

showing examples of alteration.
a Sodic alterated rock as albite
stockwork veinlets in quartz
diorite from Caimanes–Illapel
pluton. b Sodic–calcic altered red
sandstone from Romero area with
some beds partially altered to
albite and epidote
248
Fig. 14 Photographs showing
examples of potassic alteration.
a b
K-spar potassium feldspar, bt
biotite, chl chlorite, mt magnetite.
a Hand sample of sandstone from
El Espino prospect with bt + mt
disseminated secondary biotite
and magnetite alteration
assemblage. b Hand sample of
andesite from El Espino prospect
with K-feldspar and chlorite
cal
alteration association.
c Photomicrograph (crossed c d
polars) showing leucodiorite
from Romero area replaced
mostly by K-feldspar and lesser
epidote and biotite. Primary
plagioclase is replaced by
K-feldspar and biotite.
d Photomicrograph (crossed
polars) showing secondary
biotite replaced by chlorite
to chlorite and potassium feldspar generally being replaced by
sericite, clays, and chlorite; potassium feldspar is more com-
monly preserved than biotite. Potassium feldspar either re-
places original plagioclase or replaces albite formed during
earlier sodic or sodic–calcic alteration.
Secondary biotite accompanied by disseminated subhedral
magnetite was found in several deep drill holes at the El
Espino deposit (Fig. 14a). The style of alteration is typical of
that observed in other Chilean IOCG deposits such as
Candelaria (Marschik and Fontbote 2001). However, its ex-
tent is poorly constrained. Potassic alteration assemblages
containing potassium feldspar, commonly with hematite
(Fig. 14b), are most common in the El Espino district. The
age relationships between the biotite-bearing and potassium
feldspar-bearing potassic assemblages are currently unclear.
While it is possible that the different potassic mineral assem-
blages simply represent originally different protolitths (Barton
and Johnson 1996), they may also represent fundamentally
different assemblages formed at different times and in differ-
ent structural levels.
Volcanic and intrusive rocks affected by potassic alteration
contain interstitial metasomatic potassium feldspar. In pyro-
clastic and sedimentary rocks, potassium feldspar partially or
totally replaces albite either in the matrix or in previously
altered fragments. Potassium feldspar alteration is selective,
forming bands in thin bedded siltstone or rims around clasts.
Locally, potassium feldspar has pervasively replaced all the
primary minerals in clastic sedimentary rocks.
The eastern side of Romero area displays extensive evi-
dence of potassic and potassic–calcic alteration. A conglom-
erate of the Quelen Member in the Romero area contains
rounded pods (3–5 cm diameter) of epidote grading outward
to interstitial pink potassium feldspar as haloes around the
Miner Deposita (2014) 49:235–259
K-spar
2 cm 2 cm
K-spar
bt bt
chl
200 m 200 m
pods. Some pods have specular hematite in their centers. The
least altered leuco-monzonite sample located at medium ele-
vations in this area displays interstitial potassium feldspar
(10 % of the rock), disseminated magnetite, and ferromagne-
sian minerals that are replaced by actinolite and chlorite. A
more altered sample displays secondary biotite and potassium
feldspar. Potassium feldspar replaces plagioclase phenocrysts
and is commonly intergrown with minor biotite, actinolite,
epidote, and/or chlorite (Fig. 14c, d). Secondary biotite
accompanied by disseminated subhedral magnetite was
found deep at El Espino deposit (few meters of core) and
its distribution is unclear.
Calcic alteration
Calcic alteration affected a northwest-trending area of approx-
imately 25 km2 extending from the El Espino deposit to the
Romero prospect (Fig. 12). Calcic alteration mineral associa-
tions contain epidote, actinolite, and chlorite with lesser calcite,
titanite, apatite, and quartz and minor garnet (andradite) in
calcareous sedimentary rocks. The most common calcic alter-
ation associations are epidote–actinolite and epidote–chlorite
(Fig. 15a). A first stage of calcic alteration is characterized by
partial replacement in volcanic rocks and pervasive replace-
ment in sedimentary rocks that locally obliterates their primary
texture. Calcic alteration epidote replaces igneous feldspar
and mafic minerals and cuts hydrothermal albite and potassi-
um feldspar. Epidote occurs as both fine-grained anhedral
aggregates and well-developed crystals up to 10 mm in length.
It occurs as veinlets, disseminations, or massive replacements
of the rock. Actinolite occurs as acicular aggregates with
crystal lengths averaging 0.5–1 cm, but ranging up to 5 cm;
it is commonly disseminated but locally can pervasively
Miner Deposita (2014) 49:235–259 249

replace host rocks. Chlorite replaces igneous ferromagnesian
minerals as well as hydrothermal actinolite and biotite. Epi-
dote and actinolite associations, sometimes with calcite, are
accompanied by abundant magnetite or less frequently hema-
tite (Fig. 15b). These mineral associations may contain mag-
netite, ilmenite, pyrite, and chalcopyrite with minor
bornite and covellite (Fig. 15c, d). Sulfides replace iron
oxide minerals or form minute inclusions in quartz
(Fig. 15c, d). Minor chalcopyrite, bornite, pyrite, and
native gold, together with acicular actinolite, were found
in quartz grains around or within replacive epidote–actinolite
pods. Chalcopyrite either formed later as inclusions in idio-
blastic pyrite (Fig. 15e, f) or as partial replacement of
pyrite.
A second stage of calcic alteration is characterized by iron
oxide- and sulfide-bearing veinlets with actinolite selvages
that cut earlier calcic, sodic–calcic, and sodic alteration asso-
ciations. These veinlets range in width from 1 to 10 mm and
contain actinolite, epidote, and quartz with either magnetite or
specular hematite and pyrite and chalcopyrite. Specular he-
matite in some veinlets has been replaced by mushketovite
(magnetite pseudomorphs of hematite) related to carbonate
deposition. Many of the veins display actinolite selvages that
are commonly 5–10 mm wide. Some actinolite selvages grade
outwards to epidote with minor intergrown chlorite.
Calcic alteration associations also occur in specular
hematite-bearing breccias found at low elevations within
the leuco-monzonite unit in the Romero prospect area.
These breccias contain fragments replaced by albite, scap-
olite, potassium feldspar, or quartz in a matrix of actino-
lite with specular hematite and disseminated chalcopyrite
and pyrite.
Hydrolytic alteration
Hydrolytic alteration associations occur within hydrothermal
breccia zones, around a mineralized manto body at the El
Espino deposit, and in veins (Fig. 16a, b). Hydrolytic
alteration associations contain variable amounts of quartz,
calcite, sericite (illite and phengite), chlorite, iron oxide
minerals, dominantly hematite, and sulfides (Fig. 16a–d);
some hydrolytic associations contain minor rutile and Na–
Fe tourmaline. Hydrolytic alteration associations contain the
vast majority of sulfides in the El Espino mining district.

Fig. 15 Photomicrographs a b
showing examples of calcic
alteration associations. ab albite, hm
act actinolite, cal calcite, epi act ab cal
epidote, qz quartz, hm specular
hematite, mt magnetite, bn hm
bornite, cpy chalcopyrite, py epi
pyrite. a Conglomerate from epi
Romero area replaced by act
actinolite and epidote
overprinting earlier albite. 1 cm 1 mm
b Same conglomerate as A
showing actinolite, epidote, c d
cal
calcite, and hematite (crossed epi cal
polars). c Conglomerate from bn epi
bn
Romero area showing quartz with
hm hm
inclusions of acicular actinolite
cpy
crystals and opaques (crossed
polars). d Same as f, but with
reflected light showing that
opaques are bornite and qz qz
chalcopyrite replacing hematite.
e Mineralized sandstone from El act 100 m hm act 100 m
Espino area showing pyrite and
chalcopyrite (reflected light). e f mt
f Pyrite and chalcopyrite
replacing magnetite in siltstone
from El Espino deposit
pervasively altered to actinolite qz
and minor epidote (reflected light)
py
cpy
py cpy
act
mt
100 m 100 m
250 Miner Deposita (2014) 49:235–259

Hydrolytic stage hydrothermal breccias are found at the El
Espino, Romero, and Llahuin areas. These hydrothermal brec-
cias contain fragments with muscovite replacing earlier
formed alteration minerals such as albite and potassium feld-
spar in a matrix of chlorite and specular hematite.
Alteration zones adjacent to El Espino manto commonly
contain a white mica–chlorite–specular hematite assemblage.
Both hydrothermal breccias and mantos are commonly
overprinted by 1–2 cm wide veinlets of specular hematite,
minor quartz, and chalcopyrite.
Three stages of hydrolytic alteration/mineralization were rec-
ognized from cross-cutting vein relationships. The earliest veins
contain quartz and sulfides. These are cut by veins containing
hematite and sulfides with variable amounts of quartz (Fig. 16d).
The hematite-sulfide veins have well to poorly developed sel-
vages of white mica and chlorite. The latest veins are composed
of quartz, calcite, sulfide and minor iron oxide (Fig. 16c).
Hydrolytic alteration assemblages commonly contain
chalcopyrite, pyrite, and specular hematite. Sulfides and
hematite at the El Espino deposit occur in veins and within
a manto within a favorable fine-grained volcaniclastic
unit of the Espino Member. Pyrite and chalcopyrite are
coexisting with chalcopyrite formed later replacing pyrite
(Fig. 16e, f). Minor amounts of bornite, galena, and
hypogene chalcocite are present locally as replacements
of chalcopyrite. Trace native gold is present as inclusions
in chalcopyrite.
Calcite veins and argillic alteration
The final hypogene alteration and mineralization event in
the Espino district resulted in the formation of calcite–
barite–(quartz) veins that may contain chalcopyrite, pyrite,
and/or galena. These veins have selvages composed of various
combinations of chlorite, quartz, calcite, illite, clinochlore,
montmorillonite, and laumontite. Thick veins of this have
been exploited by small miners for copper and locally silver,
presumably hosted in the galena. These veins are distal to the
main zones of hydrolytic alteration and mineralization and
occur found at higher elevations in the Llahuin and north of El
Espino deposit areas.
Supergene alteration and mineralization
Weathering of sulfide-rich associations in the El Espino
district has resulted in the formation of supergene copper

Fig. 16 Photographs showing a b

hydrolytic alteration associations.
cal calcite, chl chlorite, cpy chl
chalcopyrite, hm specular cpy cpy
hematite, qz quartz, py pyrite, ser py
sericite. a Hematite-sulfide hm
hm py ser
veinlet with chlorite selvages in
sandstone from Romero area.
b Breccia within 1 m wide vein in
chl
Romero area, showing massive
chalcopyrite accompanied by 2 cm 1 cm
chlorite and sericite and cut by
hematite veinlet. c Calcite– c ser d py
chalcopyrite veinlet in diorite
ser+chl
from El Espino deposit hm1
overprinting specular hematite– chl cal
sericite–chlorite–quartz veinlet. qz
d Veinlet in sandstone from El ser
Espino deposit showing two hm2
hm qz
stages of hematite, the first shows chl
actinolite altered to chlorite and cpy
the second shows sericite, quartz 2 cm
hm 2 cm
and minor chlorite (reflected
light). e Mineralized sandstone
from Romero area showing e f
chalcopyrite inclusions in pyrite cpy
cpy hm
(reflected light). f Mineralized
sandstone from El Espino deposit py
showing chalcopyrite after pyrite cpy
(reflected light)
py

py
Miner Deposita (2014) 49:235–259
oxides and limited amounts of supergene chalcocite. Supergene
alteration also resulted in the formation of clays. Supergene
alteration has been observed along fault zones and is particu-
larly well developed along the Tamara fault zone (Fig. 6).
Vertical and lateral distribution of alteration
and mineralization
Alteration assemblages in the El Espino mining district
display a distinct vertical and lateral zonation (Fig. 17). Both
the El Espino and Romero prospects contain areas at low to
intermediate elevations (1,000–500 m deep from Llahuin
area) that contain sodic alteration assemblages that have been
overprinted by sodic–calcic, potassic, and calcic alteration
assemblages. The generally high elevation Llahuin area
contains well-developed hydrolytic alteration assemblages.
Hydrothermal alteration was centered on high angle faults
with alteration generally decreasing in intensity and complexity
outward from these structures.
Sodic alteration affected over 100 km2 in the district. Sodic
alteration was most intense along north–south- and NE-
trending regional lineaments (Fig. 12). Sodic alteration is best
developed at low elevations and only minor zones of sodic-
altered rocks are found at higher elevations, primarily in the
Llahuin area. Sodic–calcic altered zones are spatially more
restricted than sodic-altered rocks and cover an area of
approximately 50 km2. Sodic–calcic altered rocks surround
dioritic intrusions located in the southern end of the Llahuin
plutonic suite and are present in structural zones within and
between the Espino and Romero areas. Sodic–calcic altered
zones are best developed at low to medium elevations (1,000–
500 m deep from Llahuin area) but may extend to higher
elevations in the Llahuin area and in the very far north of
the district.
Calcic altered rocks occur primarily in an area 5 km long×
2 km wide from El Espino deposit on the west to the Romero
area on the east (Fig. 12). Calcic altered rocks occur at low
Fig. 17 Schematic EW cross-
section showing vertical
distribution of alteration types in
the El Espino mining district.
Note that intense calcic alteration
was confined largely to mixed
volcanic and sedimentary rocks
adjacent to the mostly sodically
and lesser potasically altered
Llahuin pluton. The location of
the section is illustrated in
figure 11. Mineral abbreviations:
act actinolite, chl chlorite,
hm specular hematite, ser sericite,
tm tourmaline
251
elevations (1,000–800 m depth from Llahuin area) in the El
Espino deposit area and at medium to low elevations (1,000–
500 m depth) in the Romero area. While surface exposures of
calcic-altered rocks contain minor specular hematite or mag-
netite, pyrite, and traces of chalcopyrite, deep exposures of
this alteration type at the El Espino deposit contain zones of
massive magnetite cut by specular hematite veins with locally
significant amounts of pyrite and chalcopyrite.
Potassic-altered rocks occur as small zones both within and
outside zones of sodic alteration (Fig. 11). Potassically altered
rocks are found at both low (El Espino) and high (Llahuin)
elevations. Extensive zones with hydrothermal potassium
feldspar are common present within intrusions in the Llahuin
area. Hydrothermal biotite accompanied by K-feldspar occurs
deep at the eastern margin in the Romero area. Hydrothermal
biotite at the Romero prospect area appears to have been more
widespread but was almost completely replaced by later calcic
and hydrolytic alteration assemblages.
Hydrolitic alteration assemblages are most common at
medium to high elevations throughout the district. Hydrolytic
alteration is concentrated in veins that served as feeders for El
Espino manto deposit. Hydrolytic assemblages appear to
change mineralogy with depth. Iron oxide-rich hydrolytic
veins at El Espino and Romero grade upward into quartz veins
with little to no hematite at Llahuin. At the highest elevations
in the district, veins are dominated by argillic assemblages and
contain dominantly calcite and barite with minor argentiferous
sulfides..
Age of alteration and mineralization
The age of hydrothermal alteration and mineralization in the
El Espino district was investigated by Lopez (2012) through
40
Ar- 39 Ar isotopic analysis of hydrothermal minerals
(Table 1). Analysis of potassium feldspar, separated from an
irregular calcite vein developed within a potassically altered
biotite–magnetite assemblage from deep within the Espino
252
deposit, yielded an age of 86.09±0.45 Ma (Table 1). Analysis
of actinolite, from a calcic alteration veinlet containing chal-
copyrite, actinolite, epidote, and minor magnetite at the El
Espino deposit, yielded an age of 88.4±1.2 Ma (Table 1). The
age of the hydrolytic alteration was determined from
40
Ar–39Ar analyses of white micas (Table 1). Analysis of
white mica from a core sample with a hydrolytic quartz-
sulfide veinlet at El Espino yielded an inverse isochron age
of 87.9±0.6 Ma (Table 1). White mica from a specular hema-
tite veinlet at Espino yielded a similar plateau age of 87.9±
0.6 Ma (Table 1).
Geochronological U–Pb and 40Ar/39Ar data indicate that
hydrothermal alteration was coeval with magmatic intrusive
activity. One particular dioritic intrusion (88.5 Ma) preceded
the calcic stage (88.4 Ma), which was accompanied by
iron oxide copper and gold mineralization. Hydrolytic
alteration, related to economic iron oxide copper and gold
mineralization, came immediately after at 87.9 Ma. It also
appears that hydrothermal alteration and mineralization
may have been accomplished in a short period of two to
three million years.
Sulfur isotopes of sulfides from calcic and hydrolytic
alteration associations
Sulfur isotopic analyses were performed on sulfide minerals
collected from calcic, hydrolytic, and late calcite vein associ-
ations across the district (Table 2). Samples were acquired
from a range of locations to investigate potential changes in
sulfur isotopic composition vertically and laterally within the
hydrothermal system. Single analysis of gypsum from the
Espino Member of the Quebrada Marquesa Formation yielded
a δ34S value of 12.4 ‰. Single analysis of diagenetic pyrite in
sedimentary rocks of Espino Member yielded a δ34S value of
−7.3 ‰.
Sulfides extracted from veins and rock replacements
related to calcic alteration yielded δ34S values between
−4.0 and +2.4 ‰, with a mean value around −1 ‰ (Figs. 18
and 19). Sulfides within hydrolytic altered rock yielded
δ34S values between −4.4 and +6.2 ‰, with a mean value
Table 1 40Ar/39Ar geochronology
data for alteration ages Sample Locality
ERD-6 247.4 Espino
ERD-6 128 Espino
ERD-6 142.3 Espino
EDH-3 246 Espino
Rab-01 Espino
179682 Romero
172261 Llahuin
Miner Deposita (2014) 49:235–259
around 0 ‰ (Figs. 18 and 19). Copper sulfide-bearing
veins lacking iron oxides yielded δ34S values between
−4.3 and +1.0 ‰, whereas sulfides from veins containing
iron oxide minerals yielded slightly higher δ34S values of
between −4.3 and +6.1 ‰. Sulfides within late stage
calcite veins are distinctively lower with δ34S values between
−4.8 and −9.7 ‰ (Fig. 18).
Although the sulfur isotopic values of pyrite and chalco-
pyrite in the calcic and hydrolytic associations overlap, there
are slight differences in isotopic compositions. Pyrite values
are generally higher and range from −2.2 to +6.1, whereas
chalcopyrite values range from −4.4 to +4.5 ‰. Some samples
with coexisting chalcopyrite and pyrite have significantly
different isotopic values, suggesting that chalcopyrite formed
by utilizing reduced sulfur in the hydrothermal fluid rather
than incorporating sulfur from pre-existing pyrite (Ohmoto
and Goldhaber 1997).
The wide range of sulfur isotope compositions are compat-
ible with two sources variably mixed, a sulfur source of δ34S
close to 0 ‰ and a sulfate source with variable degrees of
reduction. The sulfur isotope composition range related to
calcic alteration is relatively more restricted (range of 8 ‰)
with a mean near 0 ‰. That alteration surrounds a dioritic
intrusion. The relatively smaller range around 0 ‰ and
pattern of the alteration suggest a magmatic source for the
former of the fluids. Hydrolytic stage sulfur isotope ratios
show a wider range (11 ‰), generally higher than in the
calcic stage, suggesting incorporation of sulfur derived
from gypsum. High temperature reduction of sulfate
may have occurred during the convective circulation of
reduced magmatic hydrothermal fluids through the gyp-
sum beds of the Quebrada Marquesa Formation. Sulfur
isotope ratios in the late calcite veins suggest incorporation of
biogenic sulfur.
Hydrothermal sulfides in the district show a trend toward
higher sulfur isotope values with stratigraphic height in the
Quebrada Marquesa Formation (Fig. 20). The greatest
variability of sulfur isotopic values occurs within the lower
marine, locally gypsiferous sedimentary rocks of the Espino
Member with δ34S values ranging from −9.7 to +2.4 ‰,
whereas the sulfides in the overlying continental conglomerate
Material Age±2σ Ma Type Alteration type
Actinolite 88.4±1.2 Inverse isochron Calcic
Sericite 87.9±0.6 Inverse isochron Hydrolytic
Sericite 87.9±0.6 Plateau Hydrolytic
K-Feldspar 86.21±0.41 Plateau Calcite vein
Muscovite 98.9±2.2 Inverse isochron Hydrolytic
Muscovite 94.17±0.49 Total fusion Hydrolytic
Illite 91.71±0.47 Total fusion Hydrolytic
Miner Deposita (2014) 49:235–259 253

Table 2 Sulfur isotope data of mineralized rocks from El Espino mining district

Rock description Alteration and mineralization S isotopes

Sample Locality Host rock Morphology Mineralogy Alteration type Sulfide δ34S

EDH4-83 Espino Siltstone Siltstoneiron oxide–sulfide vein alb-act-chl-hm-mushk-cal-py-cpy Sodic–calcic py −1.51

ERD6-242 Espino Andesite Iron oxide–sulfide vein act-epi-calc-cpy-hm Calcic cpy −3.66
ERD9-137 Espino Sandstone Rock replacement epi-act-chl-py-cpy Calcic py −3.51
ERD4-174 Espino Sandstone Rock replacement epi-chl-mgt-cpy-py Calcic cpy −2.94
ERD4-174 Espino Sandstone Rock replacement epi-chl-mgt-cpy-py Calcic py −1.36
179694 Espino Siltstone Rock replacement epi-act-cpy-py Calcic cpy −1.26
ERD6-236 Espino Siltstone Rock replacement chl-cal-mgt-py-cpy Calcic py −0.89
ERD6-236 Espino Siltstone Iron oxide–sulfide vein act-qtz-cal-mushk-cpy-py Calcic py −0.83
ERD6-236 Espino Siltstone Iron oxide–sulfide vein act-qtz-cal-mushk-cpy-py Calcic cpy −0.06
ERD4-136 Espino Siltstone Rock replacement alb, epi-act-mgt-py-cpy Calcic py 0.27
179695 Espino Diorite Iron oxide–sulfide vein act-qtz-mgt-calc-py Calcic py 2.58
ERD5-165 Espino Calc. siltstone Calcite vein chl-ser-cal-cpy Calcite vein cpy −9.69
ERD7-179 Espino Siltstone Calcite vein calc-hm-cpy Calcite vein cpy −9.14
ERD6-83 Espino Diorite Calcite vein alb-act-chl-cpy (rock), calc (vein) Calcite vein cpy −4.73
172271 Llahuin Diorite Quartz sulfide–iron oxide vein chl-ser-qtz-calc-hm-cpy Hydrolytic cpy −4.30
ERD6-128 Espino Sandstone Quartz sulfide–iron oxide vein chl-ser-hm-mushk-qtz-calc-cpy Hydrolytic cpy −4.20
179553 Romero Leucodiorite Quartz vein chl-ser-hm-cpy-py Hydrolytic cpy −2.65
172252A Romero Conglomerate Quartz–iron oxide vein calc-qtz-chl-ser-hm-mushk-cpy Hydrolytic cpy −2.26
179682 Romero Conglomerate Iron oxide–sulfide breccia chl-calc-(ser)-cpy-py Hydrolytic py −2.00
ERD5-176 Espino Sandstone Rock replacement chl, calc-ser-mushk-cpy Hydrolytic cpy −1.79
179553 Romero Leucodiorite Quartz vein chl-ser-hm-cpy-py Hydrolytic py −1.59
179534A Romero Conglomerate Rock replacement chl-ser-mgt-hm-cpy Hydrolytic cpy −1.66
179534B Romero Conglomerate Iron oxide vein hm-chl-cpy Hydrolytic cpy −1.46
ERD5-176 Espino Sandstone Iron oxide–quartz vein chl-ser-cal-mushk-cpy Hydrolytic cpy −0.78
179550 Romero Diorite Rock replacement chl-ser-(hm)-py-cpy Hydrolytic py −0.29
179689 Espino Andesite Quartz vein chl-ser-hm-calc-py-cpy Hydrolytic py 0.59
179682 Romero Conglomerate Iron oxide–sulfide breccia chl-calc-(ser)-cpy-py Hydrolytic cpy 1.13
179515 Llahuin Diorite Quartz vein chl-ser-(hm)-cpy Hydrolytic cpy 1.04
EDH4-157 Espino Sandstone Iron oxide–sulfide vein chl-ser-mgt-py, hm-mgt-cpy Hydrolytic cpy 1.87
179696 Romero Conglomerate Iron oxide–sulfide vein chl-ser-hm-mgt-calc-cpy-py Hydrolytic cpy 4.60
179696 Romero Conglomerate Iron oxide–sulfide vein chl-ser-hm-mgt-calc-cpy-py Hydrolytic py 6.38
179534B Romero Conglomerate Iron oxide breccia hm-chl-cpy Hydrolytic cpy 0.87
179683 Romero Conglomerate Disseminated ser-clays-py, cpy veinlets Hydrolitic/argillic cpy 0.36
172255 Romero Diorite Quartz vein qtz-chl-py Hydrolytic py 4.22

Quelen Member have heavier values of −2.7 to +6.2 ‰.
These compositions suggest that isotopically heavy sulfur
was contributed to the hydrothermal fluids during upward
fluid migration.
Calculation of the precipitation temperature of coexisting
(i.e., textural equilibrium) chalcopyrite and pyrite in calcic
alteration associations using the method of Ohmoto and Rye
(1979) and Campbell and Larson (1998) yields temperatures
between 529 and 280 °C. Hydrolytic alteration sulfide yielded
temperatures of 216 °C (Table 3).
Fluid inclusion studies
Eight samples of quartz from veins with iron oxides and sulfides
were surveyed fluid inclusions suitable for microthermometric
study. Homogenization temperatures were collected only
from assemblages of inclusions that showed consistent
liquid to vapor volumetric proportions and that yielded
consistent results (Goldstein and Reynolds 1994). Such
assemblages of inclusions were very rare, perhaps because
of overprinting of hydrothermal events with concomitant
254
Fig. 18 Sulfur isotope 7
compositions of chalcopyrite and
pyrite organized by alteration
stages for calcic, hydrolytic, and 6
calcite veins. Calcite veins sulfide
correspond to chalcopyrite. Both
sedimentary gypsum and
5
diagenetic pyrite sulfur isotope
compositions are also included
for comparison
Frequency
4
3
0
-10 -9 -8 -7 -6
recrystallization of quartz and post-entrapment changes of
the fluid inclusions.
A core sample from Espino deposit (ERD-6, 79.2 m
depth), is a late calcic alteration stage quartz veinlet with
intergrown hematite and chalcopyrite in an amphibole
diorite host rock. The veinlet displays euhedral quartz
with no evidence of quartz annealing (Fig. 21), though
the sample did contain many fluid inclusion assemblages
(FIAs) with inconsistent liquid to vapor ratios. The FIAs
measured were intimately associated with tiny specular
hematite and acicular actinolite solid inclusions within
quartz and thus are deemed primary in origin. These
primary inclusions contain transluscent halite crystals. Three
FIAs yielded consistent homogenization temperatures (T h)
between 280 and 295 °C. Salinities were between 32 and
34 wt% NaCl equivalent. No other FIAs at higher T h were
found in this vein sample.
A second core sample from a calcically altered siltstone
deeper in the El Espino deposit (ERD-6, 236.8 m depth)
contains an actinolite and magnetite assemblage that is
overprinted by a second alteration association composed of
calcite, quartz, mushketovite, chalcopyrite, sericite, and
chlorite. Euhedral quartz associated with the second calcic
alteration association is intergrown with acicular fibers of
actinolite and contains growth zones along the margins of
the vein. Liquid/vapor ratios were not consistent in these
inclusions due to necking; however, salinities from these
primary inclusions yield ∼15 wt% NaCl equivalent.
Sample number 179689 is from an intermediate elevation
north of the El Espino deposit. This sample contains a mineral
Miner Deposita (2014) 49:235–259
Calcite veining
Hydrolytic alteration
Calcic alteration
Diagenetic pyrite
Gypsum
-5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12
34S (o/ )
oo
association of quartz, pyrite, chalcopyrite, specular hematite,
epidote, actinolite, chlorite after actinolite, and sericite. Most
FIAs hosted by quartz show inconsistent liquid/vapor ratios,
but one FIAwas found that yielded consistent homogenization
temperatures at 340–350° C.
As there is no evidence of brine-vapor immiscibility in all
samples surveyed, T h only provides a minimum temperature
of formation conditions. A pressure correction must be ap-
plied to get the true formation conditions. Although the depth
of formation is unknown, sample 179689 displays textures
such as wispy inclusion texture and recrystallized quartz in-
dicative of formation under lithostatic conditions (Reynolds,
2012, personal communication). If a 350 °C temperature is
pressure corrected to 425 °C (assuming that ductile deforma-
tion styles would occur at such temperatures under lithostatic
load), then the pressure required would be roughly 700–1,000
bars for a saline brine, corresponding to a minimum depth of
formation of roughly 3–4 km, consistent with the estimated
thickness of the Late Cretaceous lithostatic load (Salamanca
Formation) in the area.
Discussion
Early sodic alteration (albite) was the most aerially extensive
and external alteration event in the district and is spatially
related to the Llahuin and Illapel–Caimanes plutons especially
along major fault zones and lineaments within and around
these plutons. Although best developed at stratigraphically
deep levels, i.e., ∼1,000 m deep from the top of the alteration
Miner Deposita (2014) 49:235–259 255

exposed higher in the Llahuin area, the sodic alteration as-
semblage extends upward in the El Espino mining district to
the near surface in Espino and Romero areas where it gener-
ally seems to transition into a sodic–calcic assemblage com-
posed of albite and epidote. Although some units of Llahuin
suite are affected by pervasive sodic alteration, other units
such as a diorite pluton and sills in the Espino deposit are not
affected by this alteration, whereas other units higher in the
Llahuin area show albite veining which might have developed
later. The distribution of intense sodic alteration is compatible
with it being developed within inflow zones to the broad
hydrothermal system, as proposed by Barton and Johnson
(2000) for a number of IOCG systems.
Sodic–calcic alteration (albite–epidote–actinolite) is
relatively spatially more restricted than sodic alteration and
grades into a center of calcic alteration assemblages (actino-
lite–epidote–iron oxide) displaying a zoned pattern around the
southern end of the Llahuin Pluton.
Potassic alteration in the El Espino district is relatively
restricted in extent. Deep, biotite–magnetite assemblages,
similar to those at Candelaria, are present but are poorly
known due to a lack of deep drilling. Higher level potassium

Fig. 19 Sulfur isotope a

compositions for pyrite and 4
chalcopyrite in a calcic and b Calcic
hydrolytic alteration associations

pyrite
3

chalcopyrite
Frecuency

0
-8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8
34S (o/
oo)

b 7
Hydrolytic
6

pyrite
5
chalcopyrite

4
Frecuency

0
-8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8
34S (o/
oo)
256 Miner Deposita (2014) 49:235–259

Fig. 20 Sulfur isotope 9

compositions organized by
location and therefore, 8
stratigraphic level. El Espino
sulfides occur in the Espino
7 Llahuin (n=2)
Member, whereas Romero
sulfides occur stratigraphically Romero (n=13)
higher in the Quelen Member 6
Espino (n=20)
5

Frecuency
4

0
-10 -9 -8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6 7 8 9 10
34S ( o/
oo)

feldspar-bearing potassic assemblages are better developed at medium levels (i.e., 1,000–500 m deep from the top of the
the current level of exposure of the system. Cross-cutting exposed alteration in the Llahuin area). The calcic alteration
relationships suggest that potassium feldspar-bearing as- assemblage extends upward and outward transitioning into a
semblages cut early sodic alteration assemblages but were sodic–calcic assemblage dominated by albite–actinolite–
locally formed synchronous with potassic–calcic altered epidote(−scapolite). Significant amounts of iron oxides are
rocks. In the Romero area, spatially restricted potassic– associated with calcic alteration assemblages. Geochronolog-
calcic zones developed within the calcic area that are related ical data indicate that calcic alteration was synchronous with
to iron oxide mineralization. However, potassic alteration intrusive magmatic activity in the district.
zones do not always display a close spatial relationship to Hydrolytic alteration assemblages (chlorite–sericite–
sodic, sodic–calcic, and calcic alteration zones. The spatial quartz–hematite) in the El Espino district occur along faults
and temporal distribution of potassic alteration zones could and veins. These asemblages are best developed at medium to
be evidence that they developed as outflow zones as is high stratigraphic levels, i.e., 500 to 0 m deep from the top of
hypothesized for several other IOCG districts (Barton and the exposed alteration in the Llahuin area. Although many
Johnson 2000). hydrolytic zones cut rocks that were previously sodic, sodic-
The calcic alteration zone forms the core of the large-scale calcic, or calcic altered, some hydrolytic alteration zones
alteration system in the district. It postdates sodic alteration, occur in relatively unaltered rocks along mineralized veins.
but is probably gradational in time and space with sodic– Hydrolytic veins are feeders to a zone of manto-type alteration
calcic and locally potassic–calcic alterations. The calcic and mineralization within favorable volcano-sedimentary
alteration zone is best developed at stratigraphically deep to lithologies in the El Espino deposit. Sulfides (pyrite and
chalcopyrite) are largely confined to calcic and hydrolytic
alteration assemblages.
Table 3 Estimates of the sulfur isotope fractionation temperature derived The paragenetic sequences in the El Espino and Candelaria–
from sulfur isotope compositions of coexisting chalcopyrite and pyrite for Punta del Cobre IOCG districts are distinct. The economic iron
each alteration type {T(°K)=[(0.45×106)/(δ34Spy −δ34Scpy)]1/2
oxide and sulfide mineralization are related to calcic–potassic
Location Sample δ34Spy (‰) δ34Scpy (‰) Alteration T (°C) alteration zones in Candelaria (Marschik and Fontbote 2001),
stage while in El Espino, the bulk of the iron oxide and copper
mineralization occurs with hydrolytic alteration. Alteration
Espino ERD6-236 −0.31 −1.01 Calcic 1st 523
stage
distribution and paragenesis for the early and late alteration
Romero 179553 −1.58 −2.36 Calcic 1st 486 stages in the El Espino district is similar to that seen in the
stage Manto Verde district in northern Chile (Benavides et al. 2007).
Espino ERD4-174 −1.43 −3.01 Calcic 2nd 261 Both districts show regional albitization and then local hydro-
stage
Romero 179696 6.37 4.50 Hydrolytic 218
lytic alteration related to economic iron oxide and sulfide
mineralization.
Miner Deposita (2014) 49:235–259
Fig. 21 Photomicrographs
showing quartz growth zones
with primary inclusions (a) and
primary inclusions coexisting
with acicular actinolite crystals
within quartz growth zones (b)
Extensive potassium and iron metasomatism was not seen
in El Espino mining district as it has been described for other
deposits such as Candelaria and Raul Condestable (Marschik
and Fontbote 2001; de Haller 2006). In the El Espino mining
district, potassic metasomatism occurred only locally in the
Espino, Romero, and Llahuin areas, within or outside sodic,
sodic–calcic, and calcic altered areas. Isolated small zones of
potassium feldspar and magnetite were even identified in the
Arqueros formation to the west of the district sometimes
spatially related to dioritic intrusions.
The host rocks, paragenetic sequence, and alteration pat-
terns at El Espino and the Raul-Condestable district in Peru
(de Haller 2006) are very similar. At Raul-Condestable, the
calcic alteration zone is developed in a volcanic and sedimen-
tary sequence and grades upward into a hydrolytic zone and
outward into a sodic–calcic zone. In both districts iron oxide
and sulfide mineralization are related to calcic and hydrolytic
stages of hydrothermal alteration (de Haller et al. 2006). The
potassic core (biotite) described at Raul-Condestable is either
weakly developed or not exposed in the El Espino district.
Extensive biotite alteration might have taken place in the
Romero area, but it has been masked by the later pervasive
and extensive chloritization. There is surface evidence of
secondary biotite in that area which is overprinted by either
calcic or hydrolytic assemblages. The core of the alteration
pattern at El Espino district is given by the calcic alteration
zone, dominated by actinolite, epidote, iron oxide, and sulfide.
This type of alteration is mineralized and pervasive in Raul-
Condestable deposit where it surrounds a potassic core
(secondary biotite) related to tonalite intrusions (de Haller
2006), suggesting that a potassic core in El Espino district
might be still unexposed beneath the Llahuin area and that
significant undiscovered deposits may exist in calcic-altered
zones deeper within the system.
Sulfur isotopic compositions of sulfides in calcic assem-
blages show a wide range of values with a mean near 0 per
mile (Fig. 18) that may be interpreted as consistent with a
mixture of two sources, one magmatic and one external with
variable mixing. The alteration pattern and timing of alteration
and magmatism suggests that dioritic intrusions played a role
in the formation of the system providing heat, fluid, and
257
probably sulfur. This magmatic source might have progres-
sively mixed with a sulfate-derived source. In contrast, in
hydrolytic assemblages, sulfur isotopic compositions of sul-
fides show a much wider spread, more clearly suggesting the
involvement of a sulfate-derived source. Under the moderate
temperature, relatively oxidizing conditions indicated by the
mineralogy and fluid inclusions, marine sulfate is likely to be
an important sulfur source in the hydrothermal system. The
individual data sets of sulfur isotopic compositions show wide
spreads, and the coexisting minerals (as indicated in the para-
genesis) show that most formed with iron oxide, especially
hematite. All this evidence is consistent with partial reduction
of heavy marine sulfate. This is what is observed in other areas
such as Raul-Condestable (de Haller 2006) and modern Salton
Sea geothermal system in Southern California. The close
spatial and temporal association of well-altered zones with
generally intermediate composition intrusions suggests that
part of Llahuin plutonic suite (including possible unexposed
plutons) probably provided heat and contributed fluid and
sulfur early to the hydrothermal system, but the bulk of iron
oxide, copper, and gold mineralization occurred relatively late
in the system by mixing with a fluid containing marine-
derived sulfate.
Estimates of the sulfur isotope fractionation temperature
show a wide range. These estimates assume that sulfur isotope
fractionation factors are correct and that samples analyzed did
not have microscopic inclusions of another sulfide. The esti-
mation of fluid temperature indicated by the high quality fluid
inclusion study performed seems to better represent the con-
ditions of the fluids responsible for iron oxide, copper, and
gold precipitation. The fluid responsible for specular hematite
and sulfide mineralization in El Espino deposit was saline and
moderate temperature, which is consistent with results
obtained by Rieger et al. (2012) for the Manto Verde district.
Homogenization temperatures (T h) measured in El Espino
quartz hosted inclusions within veins containing hematite
were between 280 and 350 °C, consistent with quartz hosted
inclusions related to hematite formation in Manto Verde,
which were in the range between 208 and 470 °C (Rieger
et al. 2012). Early magnetite formation in quartz fluid inclu-
sions at Manto Verde deposit occured around 435 °C and
258
reached up to 530 °C (Rieger et al. 2012), suggesting that
calcic alteration related to massive magnetite formation
may have occurred at that similar range of temperature at
El Espino district.
Conclusions
The paragenetic sequence and structural/stratigraphic controls
of alteration and mineralization are similar to those observed
at a number of other Andean IOCG systems. As is typical of
many Andean systems (Sillitoe 2003), an early large-scale
sodic alteration event was followed by a complex series of
sodic–calcic, potassic, and calcic alteration events, which in
turn were followed by a late, and generally high-level hydro-
lytic alteration stage. As at a number of other Andean systems,
sulfide precipitation in the El Espino mining district took place
with calcic and hydrolytic associations. Unlike the Candelaria
(Marschik and Fontbote 2001) and Raul-Condestable deposits
(de Haller et al. 2006), where the bulk of sulfides formed with
calcic–potassic and calcic alteration associations, respectively,
the majority of the sulfides currently observed at El Espino
district deposits occur in hydrolytic alteration associations
overprinting calcic alteration.
Iron oxides in the El Espino district display a general tem-
poral trend from early magnetite associated with sodic, sodic–
calcic, potassic alteration, and early calcic to later hematite
associated with calcic and hydrolytic alteration. This overall
change in mineralogy may reflect declining temperature of
hydrothermal fluids through time or a progressive increase of
the oxidation state of the fluids, perhaps due to fluid mixing with
a more oxidized, meteorically derived fluid. The presence of
mushketovite with some calcic alteration mineral associations
may reflect a late temperature increase during an overall cooling
trend or a change to slightly more reducing conditions during an
overall higher oxidation trend.
The El Espino mining district appears to lack bodies of
massive magnetite–apatite that are present at a number of
Andean deposits including Manto Verde (Rieger et al. 2010)
and the Marcona-Mina Justa deposits in Peru (Chen et al.
2011). Such deposits may be absent or may be present below
the current level of erosion.
Hydrothermal fluid flow in the El Espino mining district
was channeled along high angle, brittle faults and related
extension fractures that developed in a right-stepping jog
locally along a major north-striking dextral fault system.
Mantos were developed within the mixed volcano-sedimentary
sequence of the district, particularly beneath relatively imper-
meable limestone beds. Mineralized breccias along structures
and particular beds are locally present in the El Espino district
but are not well developed at the current level of erosion.
Distal, hydrolytic, and argillic stage calcite–barite veins with
Miner Deposita (2014) 49:235–259
minor copper and silver are interpreted to represent the
highest-level expression of the hydrothermal system.
Fluid inclusion provides evidence of a minimum fluid
temperature of 425 °C (pressure corrected) and minimum
depth of formation of 3–4 km for the formation of quartz–
hematite–actinolite veins related to the second stage of calcic
alteration. Sulfur isotopes, alteration mineralogy, alteration
patterns, and timing of magmatism and alteration suggest that
early high temperature magmatically derived fluids were
mixed with cooler, saline, oxidized fluids that included
marine-derived sulfate. The close spatial and temporal associ-
ation of well-altered calcic zones with generally intermediate
composition ∼88 Ma intrusions suggests that these plutons
could have provided both heat and fluid in the early stage of
the IOCG system.
The Andean IOCG systems in Chile generally become
younger to the south. Manto Verde’s age range between 123
and 117 Ma, Candelaria–Punta del Cobre has been constrained
to 116–110 Ma (Sillitoe 2003), whereas El Espino deposit, with
an apparent age of approximately 88 Ma, represents one of the
youngest and southernmost systems yet defined. The relatively
shallow level of erosion of the El Espino system compared to
older systems farther north in Chile suggests that significant
undiscovered deposits may exist in calcic-altered zones deeper
within the system.
Acknowledgements This work was supported by the National Science
Foundation project EAR-0207217. Assistance from Teckcominco for
field work logistics and chemical rock analysis and assistance from John
Humphrey and Jim Reynolds (Fluidinc) on the sulfur isotope and fluid
inclusion studies, respectively, are gratefully acknowledged. GPL also
acknowledges invaluable help from the Society of Economic Geologists
through Terrones and McKinstry student research grants, from a
Newcrest Resources Economic Geology Fellowship, and from Sarah
Gleeson (University of Alberta) for discussions and access to facilities.
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