Economic Geology, v. 112, pp.

295318

Contrasting Tectonic Settings and Sulfur Contents of Magmas Associated with

Cretaceous Porphyry Cu Mo Au and Intrusion-Related Iron Oxide Cu-Au Deposits
in Northern Chile*
Jeremy P. Richards,1, Gloria P. Lpez,1 Jing-Jing Zhu,1,2 Robert A. Creaser,1 Andrew J. Locock,1 and A. Hamid Mumin3
1 Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, Alberta T6G 2E3, Canada
2 State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, PR China
3 Department of Geology, Brandon University, 270-18th Street, Brandon, Manitoba R7A 6A9, Canada

Abstract
Porphyry Cu Mo Au and iron oxide copper-gold (IOCG) deposits share many similarities (e.g., Fe, Cu,
and Au contents), but also have important differences (e.g., the predominance of sulfide minerals in porphyry
deposits and iron oxides in IOCG deposits). Genetic comparisons are complicated by the broad definition of
IOCG deposits; here we restrict our study to IOCG deposits that are related to igneous intrusive systems. In
the Mesozoic Coastal Cordillera of northern Chile, both porphyry and IOCG deposits occur in close spatial and
temporal proximity, offering the chance to examine what controls their different modes of formation. From
detailed examination of the timing, geochemistry, and tectonic setting of associated igneous rocks, based on
new and published data, we find that rocks associated with mid-Cretaceous IOCG deposits (~125110 Ma) are
largely indistinguishable from those associated with slightly earlier (>125 Ma) and later (<110 Ma) porphyry
Cu Mo Au deposits. Magmas related to IOCG deposits were formed during a brief period of back-arc
transtension in the mid-Cretaceous and are, on average, somewhat more mafic (dioritic), locally alkaline, and
isotopically primitive compared to granodioritic magmas associated with porphyry deposits formed during nor-
mal contractional arc tectonics in the later Cretaceous. However, these compositional ranges overlap, and the
differences are not clear enough to be diagnostic.
We measured the SO3 content of igneous apatite from selected samples of these rocks to test the hypothesis
that the difference in sulfur content of the ore deposits was due to differences in sulfur content of the associated
magmas. Early igneous apatite crystals occurring as inclusions in silicate phenocrysts from the Carmen de And-
acollo porphyry Cu-Au deposit (Re-Os molybdenite ages of 103.9 0.5 Ma, 103.6 0.5 Ma) are significantly
richer in S (0.25 0.17 wt % SO3, n = 69) than similar apatite crystals from two IOCG deposits (Candelaria,
Casualidad) and a sample of regional mid-Cretaceous igneous rock from near Productora (0.04 0.02 wt %
SO3, n = 76). Using published partition coefficients for S between apatite and oxidized silicate melt, we semi-
quantitatively estimate corresponding magmatic sulfur contents of ~0.02 wt % S in the Carmen de Andacollo
magmas versus ~0.001 to 0.005 wt % S in the IOCG-associated magmas. This is an order of magnitude dif-
ference, and the opposite of what would be expected if the difference were due to bulk magma composition
(sulfur solubility is generally higher in mafic magmas, whereas here the S content is higher in the more felsic
porphyries). We conclude that the porphyry-forming magmas indeed had higher S contents than the IOCG-
related magmas and suggest that these differences reflect different petrogenetic processes. During normal sub-
duction, magmas derived from the metasomatized mantle wedge are hydrous, moderately oxidized, and S rich,
and have the potential to generate S-rich porphyry-type deposits. In contrast, in back-arc extensional settings,
upwelling asthenospheric melts carry a weaker subduction signature, including lower S contents. Interaction of
these S-poor magmas with previously subduction modified upper plate lithosphere is more likely to give rise to
S-poor IOCG deposits.

Introduction oxides (as opposed to Fe sulfides), with or without Cu and Au

Sulfur-rich porphyry Cu Mo Au deposits are formed by
the precipitation of sulfide minerals (pyrite, chalcopyrite,
molybdenite) from hydrothermal fluids exsolved from shal-
lowly emplaced calc-alkaline magmas in volcanic arcs, typi-
cally generated in response to oceanic lithosphere subduction
(Burnham, 1979; Richards, 2003; Cooke et al., 2005; Sil-
litoe, 2010). In contrast, sulfur-poor iron oxide copper-gold
(IOCG) deposits include a wide range of different deposit
types, broadly linked by the prevalence of hydrothermal Fe
Corresponding author: e-mail, Jeremy.Richards@ualberta.ca
*A digital supplement to this paper is available at http://economicgeology.org/
and at http://econgeol.geoscienceworld.org/.
mineralization (Hitzman, 2000; Williams et al., 2005, 2010;
Hunt et al., 2007; Groves et al., 2010). The broadness of this
definition, as well as the capacity of oxidized saline fluids to
transport Fe Cu Au in a variety of geologic settings, has
led to controversy over the origin(s) of this group of deposits
(e.g., Barton and Johnson, 1996, 2000; Pollard, 2000; Williams
et al., 2005; Williams, 2010; Barton, 2014). However, within
this group there is a subset of deposits that is more clearly
associated with igneous rocks and fluids of possible magmatic-
hydrothermal origin (Pollard, 2000; Sillitoe, 2003). Richards
and Mumin (2013a, b) have referred to these as magmatic-
hydrothermal IOCG deposits, but, for simplicity, we use the
general term IOCG below. They share many features with

2017 Gold Open Access: this paper is published under the terms of the CC-BY license.

Submitted: October 2, 2015

0361-0128/17/4470/295-24 295 Accepted: August 8, 2016
296 RICHARDS ET AL.

porphyry systems (e.g., Cu-Au-Mo-Fe metal association and 1,000km (Fig. 1a; Sillitoe, 2003). The largest IOCG depos-
broad tectonic setting and magmatic affinity) but also have its within this part of the belt are Candelaria (116110 Ma;
important differences (such as more extensive development 501Mt at 0.54% Cu, 0.13 g/t Au, and 2.06 g/t Ag) and Man-
of high-temperature sodic, sodic-calcic, and potassic iron toverde (121117 Ma; 440 Mt at 0.56 % Cu and 0.12 g/t Au).
alteration envelopes, and more restricted development of The largest porphyry Cu-Au deposit is Carmen de Andacollo
lower-temperature phyllic and argillic alteration in IOCG (104 Ma; proven and probable reserves of 417 Mt at 0.34%
systems compared to porphyry systems; Hitzman et al., 1992; Cu and 0.12 g/t Au; Table 1).
Mumin et al., 2010). Small Early Cretaceous (>125 Ma; Berriasian-Barremian)
Richards and Mumin (2013b) explained some of these dif- porphyry Cu-Au deposits occur at 22S (e.g., Antucoya,
ferences, in particular the smaller acidic alteration zones in 142Ma; Tovaku, 132 Ma; Maksaev et al., 2006) and at 33S
IOCG deposits, as reflecting lower abundances of S (SO2) in (e.g., Colliguay, ~129 Ma; Maksaev et al., 2010) and appear to
the ore-forming fluids compared to porphyry fluids. As S-rich have formed during a short period of synchronous transpres-
porphyry fluids cool, the SO2 disproportionates to form H2S sion at 22S (Maksaev et al., 2006) or continental arc extension
and H2SO4 (sulfuric acid), leading to widespread develop- at 33S (Creixell, 2007). In contrast, IOCG (and magnetite-
ment of acidic alteration at shallow levels (Burnham, 1979; apatite) deposits formed predominantly in the mid-Creta-
Candela, 1992; Field et al., 2005; Richards, 2011b, 2015); this ceous (~125~110 Ma; Aptian-Albian; Gelcich et al., 2005;
happens to a lesser extent in S-poor IOCG fluids. Another Arvalo et al., 2006; Rieger et al., 2010; Tornos et al., 2010)
important difference is the broader range of metals found in and are located in a tectonically distinct but spatially super-
IOCG versus porphyry deposits, including, in some deposits, imposed belt from 25 to 34S. These deposits have been
the presence of abundant U, rare earth elements (REEs), P, described as spatially and temporally related to the culmina-
Co, Ni, and Bi. The increased variety of metals is attributed tion of a period of back-arc extension that developed along the
to the much greater influence of fluid reactions with crustal continental margin from the Late Jurassic to mid-Cretaceous
rocks and the resultant metal fluxing that occurs in giant (Oyarzun et al., 1999; Grocott and Taylor, 2002; Sillitoe, 2003)
IOCG hydrothermal systems (in addition to magmatic contri- or, alternatively, as having formed in response to the initiation
butions), and the more common occurrence of mafic country of basin inversion in the mid-Cretaceous (Chen et al., 2013).
rocks around many IOCGs (Somarin and Mumin, 2012; Rich- Porphyry Cu-Au-(Mo) deposits, including the large Carmen
ards and Mumin, 2013b; Barton, 2014). de Andacollo porphyry Cu-Au deposit (104Ma), again began
The Mesozoic Coastal Cordillera of northern Chile is to form in the later Cretaceous (<110 Ma; Cenomanian-
uniquely suited to compare the characteristics and controls Turonian) between 25 and 32S, following the resumption
on ore formation in porphyry and IOCG deposits because of arc magmatism during or after basin inversion (Maksaev
both deposit types occur in a broadly coeval (Cretaceous), et al., 2010). We group igneous rocks and associated ore
50- to 80-km-wide belt that runs parallel to the coast for over deposits into three broad temporal groupings that relate to
24S
Extension Sinistral transtension Contraction
N Legend
Chile (1) (i)
(1,2) (3) (1)
Tropezon (110 Ma) Porphyry CuMoAu
Casualidad (10094 Ma) (> or < 1 Mt Cu)
26S Todos los Santos (118 Ma)
Santo Domingo (124 Ma) IOCG (> or < 1 Mt Cu)
Mantoverde (121117 Ma) Inca de Oro
Cerro Negro Norte (116 Ma) (9088 Ma) (ii) Transitional
(iii)
Candelaria (116110 Ma)
Punta del Cobre (116 Ma) Los Toros (98 Ma)
28S Structural setting based on
tectonostratigraphic evidence
Cortadera (87 Ma) (4)
Productora (129 Ma) Dos Amigos (108104 Ma) Extension
Los Loros (91 Ma)
La Verde (88 Ma) (5)
Trapiche (122120 Ma) Cachiyuyo (111 Ma) (7) Contraction
Las Campanas (90 Ma)
Totora (120 Ma)
30S Pajonales (117 Ma) ?
Frontera (112 Ma) Structural setting based on
Panulcillo (115 Ma) Andacollo (104 Ma) (i) (7) (v) (7)
(6) (iv) structural evidence
Extension
Espino (9386 Ma) Llahuin (92 Ma)
Transtension
32S (9)
(vii)
Argentina (8)
Contraction
(vi)
Pacific
Ocean Colliguay (129 Ma) Transpression
(10) (i) (viii) (viii) (11)
34S
72W 70W 68W 145 135 125 115 105 95 85
Age (Ma)
Fig. 1. Distribution, timing, and tectonic setting of Cretaceous porphyry Cu-Au and IOCG deposits in the Mesozoic Coastal
Cordillera of northern Chile. (a) Geographic distribution of deposits and spatial relationship to the Atacama fault system; ages
of deposits in Ma are shown in parentheses. (b) Temporal and tectonic separation of porphyry and IOCG deposits. Sources
of data are provided in Table 1 and Appendix 1.
 TECTONIC SETTINGS AND S CONTENTS OF MAGMAS ASSOCIATED WITH CRETACEOUS DEPOSITS, CHILE 297

Table 1. Cretaceous Porphyry and IOCG Deposits of the Coastal Cordillera of Northern Chile

Metal
Deposit/prospect association Resource Age (Ma) References

Porphyry
Inca de Oro Cu-Au-Ag 389 Mt at 0.39% Cu, 0.1 g/t Au 9088 (U-Pb Zr) Maksaev et al. (2010)
Los Toros Cu 98 Maksaev et al. (2007)
Dos Amigos Cu-Au 36 Mt at 0.36% Cu 108106 (U-Pb Zr) Almonacid (2007)
Totora Cu-Au 120121 (U-Pb Zr) Maksaev and Llaumet (2015)
La Union (Frontera) Cu-Au 50.5 Mt at 0.4% Cu, 0.2 g/t Au 112 (U-Pb Zr) Creixell et al. (2015);
Maksaev and Llaumet (2015)
Pajonales Cu-Au 117 (U-Pb Zr) Morelli (2008)
Punta Colorada Cu-Au 109 (U-Pb Zr) Creixell et al. (2015)
Cachiyuyo Cu-Au 111 (U-Pb Zr) Creixell et al. (2015)
La Verde Cu-Au 88 (U-Pb Zr) Creixell et al. (2015)
Elisa Cu-Au 92 (U-Pb Zr) Creixell et al. (2015)
Cortadera Cu-Au 87 (U-Pb Zr) Creixell et al. (2015)
Las Campanas Cu-Au 90 (U-Pb Zr) Creixell et al. (2015)
Los Loros Cu-Au 91 Maksaev et al. (2010)
Carmen de Andacollo Cu-Au-Mo Proven and probable reserves 104 (U-Pb Zr; Re-Os Mo) Maksaev et al. (2010); Teck
of 417 Mt at 0.34% Cu and Resources Limited, 2016;
0.12 g/t Au this study
Llahuin Cu-Au-Mo 145 Mt at 0.4% Cu equiv 92 (Ar-Ar Bt) Maksaev et al. (2010)
Colliguay Cu-Au 129 (K-Ar WR) Maksaev et al. (2010)

IOCG
Tropezon Cu-(Mo-Au) ~1.5 Mt Cu 110 (U-Pb Zr) Tornos et al. (2010)
Casualidad Cu-Au 400 Mt at 0.55% Cu 100 (U-Pb Zr), 10094 (Ar-Ar Bt, Kovacic (2014)
Kspar), 9484 (Ar-Ar Act)
Todos Los Santos Cu-Au 118 (Ar-Ar Act) Gelcich et al. (2005)
Santo Domingo Cu-Fe-Au 417 Mt at 0.25% Cu, 27% Fe, 124 (U-Pb Zr, Tn) Daroch et al. (2015)
0.032 Au g/t
Mantoverde Cu-Au 440 Mt at 0.56% Cu, 0.12 g/t Au 121117 (K-Ar Ser) Rieger et al. (2010)
Cerro Negro Norte Fe-(Cu-Au) 100 Mt at 65% Fe 116 (U-Pb Tn) Raab (2002)
Candelaria-Punta del Cobre Cu-Au-Ag 501 Mt at 0.54% Cu, 0.13 g/t Au 116110 (Ar-Ar Bt; Re-Os Mo) Arvalo et al. (2006);
Marschik and Fontbot (2001)
Productora1 Cu-Au-(Mo) 214.3 Mt at 0.48% Cu, 0.1 g/t Au, 128.9 (Re-Os Mo), 130 (U-Pb Zr) Marquardt et al. (2015)
138 ppm Mo
Trapiche Cu-Au 122120 (Ar-Ar Act) Creixell et al. (2015)
Panulcillo Cu-Au 0.5 Mt at 2.753% Cu, 0.51 g/t Au 115 (K-Ar Phl) Diaz and Corvaln (2015)
El Espino Cu-Au 145 Mt at 0.55% Cu, 0.22 g/t Au 9389 (U-Pb Zr); 8886 Del Real and Arriagada (2015);
(Ar-Ar Act, Ser, Kspar) Lpez et al. (2014)

Abbreviations: Act = actinolite, Bt = secondary biotite, Kspar = secondary potassium feldspar, Mo = molybdenite, Phl = phlogopite, Ser = sericite, Tn =
titanite, WR = whole rock, Zr = zircon
1Deposit type is transitional between porphyry and IOCG

tectonic setting as follows: early Cretaceous (extension), mid-
Cretaceous (transtension), and late Cretaceous (contraction).
Because the tectonic setting changed diachronously from
north to south over intervals of 10 to 15 m.y., these terms do
not correspond exactly to formal stratigraphic period subdivi-
sions (epochs), and there is some temporal overlap between
groups.
Evidence for a magmatic hydrothermal origin for several of
these Chilean IOCG deposits has been reported, including at
Candelaria and Mantoverde (Marschik and Kendrick, 2015)
and Tropezon (Tornos et al., 2010, 2012), and several smaller
IOCG deposits occur in close proximity to coeval intrusions
with alteration patterns apparently centered on those plutons
(e.g., El Trapiche veins, Creixell et al., 2009; El Espino, Lpez
et al., 2014). In contrast, Barton and Johnson (1996, 2000)
argue that the ore-forming fluids were basinal brines, albeit
with convection driven by the heat from coeval magmatism.
In this paper, we adopt the hypothesis that the Chilean IOCG
and porphyry deposits are both of magmatic-hydrothermal
origin, and that their contrasting styles of ore formation relate
to differences in the tectonic setting and chemistry of the
associated magmas. We combine new and published geochro-
nological and geochemical data for igneous rocks associated
with Cretaceous porphyry and IOCG deposits in the Coastal
Cordillera with published structural information to show that
porphyry and IOCG deposits formed in distinct tectono-
magmatic settings. The bulk compositions of the associated
igneous rocks are almost indistinguishable, but we present
data from analysis of igneous apatite to suggest that the por-
phyry-forming magmas were S rich compared to their IOCG
counterparts, consistent with the difference in S content of
porphyry (S rich) and IOCG (S poor) ore deposits.
Mesozoic Tectonomagmatic Setting and
Metallogeny of Northern Chile
Arc magmatism related to subduction has taken place along the
Chilean segment of the Gondwana supercontinental margin
since the late Paleozoic (Parada et al., 2007). Mid-Jurassic to
298 RICHARDS ET AL.
Cretaceous magmatism mostly developed ~100 km to the west
of the Paleozoic arc (Parada et al., 2007). Extensional tecton-
ics affected the arc from the mid-Jurassic to early Cretaceous,
with intra-arc and back-arc basin formation occurring in the
mid-Cretaceous, followed by tectonic inversion in the mid- to
late Cretaceous (Charrier et al., 2007). These tectonic changes
are interpreted to reflect alternating periods of subduction
coupling and decoupling between the down-going and overrid-
ing plates, with the generation of periods dominated by con-
tractional and extensional tectonics, respectively, in the upper
plate (Scheuber and Gonzalez, 1999). Of particular relevance
to this study, early Cretaceous extension and mid-Cretaceous
transtension occurred during a period of low convergence rate
and weak plate coupling that may reflect slab rollback. This was
followed by contraction in the mid- to late Cretaceous, caused
by an increase in convergence rate in response to global-scale
plate reorganization (Matthews et al., 2012).
Early Cretaceous magmatism in the Coastal Cordillera
between 25 and 34S was generated in a broadly extensional
tectonic regime that caused rifting and crustal thinning (Parada
et al., 2007). It was characterized by relatively primitive calc-
alkaline to shoshonitic lavas that built thick (510 km) subaerial
volcanic sequences (Vergara et al., 1995; Morata and Aguirre,
2003; Parada et al., 2005; Charrier et al., 2007; Girardi, 2014).
By the mid-Cretaceous, the tectonic setting had become pre-
dominantly transtensional (Brown et al., 1993; Arvalo et al.,
2003) and was characterized by episodic volcanism and sedi-
ment deposition in intra-arc and back-arc shallow marine and
continental basins (Fig. 1b; Morata and Aguirre, 2003). The
transition from extensional to transtensional tectonics was
slightly diachronous from north to south, and represents the
progression of continental arc rifting southward with time,
beginning in the north in the Barremian (~130 Ma) and reach-
ing its maximum in the Aptian-Albian (~120 Ma). Plutonic com-
plexes were emplaced during both tectonic stages, controlled by
crustal-scale fault zones that evolved into the Atacama fault sys-
tem in the Valanginian-Barremian (144126 Ma; Brown et al.,
1993). The Atacama fault is an early dip-slip and later sinistral
transtensional N-trending fault system that extends for more
than ~1,000 km parallel to the continental margin (Fig. 1a) and
is interpreted to have formed in response to oblique subduction
(Scheuber and Andriessen, 1990; Brown et al., 1993; Palacios
et al., 1993); it is the primary structural control on the location
of IOCG deposits in Chile (Sillitoe, 2003; Creixell et al., 2009).
Crustal extension ended in the Albian-Cenomanian (11095
Ma) with a return to contractional tectonics that produced
crustal shortening and thickening, basin closure, rapid uplift,
and a marked eastward shift of magmatism (Parada et al., 2002,
2005; Arancibia, 2004; Maksaev et al., 2010).
The spatiotemporal distribution of Cretaceous IOCG and
porphyry Cu-Au deposits in northern Chile between 25 and
34S is shown in relation to these tectonomagmatic periods
in Figure 1b. Here it can be seen that, although the deposits
roughly overlap spatially, IOCG deposits are broadly sepa-
rated in time from younger porphyry Cu-Au deposits at ~110
to 100Ma, which also marks the time of the major tectonic
change from transtension to contraction. During the initial
stages of arc rifting in the Late Jurassic-early Cretaceous,
only a few small porphyries were developed (e.g., Antu-
coya, Colliguay). This was followed by the early formation
of magnetite-apatite deposits (Gelcich et al., 2005; Creix-
ell et al., 2009) and then IOCG deposits during the main
stage of rifting and back-arc basin development in the mid-
Cretaceous (~125~110 Ma, Aptian-Albian; Oyarzun et al.,
1999). This tectonic relationship appears to be consistent with
IOCG deposits globally, which are commonly found to be
associated with extensional events, including postcollisional,
intracontinental, back-arc, and intra-arc rift settings (Williams
et al., 2005; Corriveau and Mumin, 2010; Skirrow, 2010).
Porphyry Cu-Au-(Mo) deposit formation returned in the late
Cretaceous with the resumption of subduction-related mag-
matism during and after tectonic inversion. Apparent excep-
tions to this three-part deposit distribution (e.g., the small,
mid-Cretaceous Totora, Pajonales, and Cachiyuyo porphy-
ries, and the late Cretaceous Casualidad and El Espino IOCG
deposits; Fig. 1) may reflect uncertainties in age determina-
tion, lithospheric heterogeneities, or delayed response to tec-
tonic changes.
Sampling
Fifty-four samples of volcanic and intrusive igneous rocks associ-
ated with the Carmen de Andacollo, Frontera, and Dos Amigos
porphyry Cu Au Mo deposits, the transitional Productora
deposit, and the Candelaria, Casualidad, Espino, and Man-
toverde IOCG deposits from the Coastal Cordillera of north-
ern Chile between 26 and 32S (Fig. 1) were collected from
drill core and outcrops in July 2015. Where possible, intrusive
rocks thought to be directly related to mineralization (coeval,
cospatial) were collected; other samples were from broadly
coeval intrusions or volcanic rock outcrops in the vicinity of
the deposits (based on regional geologic maps). Least-altered
samples were targeted for collection, but most of the rocks have
undergone either low-grade regional metamorphism (result-
ing in minor chloritization of ferromagnesian silicate miner-
als and partial saussuritization of plagioclase) or hydrothermal
alteration due to proximity to the ore deposits. Two samples of
quartz-molybdenite veins were collected from the Carmen de
Andacollo porphyry Cu-Au deposit for Re-Os dating.
The rocks were studied petrographically to determine the
degree of alteration and to seek unaltered accessory minerals
such as zircon and apatite for electron microprobe analysis.
Analytical Methods
Whole-rock geochemistry
Thirty-nine least-altered samples from the collected suite
were submitted to Activation Laboratories Ltd. (Ancaster,
Ontario) for analysis using the 4E-Research analytical pack-
age, which combines instrumental neutron activation analysis
and lithium metaborate/tetraborate fusion inductively coupled
plasma-mass spectrometry for determination of 62 elements.
Analyses of standards and duplicates indicate that accuracy
for major elements is typically within 5 relative %, and 10 rela-
tive % for minor and trace elements. The ferrous iron (FeO)
content of the rocks was also determined by titration.
Electron microprobe analyses
Polished thin sections of all samples were examined for the
presence of igneous accessory minerals such as zircon and
apatite. Because of the relatively mafic nature of many of
 TECTONIC SETTINGS AND S CONTENTS OF MAGMAS ASSOCIATED WITH CRETACEOUS DEPOSITS, CHILE 299

the samples, few contained zircon in thin section, so zircon
chemistry was not attempted. A larger number of samples
contained apatite, although care was needed to distinguish
between igneous and hydrothermal (or late-stage) apatite.
The latter was common in the groundmass of altered samples,
and clearly hydrothermal apatite (intergrown with hydrother-
mal minerals such as quartz and sulfides) typically had thin,
elongated prismatic habits (200-m length; Fig. 2a). Apatite
crystals with unequivocally igneous origin were distinguished
by their inclusion within phenocrysts (mainly plagioclase and
biotite). The igneous apatite crystals had stubby prismatic
habits (2050-m length; Fig. 2b-d).
Compositional data were acquired with a Cameca SX100
electron microprobe using wavelength-dispersive spectros-
copy and Probe for EPMA software (Donovan et al., 2015).
For sessions in which seven elements (F, Na, Si, P, S, Cl,
and Ca) were measured, the following conditions were used:
10-kV accelerating voltage, 20-nA beam current, and 5- to
10-m beam diameter. Total count times of 30 s were used
for both peaks and backgrounds. The X-ray lines, analyzing
crystals, and standards were as follows: F K, PC0, topaz;
Na K, TAP, tugtupite; Si K, TAP, topaz; P K, PET,
fluorapatite; S K, PET, anhydrite (intensity data aggregated
from two spectrometers; Donovan et al., 2011); Cl K, PET,
tugtupite; and Ca K, PET, fluorapatite. The calculated limits
of detection (as element, rounded to the nearest 10 ppm) at
99% confidence were as follows: F, 570 ppm; Na, 130 ppm;
Si, 120ppm; P, 170 ppm; S, 80 ppm; Cl, 290 ppm; and Ca,
280 ppm. To check for interference from third-order P K
on F K, the signal from synthetic GaP was examined with
the PC0 crystal: no significant interference from P on F was
detected under the conditions of analysis.
For sessions in which nine elements (F, Si, P, S, Cl, Ca,
Mn, Fe, and As) were measured, the following conditions
were used: 15-kV accelerating voltage, 20-nA beam cur-
rent, and 5-m beam diameter. The X-ray lines, analyzing
crystals, standards, and count times (seconds) on both peaks
and backgrounds were as follows: F K, PC0, topaz, 60 s;
Si K, TAP, topaz, 40 s; P K, PET, fluorapatite, 30 s; S K,
PET, anhydrite, 30 and 40 s (intensity data aggregated from

(a) CAN-2 Ap (b) CAS-2

0.01% 0.01%
sulfide
Plag Plag
Qz

Plag Qz
Amph
0.08%
0.07%
Qz Ap
sulfide Plag
Qz
0.02%
Qz Ap Amph
sulfide Plag

(c) CDA-8 (d) CDA-2

Qz
Biotite
Ap 0.45%
0.06% Biotite
Ap
0.41%
0.27%
Ap
Chl

0.15%
Chl

Qz

Fig. 2. Photomicrographs of apatite crystals in samples from (a) Candelaria (CAN-2), (b) Casualidad (CAS-2), and (c, d)
Carmen de Andacollo (CDA-8, CDA-2). Concentrations of SO3 in apatite crystals are shown in red (wt %); higher concentra-
tions are observed in apatite from porphyry-related samples (Carmen de Andacollo) compared to the IOCG-related samples
(Candelaria, Casualidad). Some apatite microphenocrysts from Carmen de Andacollo show zonation from SO3-rich cores to
SO3-poorer rims (d). Abbreviations: Amph = amphibole, Ap = apatite, Chl = chlorite, Plag = plagioclase, Qz = quartz.
300 RICHARDS ET AL.

measurements on two spectrometers; Donovan et al., 2011);
Cl K, PET, tugtupite, 40 s; Ca K, PET, fluorapatite, 30 s;
Mn K, LIF, spessartine, 40 s; Fe K, LIF, spessartine, 40 s;
and As L, TAP, synthetic GaAs, 40 s. The calculated limits
of detection (as element, rounded to the nearest 10 ppm) at
99% confidence were as follows: F, 460 ppm; Si, 110 ppm;
P, 260 ppm; S, 70 ppm; Cl, 150 ppm; Ca, 170 ppm; Mn,
170ppm; Fe, 160ppm; and As, 180 ppm.
In all sessions, time-dependent intensity corrections for F
and Cl were carried out (peak count times divided into six
intervals) with Probe for EPMA software (Donovan et al.,
2015), following Nielsen and Sigurdsson (1981), Stormer et
al. (1993), and Henderson (2011). Intensity data for all ele-
ments were reduced following the methods of Armstrong
(1995). Oxygen was calculated by stoichiometry and included
in the data reduction, as was the correction for oxygen equiva-
lence of the halogens (F and Cl).
Re-Os dating
A molybdenite mineral separate was made for each sample
by metal-free crushing followed by gravity and magnetic con-
centration methods described in detail by Selby and Creaser
(2004). The 187Re and 187Os concentrations in molybdenite
were determined by isotope dilution mass spectrometry using
Carius tube, solvent extraction, anion chromatography, and
negative thermal ionization mass spectrometry techniques.
A mixed double spike containing known amounts of isotopi-
cally enriched 185Re, 190Os, and 188Os was used (Markey et al.,
2007). A ThermoScientific Triton mass spectrometer with a
Faraday collector was used for isotopic analysis. Total blanks
for Re and Os are less than 3 and 2 pg, respectively, which are
insignificant for the Re and Os concentrations in molybde-
nite. The molybdenite HLP-5 (Markey et al., 1998) was ana-
lyzed as a standard, and over a period of two years an average
Re-Os date of 221.56 0.40 Ma (1 s.d. uncertainty, n = 10)
was obtained. This value is within the uncertainty of the 221.0
1.0 Ma age reported by Markey et al. (1998).
Re-Os Age of the Carmen de Andacollo
Porphyry Cu-Au Deposit
The Carmen de Andacollo porphyry Cu-Au deposit has previ-
ously been dated at 104 3.3 Ma by U-Pb analysis of zircons
in the ore-forming porphyry intrusions (Maksaev et al., 2010),
and at 104 3 and 98 2 Ma by K-Ar analysis of phyllic- and
potassic-altered rocks, respectively (Reyes, 1991). We have
dated two samples of molybdenite from B-type quartz veins in
the deposit, which yielded statistically indistinguishable ages
of 103.9 0.5 and 103.6 0.5 Ma (2s errors; Table 2), in good
agreement with the U-Pb date for magmatism of Maksaev et
al. (2010).
Cretaceous Igneous Geochemistry
Whole-rock major and trace element geochemical data for 125
igneous rocks coeval with either IOCG or porphyry deposits
from the Coastal Cordillera between 25 and 34S were com-
piled from the literature and combined with our 40 new anal-
yses (new data are listed in Table 3 and Supplementary Table
S1, and data from the literature are listed in Supplementary
Table S2). These rocks are divided into three groups, based
on the tectonomagmatic periods described above: early Cre-
taceous, related to a few small porphyry Cu-Au deposits and
early stages of arc rifting; mid-Cretaceous, related to IOCG
deposits and back-arc transtension; and late Cretaceous,
related to porphyry Cu-Au-(Mo) deposits and a return to con-
tractional tectonics and arc magmatism. Note that, because
of diachronous changes in tectonic style from north to south
over periods of 10 to 15 m.y., the terms early, mid-, and
late Cretaceous do not correspond exactly to formal strati-
graphic divisions, but are approximately separated at ~125
and ~110 Ma, respectively.
Volcanic and plutonic rocks from the three tectonomag-
matic groups are mostly metaluminous, calc-alkaline to high-
K calc-alkaline, and range in composition from andesite
(diorite) to dacite (granodiorite). Samples of igneous rocks
directly associated with porphyry and IOCG deposits show
a similar compositional range on a total alkali-silica diagram
(Fig. 3), although it is evident that the porphyry-related rocks
are mostly more felsic (diorite to granodiorite) compared to
those associated with IOCG deposits (mostly gabbroic diorite
to diorite). The apparently alkaline composition of several of
these samples (especially from IOCG deposits) might be due
to variable degrees of hydrothermal alteration (sodic-calcic or
potassic), which was unavoidable in these suites of ore-asso-
ciated rocks. However, on a plot of immobile element ratios
(Zr/Ti versus Nb/Y; Fig. 4; Winchester and Floyd, 1977), a
small number of mid-Cretaceous and IOCG-related samples
do plot in more alkaline fields (alkali gabbro and syenite), sug-
gesting that some of these samples are genuinely alkaline in
composition. Nevertheless, the majority of the samples over-
lap in the gabbro-diorite-granodiorite fields in Figure 4, with
no clear distinction between age groups or association with
porphyry and IOCG deposits.
On primitive mantle-normalized extended trace element
(Fig. 5) and chondrite-normalized REE (Fig. 6) diagrams,
the porphyry and IOCG suites display almost indistinguish-
able patterns: enrichments in large-ion lithophile elements

Table 2. Re-Os Molybdenite Age Data from the Carmen de Andacollo Porphyry Cu-Au Deposit

Total Model
Re 187Re 187Os common age 2 with
Sample no. Location Description (ppm) 2 (ppb) 2 (ppb) 2 Os (pg) (Ma)1 (Ma)2

CDA-4 DDH 11-41 Quartz-molybdenite vein 405.2 1.3 254,683 805 441.4 0.3 2.6 103.9 0.5
at 396.4 m in Porphyry D
CDA-12 DDH 13-09 Quartz-molybdenite vein 556.9 1.8 350,059 1,106 604.8 0.4 1.0 103.6 0.5
at 383.2 m in andesitic country rock

1Model age calculated from the equation t = ln (187Os/187Re + 1)/, where t = model age and = 187Re decay constant, and assuming no initial radiogenic Os
2 = 187Re decay constant, 1.666 1011 yr1 (Smoliar et al., 2006)
 Table 3. Whole-Rock and Trace Element Geochemical Data for Igneous Rock Samples from the Coastal Cordillera of Northern Chile Between 25 and 34S
Sample no. ESP-1 ESP-2 ESP-3 CDA-1 CDA-2 CDA-3 CDA-7 CDA-9 CDA-10 FR-1
Frontera-Mine
Locality Espino Espino Espino Andacollo Andacollo Andacollo Andacollo Andacollo Andacollo La Union
Biotite, Less altered, gypsum- Quartz-
Chlorite, disseminated chalcopyrite- chalcopyrite
Alteration/ calcite veins Chlorite, chalcopyrite- Chlorite- iron oxide veinlets, veinlets, gypsum- Epidote, clays,
mineralization (skarn in wall rock) K-feldspar pyrite (sericite) 2 biotite iron oxide weak potassic
TAS Gabbroic Gabbroic Gabbroic Basaltic trachyandesite
classification1 diorite diorite diorite Monzonite Granodiorite Granodiorite (mugearite) Granodiorite Monzonite Granodiorite

SiO2 (wt %) 51.45 51.85 49.78 57.38 62.92 62.79 49.92 62.05 54.67 63.54
Al2O3 (wt %) 15.55 16.81 16.78 16.23 15.73 15.85 18.19 15.86 14.24 14.63
Fe2O3 (wt %) 0.98 0.69 1.35 2.33 0.97 0 5.83 0.56 1.07 3.79
FeO (wt %) 6.3 6.4 6.8 2.8 2.7 4.1 4 3.7 4.9 2.5
MnO (wt %) 0.119 0.168 0.167 0.13 0.074 0.048 0.152 0.095 0.118 0.173
MgO (wt %) 7.87 8 7.43 3.22 1.06 2.63 4.28 3.39 6.77 1.72
CaO (wt %) 8.06 9.43 7.15 5.03 4.75 4.49 3.78 5.27 5.74 3.77
Na2O (wt %) 3.44 3.11 2.98 4.05 2.68 3.46 4.86 4.34 2.83 4.11
K2O (wt %) 1.36 0.35 1.3 2.64 2.89 2.31 2.91 1.48 2.9 2.36
TiO2 (wt %) 0.647 0.693 0.711 0.558 0.375 0.489 0.929 0.517 0.651 0.368
P2O5 (wt %) 0.12 0.12 0.12 0.2 0.13 0.13 0.25 0.2 0.33 0.12
LOI (wt %) 2.33 2.25 5.59 5.37 5.19 3.31 4.54 2.76 4.29 1.31
LOI 2 (wt %) 1.63 1.53 4.82 5.06 4.89 2.85 4.1 2.35 3.74 1.03
Total (wt %) 98.94 100.6 100.9 100.3 99.78 100.1 100.1 100.6 99.06 98.66
Total 2 (wt %) 98.23 99.87 100.2 99.94 99.48 99.62 99.64 100.2 98.51 98.38
Fe2O3(T) (wt %) 7.99 7.8 8.91 5.45 3.97 4.56 10.28 4.67 6.52 6.57
Cs (ppm) 9.4 1.8 3.5 4.4 4 2.2 4.1 2 3.8 0.7
Tl (ppm) 0.27 <0.05 <0.05 0.23 0.24 0.29 0.08 0.2 0.66 0.1
Rb (ppm) 71 9 35 68 78 63 68 43 105 37
Ba (ppm) 153 209 293 508 611 683 638 217 270 626
Th (ppm) 0.52 0.49 0.48 2.9 5.76 5.21 2.44 6.07 4.96 3.13
U (ppm) 0.24 0.2 0.28 1.1 1.48 2.07 0.71 1.75 1.99 0.74
Nb (ppm) 1.8 1.7 1.7 2.7 2.9 2.6 2 2.8 3.3 2.5
Ta (ppm) 0.14 0.16 0.14 0.22 0.33 0.31 0.16 0.28 0.25 0.28
La (ppm) 7.46 6.11 7.7 15.5 18.8 16.3 16 15.9 23 11.8
Ce (ppm) 15.9 14.2 16.9 32.7 36 31.9 32.7 35.3 49.6 23.1
Pb (ppm) <5 <5 <5 6 <5 <5 18 <5 <5 10
Pr (ppm) 2.26 2.02 2.26 4.15 4.26 3.86 4.33 4.75 6.3 2.87
Sr (ppm) 489 499 365 621 234 584 738 507 358 348
Nd (ppm) 9.61 8.96 10.4 16.8 16.1 15.4 18 19.6 24.9 11.4
Zr (ppm) 58 60 60 92 91 86 66 113 115 69
Hf (ppm) 1.5 1.7 1.6 2.4 2.5 2.4 2 2.9 3 1.9
Sm (ppm) 2.74 2.31 2.58 3.55 3.16 3.09 4.25 4.06 5.26 2.54
Eu (ppm) 0.863 0.748 0.845 1.17 0.84 1.03 1.27 1.19 1.42 0.836
Sb (ppm) 1.7 0.8 1.6 1.7 1 <0.1 1.6 0.2 <0.1 2.6
Gd (ppm) 2.58 2.55 2.57 2.9 2.43 2.55 3.42 3.28 4 2.38
Tb (ppm) 0.46 0.44 0.43 0.41 0.35 0.38 0.54 0.44 0.56 0.39
Dy (ppm) 2.91 2.71 2.77 2.27 1.91 2.06 3.13 2.45 2.9 2.4
Y (ppm) 15 15 14 13 12 13 15 14 15 15
Ho (ppm) 0.58 0.56 0.55 0.44 0.36 0.39 0.59 0.46 0.54 0.5
Er (ppm) 1.65 1.73 1.67 1.26 1.08 1.09 1.73 1.29 1.49 1.5
Tm (ppm) 0.256 0.258 0.237 0.19 0.161 0.163 0.262 0.201 0.214 0.237
Yb (ppm) 1.74 1.68 1.66 1.2 1.02 1.07 1.74 1.33 1.4 1.7
TECTONIC SETTINGS AND S CONTENTS OF MAGMAS ASSOCIATED WITH CRETACEOUS DEPOSITS, CHILE

Lu (ppm) 0.29 0.277 0.263 0.183 0.163 0.17 0.285 0.21 0.223 0.28
Cr (ppm) 369 389 375 26.5 32.5 43.1 3.4 102 372 8.4
Ni (ppm) 130 140 123 17 11 16 13 38 128 3
Sc (ppm) 28.1 28.6 28.7 13.8 9.34 13.9 22.3 13.9 22.9 8.22
V (ppm) 197 208 207 145 100 141 335 133 181 83
Co (ppm) 31.5 28.6 32.1 15.4 8.1 12.3 26.3 13 23.5 10.7
Cu (ppm) 84 250 621 5 813 1,140 12 376 1,430 655
301
 Table 3. (Cont.)
302
Sample no. PR-1 PR-2 PR-3 PR-4 PR-5 PR-6 PR-7 PR-8 CAN-1
Productora- Productora Productora Productora
Rancho Hill, Productora- Productora- Productora (iron district (iron district (iron district
Locality Cachiyuyito stock Alice porphyry Alice porphyry Productora (Ruta 5 batholith) regional) regional) regional) Candelaria
Weak disseminated
pyrite-chalcopyrite, Sodic
Alteration/ Weak albite- but otherwise (albite-chlorite) Moderately Weak albite-
mineralization actinolite fairly fresh replacing hornblende altered actinolite Minor epidote
TAS classification1 Granodiorite Granodiorite Granodiorite Basaltic andesite Granodiorite Diorite Granodiorite Diorite Monzonite

SiO2 (wt %) 62.33 66.72 62.29 51.69 64.1 60.49 65.25 57.03 58.93
Al2O3 (wt %) 14.57 15.72 14.26 14.93 16.38 16.41 15.17 17.23 17.87
Fe2O3 (wt %) 2.1 0.43 6.87 2.02 1.26 0.69 2.19 0.68 2.59
FeO (wt %) 2.5 2 4.3 4.3 3.3 2.2 3 3 2.7
MnO (wt %) 0.102 0.042 0.105 0.131 0.116 0.054 0.09 0.153 0.055
MgO (wt %) 2.44 1.8 1.53 9.41 2.02 3.87 1.73 4.31 1.89
CaO (wt %) 6.17 5.77 3.66 6.12 5.64 8.66 4.39 10.1 3.81
Na2O (wt %) 3.58 4.02 3.46 4.19 3.69 4.26 3.79 4.61 6.08
K2O (wt %) 2.97 0.75 1.12 0.5 1.63 0.41 2.29 0.58 2.62
TiO2 (wt %) 0.953 0.501 0.413 0.717 0.42 1.083 0.705 1.032 0.437
P2O5 (wt %) 0.19 0.09 0.1 0.1 0.13 0.22 0.14 0.19 0.23
LOI (wt %) 0.89 1.94 0.86 4.41 1.14 1.07 1.1 1.41 1.15
LOI 2 (wt %) 0.61 1.72 0.38 3.93 0.77 0.82 0.76 1.08 0.85
Total (wt %) 99.07 100 99.44 99.01 100.2 99.67 100.2 100.7 98.67
Total 2 (wt %) 98.79 99.8 98.96 98.53 99.82 99.42 99.83 100.3 98.37
Fe2O3(T) (wt %) 4.88 2.65 11.65 6.8 4.94 3.14 5.53 4.02 5.6
Cs (ppm) 0.6 0.8 1.1 0.4 1.3 0.2 0.3 0.5 0.3
Tl (ppm) <0.05 <0.05 <0.05 <0.05 0.09 <0.05 <0.05 <0.05 <0.05
Rb (ppm) 56 20 38 17 39 6 33 14 34
Ba (ppm) 643 118 130 41 432 128 590 150 843
Th (ppm) 12 3.19 3.94 1.63 3.61 7.13 4.44 2.8 3.33
U (ppm) 1.44 0.61 1.16 2.4 1.09 1.58 0.53 0.73 1.05
RICHARDS ET AL.

Nb (ppm) 6.8 2.3 5.5 1.2 3.8 4.4 4 3.3 3.1

Ta (ppm) 0.63 0.24 0.3 0.1 0.45 0.41 0.35 0.27 0.24
La (ppm) 10.9 6.9 12.5 10.8 14.6 12.2 11.8 4.22 18.3
Ce (ppm) 27.2 15.7 25.5 21.4 30.8 33.4 29.8 12.4 36.8
Pb (ppm) <5 <5 <5 <5 <5 <5 <5 <5 <5
Pr (ppm) 3.88 2.24 3.14 2.37 3.72 4.6 4.37 2.06 4.59
Sr (ppm) 285 313 184 144 384 364 228 330 426
Nd (ppm) 18.2 9.13 12.5 8.97 14.3 19.5 20.4 10.5 18.9
Zr (ppm) 189 89 95 61 113 171 181 133 127
Hf (ppm) 4.8 2.2 2.4 1.7 2.8 4.2 4.6 3.5 3
Sm (ppm) 4.96 2.06 2.68 2.04 2.99 4.83 5.24 3.39 3.7
Eu (ppm) 1.2 0.794 0.896 0.628 0.918 1.41 1.24 1.12 1.06
Sb (ppm) <0.1 0.3 0.5 0.5 0.5 0.5 <0.1 0.2 0.7
Gd (ppm) 5.29 2.17 2.6 2.42 2.58 4.64 5.54 4.28 3.28
Tb (ppm) 0.88 0.38 0.43 0.44 0.41 0.76 0.97 0.81 0.49
Dy (ppm) 5.5 2.37 2.67 2.82 2.48 4.67 6.09 5.27 2.91
Y (ppm) 29 18 12 17 16 28 36 31 19
Ho (ppm) 1.12 0.49 0.56 0.61 0.5 0.95 1.26 1.08 0.58
Er (ppm) 3.2 1.51 1.75 1.9 1.5 2.84 3.62 3.16 1.76
Tm (ppm) 0.473 0.236 0.27 0.302 0.242 0.433 0.534 0.46 0.279
Yb (ppm) 3.12 1.67 1.86 2.19 1.68 3.05 3.59 3.11 1.91
Lu (ppm) 0.506 0.284 0.307 0.371 0.285 0.502 0.576 0.502 0.316
Cr (ppm) 47.1 25.7 230 434 34.8 86.8 26.5 31.3 9.1
Ni (ppm) 13 5 17 96 9 15 5 7 6
Sc (ppm) 20 13.8 11.7 34.5 9.7 27.5 19.9 31.2 9.25
V (ppm) 126 94 82 251 77 196 110 190 99
Co (ppm) 11.4 6.9 18.4 8.9 8.2 11.3 12.9 6.5 7.7
Cu (ppm) 25 194 1,300 7 11 5 19 15 42
 Table 3. (Cont.)
Sample no. CAN-2 CAN-3 CAN-4 CAS-1 CAS-2 CAS-3 CAS-4 CAS-5 CAS-8 CAS-9
Candelaria-
Coquimbana
Locality Candelaria Candelaria mine Casualidad Casualidad Casualidad Casualidad Casualidad Casualidad Casualidad
Albitic alteration Potassic + Propylitic
Alteration/ + hematite-Cu Weak Weak propylitic chalcopyrite (chlorite-epidote)
mineralization veins nearby propylitic (chlorite-epidote) veinlets on potassic
TAS Gabbroic Gabbroic Foid
classification1 Monzonite diorite diorite Monzodiorite Diorite Monzodiorite Granodiorite monzosyenite Monzodiorite Diorite

SiO2 (wt %) 58.34 52.88 52.8 52.87 57.82 51.26 65.03 51.48 54.19 56.66
Al2O3 (wt %) 18.38 17.53 16.58 15.12 17.99 16.96 16.7 15.99 18.14 16.93
Fe2O3 (wt %) 3.01 5.86 3.55 5.83 2.03 6.5 0.19 4.52 0.96 2.62
FeO (wt %) 3.4 3.9 6 5.9 3.3 4.9 3.5 7.3 2.1 3.3
MnO (wt %) 0.106 0.051 0.101 0.146 0.153 0.063 0.044 0.085 0.092 0.126
MgO (wt %) 1.68 4.13 4.45 5.55 3.16 5.83 1.54 5.38 3.5 4.01
CaO (wt %) 5.67 8.04 8.46 4.12 6 1.84 4.77 1.22 10.46 8.02
Na2O (wt %) 4.27 4.05 3.85 3.94 4.26 6.13 4.03 2.08 4.25 4.12
K2O (wt %) 3.66 1.1 1.17 2.29 1.15 0.71 1.25 8.12 1.49 1.19
TiO2 (wt %) 0.84 1.104 1.123 0.822 0.478 0.783 0.351 0.768 0.854 0.746
P2O5 (wt %) 0.45 0.45 0.42 0.18 0.12 0.15 0.13 0.17 0.32 0.14
LOI (wt %) 0.76 1.07 0.62 2.29 1.98 3.35 1.2 1.5 2.43 2.09
LOI 2 (wt %) 0.38 0.63 -0.06 1.63 1.61 2.8 0.81 0.68 2.19 1.72
Total (wt %) 100.9 100.6 99.8 99.72 98.8 99.02 99.13 99.42 99.03 100.3
Total 2 (wt %) 100.6 100.2 99.12 99.06 98.43 98.47 98.74 98.61 98.8 99.95
Fe2O3(T) (wt %) 6.79 10.19 10.22 12.39 5.7 11.95 4.08 12.64 3.29 6.29
Cs (ppm) 1.7 0.6 0.7 1.5 1.4 0.6 0.7 2.8 0.3 0.4
Tl (ppm) 0.05 <0.05 <0.05 0.08 <0.05 <0.05 0.06 0.33 <0.05 0.05
Rb (ppm) 90 28 31 48 26 16 26 178 44 31
Ba (ppm) 776 263 346 269 352 67 341 3,137 134 147
Th (ppm) 7.47 4.95 4.76 4.53 0.59 0.83 2.31 2.47 4.06 2.39
U (ppm) 2.2 1.41 1.65 1.23 0.23 0.28 0.36 1.31 0.59 0.78
Nb (ppm) 7.4 4 4.1 3.2 1.7 1.6 3.1 2.8 5.5 2.5
Ta (ppm) 0.57 0.29 0.3 0.27 0.16 0.13 0.41 0.2 0.31 0.23
La (ppm) 33 25.5 22.4 15.5 7.71 7.89 9.72 9.88 6.37 12.6
Ce (ppm) 72.6 57.8 51 36.8 16.9 18 19.2 23.3 28 30.2
Pb (ppm) 6 <5 <5 <5 <5 <5 <5 <5 <5 <5
Pr (ppm) 9.47 7.71 6.99 4.94 2.17 2.6 2.16 3.15 5.24 4.09
Sr (ppm) 500 561 503 236 713 77 460 209 409 409
Nd (ppm) 39.5 33 30.2 20 9.29 12.3 7.83 13.8 26.9 16.6
Zr (ppm) 100 124 130 135 75 66 77 125 96 116
Hf (ppm) 3 3.3 3.5 3.7 1.9 2 2.2 3.3 2.8 3.1
Sm (ppm) 8.81 7.4 7.06 4.6 2.27 3.17 1.28 3.78 8.07 3.92
Eu (ppm) 2.05 1.69 1.86 1.18 0.852 0.923 0.628 0.953 1.66 1.16
Sb (ppm) 0.6 0.7 0.8 0.7 0.6 0.5 <0.1 0.2 0.6 <0.1
Gd (ppm) 6.78 6.38 6.2 4.25 2.37 3.06 1.07 3.72 7.93 3.39
Tb (ppm) 1.03 0.98 0.94 0.63 0.37 0.48 0.15 0.67 1.28 0.51
Dy (ppm) 5.63 5.52 5.32 3.88 2.33 2.98 0.89 4.14 7.79 3.07
Y (ppm) 30 27 26 19 14 14 7 20 40 17
Ho (ppm) 1.08 1.06 1.06 0.79 0.46 0.6 0.17 0.84 1.46 0.59
Er (ppm) 3.06 3.08 2.89 2.24 1.38 1.69 0.46 2.39 4.14 1.86
Tm (ppm) 0.441 0.452 0.411 0.326 0.224 0.249 0.068 0.352 0.645 0.281
Yb (ppm) 2.96 2.91 2.77 2.26 1.59 1.67 0.45 2.44 4.08 1.92
TECTONIC SETTINGS AND S CONTENTS OF MAGMAS ASSOCIATED WITH CRETACEOUS DEPOSITS, CHILE

Lu (ppm) 0.48 0.449 0.467 0.362 0.259 0.262 0.073 0.39 0.569 0.308
Cr (ppm) 16.1 32.7 26 183 26.2 76.8 35.7 57 26.6 39.2
Ni (ppm) 6 14 12 42 14 32 5 33 12 15
Sc (ppm) 15.2 29.4 33 25.4 13 29.1 6.84 22.3 23.7 24.4
V (ppm) 127 316 315 201 117 233 59 83 171 213
Co (ppm) 14.6 21.3 22.5 28.2 15.3 32.7 20.2 37.9 8.9 17.8
Cu (ppm) 154 21 125 886 90 16 1,130 452 76 18
303
 Table 3. (Cont.)
304
Sample no. CAS-10 CAS-11 MV-1 MV-5 MV-10 MV-11 MV-12 DA-1 DA-2 DA-3
Mantoverde- Mantoverde- Dos Amigos- Dos Amigos-
Locality Casualidad Casualidad Laura Laura Mantoverde Mantoverde Mantoverde Dos Amigos Tricolor Tricolor
2 K-feldspar Potassic Potassic (K-feldspar, Potassic (some Potassic + minor Potassic +
Alteration/ Weak Weak propylitic with chlorite (K-feldspar, biotite, chlorite) + Potassic (some weathering to chalcopyrite- chalcopyrite-
mineralization chlorite (chlorite-epidote) overprint biotite, epidote) minor chalcopyrite Potassic weathering) clay on fractures) pyrite pyrite
TAS Basaltic trachy- Basaltic trachy-
classification1 Granodiorite Diorite Monzodiorite Monzodiorite Syenite andesite (shoshonite) andesite (shoshonite) Granodiorite Granodiorite Granodiorite
SiO2 (wt %) 61.64 59.77 46.54 50.79 57.39 51.21 49.41 64.7 65.92 66.5
Al2O3 (wt %) 14.94 15.46 15.14 16.8 16.64 14.75 16.08 13.91 14.88 14.69
Fe2O3 (wt %) 2.22 2.12 1.29 2.92 2.37 8.54 6.3 4.74 2.18 2.15
FeO (wt %) 3.7 4.4 4.7 5.9 4.1 2.9 2.9 4.3 3.2 4
MnO (wt %) 0.096 0.146 0.647 0.279 0.061 0.164 0.411 0.065 0.109 0.124
MgO (wt %) 2.44 2.94 4.65 5.25 3.06 3.23 3.27 1.76 1.55 1.5
CaO (wt %) 4.68 5.54 9.42 6.67 0.6 4.65 5.2 1.7 3.02 3.04
Na2O (wt %) 3.14 2.96 3.2 3.74 0.17 1.18 3.7 3.88 3.9 3.57
K2O (wt %) 2.97 2.76 2.17 1.85 9.81 4.05 4.13 1.83 1.48 1.94
TiO2 (wt %) 0.819 0.801 0.678 0.787 1.196 1.001 1.023 0.401 0.368 0.351
P2O5 (wt %) 0.19 0.19 0.1 0.13 0.04 0.18 0.24 0.09 0.12 0.16
LOI (wt %) 1.42 1.33 9.96 2.99 2.91 6.76 5.86 1.19 1.41 1.39
LOI 2 (wt %) 1 0.84 9.43 2.33 2.45 6.43 5.54 0.71 1.05 0.94
Total (wt %) 98.67 98.9 99.03 98.76 98.81 98.94 98.86 99.05 98.51 99.86
Total 2 (wt %) 98.26 98.41 98.51 98.1 98.36 98.62 98.53 98.57 98.15 99.41
Fe2O3(T) (wt %) 6.34 7.01 6.52 9.48 6.93 11.77 9.52 9.52 5.74 6.6
Cs (ppm) 1.8 1.7 1.8 0.5 0.7 1 1.2 2.1 0.6 0.5
Tl (ppm) 0.11 0.2 <0.05 <0.05 0.12 <0.05 0.13 0.33 0.1 0.09
Rb (ppm) 97 101 37 36 162 93 64 40 24 30
Ba (ppm) 427 368 2,230 801 1,440 377 2,753 303 654 615
Th (ppm) 13.3 11.6 2.33 3.25 3.14 2.58 4.16 2.66 3.97 3.94
U (ppm) 3.62 3.38 0.65 0.93 1.08 0.92 1.22 0.3 0.98 0.85
Nb (ppm) 5.9 5.2 2 2.9 7.1 4 5.5 3.6 3.3 3.3
Ta (ppm) 0.56 0.44 0.16 0.22 0.54 0.3 0.38 0.3 0.36 0.35
RICHARDS ET AL.

La (ppm) 22.1 20 6.32 12.9 3.43 6.87 14.7 5.81 13.4 10.8
Ce (ppm) 50.4 45.4 16.1 26.5 6.76 16.4 34 12.3 26.9 21.6
Pb (ppm) <5 8 <5 7 <5 <5 <5 7 <5 <5
Pr (ppm) 6.53 5.92 2.34 3.57 0.81 2.16 4.53 1.68 3.13 2.64
Sr (ppm) 297 323 417 490 63 50 224 269 329 321
Nd (ppm) 26.9 24.2 10.7 14.5 3.55 9.89 19.8 7.18 12.7 10.3
Zr (ppm) 259 203 62 81 108 132 124 62 69 64
Hf (ppm) 6.8 5.6 1.8 2.2 3.1 3.4 3.2 1.8 2.1 1.9
Sm (ppm) 6.45 5.64 2.69 3.44 0.87 2.4 4.7 1.8 2.75 2.31
Eu (ppm) 1.09 1.16 0.889 1.07 0.229 0.636 1.46 0.567 0.868 0.753
Sb (ppm) 1.4 1.8 5.3 1.3 0.8 1.9 1.3 0.5 0.7 1
Gd (ppm) 5.57 5.26 2.57 3.36 0.95 2.82 4.51 1.83 2.21 2.03
Tb (ppm) 0.92 0.87 0.43 0.52 0.19 0.51 0.71 0.31 0.38 0.34
Dy (ppm) 5.57 5.2 2.57 3.03 1.25 3.52 4.38 1.92 2.46 2.14
Y (ppm) 29 27 13 14 8 18 21 11 16 14
Ho (ppm) 1.12 1.05 0.5 0.6 0.27 0.8 0.86 0.4 0.52 0.45
Er (ppm) 3.24 3.04 1.34 1.68 0.88 2.51 2.43 1.2 1.61 1.37
Tm (ppm) 0.477 0.455 0.192 0.247 0.144 0.385 0.365 0.192 0.261 0.218
Yb (ppm) 3.23 3 1.27 1.64 1 2.61 2.44 1.35 1.85 1.55
Lu (ppm) 0.516 0.473 0.201 0.256 0.168 0.415 0.375 0.229 0.31 0.268
Cr (ppm) 32.1 43.6 63.3 54.3 36.3 94.7 59.7 34.4 13.4 23
Ni (ppm) 8 11 22 26 24 36 15 9 3 3
Sc (ppm) 20 23.4 27.8 27.7 22.7 24.6 27.9 8.78 7.32 7.01
V (ppm) 147 169 198 228 143 209 261 92 74 68
Co (ppm) 14.8 20.5 25.7 28.4 29 15.4 22.3 5 7.5 10.3
Cu (ppm) 111 122 12 122 214 14 230 3,190 580 1,580
LOI = loss on ignition
1Classification
schemes of Le Maitre et al. (2002) for extrusive rocks and Middlemost (1994) for plutonic rocks
 TECTONIC SETTINGS AND S CONTENTS OF MAGMAS ASSOCIATED WITH CRETACEOUS DEPOSITS, CHILE 305

Fig. 3. Total alkali-silica diagram (Le Maitre et al., 2002) showing the compositions of Cretaceous igneous rocks associated
with porphyry (blue symbols) and IOCG deposits (red symbols) in the Coastal Cordillera of northern Chile; Productora
(purple symbol) shows characteristics of both porphyry and IOCG deposits. Data are from Table 3, excluding the following
samples for reasons of extreme alteration or lack of correlation with the main suites: CAS-4 (clasts in igneous breccia); CAS-8,
9, 10, 11 (regional plutons, relationship to Casualidad deposit unclear); CDA-7 (Quebrada Marquesa Formation, andesitic
country rock); MV-10 (strong potassic alteration); MV-11, MV-12 (altered volcanic rock outcrops, relationship to Mantoverde
deposit unclear); PR-1 (Cachiyuyito stock, possibly unrelated). All of the remaining samples shown are nevertheless altered
to varying degrees, and we attribute the apparently alkaline compositions of some rocks to this effect.

1
early Cretaceous
mid-Cretaceous
late Cretaceous
IOCG
Porphyry
Rhyolite/
Granite
Trachyte
0.1
Rhyodacite, dacite/
Granodiorite
Zr/Ti

Trachyandesite/
Andesite/ Syenite
Diorite

0.01
Andesite, basalt/ Alkali basalt/
Diorite, gabbro Alkali gabbro

Sub-alkaline basalt/
Sub-alkaline gabbro

0.001
0.01 0.1 1 10
Nb/Y
Fig. 4. Zr/Ti vs. Nb/Y discrimination diagram (Winchester and Floyd, 1977) for Cretaceous igneous rocks from the Coastal
Cordillera of Chile between 25 and 34S. Regional igneous geochemical data from the literature are grouped according to
the three temporal-tectonomagmatic groups, as defined in the text. Igneous rocks related to mid-Cretaceous IOCG and late
Cretaceous porphyry deposits collected during this study are plotted for comparison. Regional Cretaceous data from Irwin
et al. (1988), Vergara et al. (1995), Cisternas et al. (1999), Parada et al. (1999, 2002), Grocott and Taylor (2002), Morata and
Aguirre (2003), Creixell (2007), Hasler (2007), and Lpez et al. (2014).
306 RICHARDS ET AL.

Fig. 5. Primitive mantle-normalized extended trace element diagrams (normalization values of Sun and McDonough, 1989)
for selected igneous rocks associated with (a) porphyry and (b) IOCG deposits in the Coastal Cordillera of northern Chile.

(LILEs: Rb, Ba, Th, U, K) and light rare earth elements
(LREEs); negative anomalies for Nb, Ta, and Ti; relative
depletions in compatible elements and middle to heavy rare
earth elements (MREEs, HREEs); and flat to listric-shaped
patterns from MREEs to HREEs. Such patterns are typical
of subduction-related igneous rocks and reflect enrichments
in fluid-mobile LILEs, retention of Nb, Ta, and Ti in insoluble
Fe-Ti oxides, and fractionation of amphibole (which preferen-
tially partitions MREEs; Gill, 1981; Green and Pearson, 1985;
Klein et al., 1997). The only noticeable difference between
 TECTONIC SETTINGS AND S CONTENTS OF MAGMAS ASSOCIATED WITH CRETACEOUS DEPOSITS, CHILE 307

Fig. 6. C1 chondrite-normalized extended trace element diagrams (normalization values of Sun and McDonough, 1989)
for selected igneous rocks associated with (a) porphyry and (b) IOCG deposits in the Coastal Cordillera of northern Chile.

these suites is the slightly greater depletion of MREEs-
HREEs in the porphyry-related suite, which can be attributed
to the more felsic (fractionated) nature of these rocks. This
characteristic is also observed in the ratios of Sr/Y and La/Yb,
which are generally more elevated in the felsic porphyry suite
compared to the more mafic IOCG suite (Fig. 7).
In an attempt to assess the relative oxidation states of the
various suites of rocks, we have assessed whole-rock Fe2O3/
FeO ratios where reported. While many of these samples are
altered to varying degrees, which will clearly affect the Fe2O3/
FeO ratio, most of the samples have values ranging from 0.18
to 5.10, corresponding to moderately or strongly oxidized
308 RICHARDS ET AL.

Fig. 7. (a) Sr/Y versus Y and (b) La/Yb versus Yb plots for selected igneous rocks associated with porphyry and IOCG deposits
from the Coastal Cordillera of northern Chile. The more adakite like compositions of many of the porphyry rocks compared
to many of the IOCG-related rocks likely reflect the more felsic compositions and greater degrees of fractionation (especially
of amphibole) of the former. Note that, with only one exception, all of these rocks have lower La/Yb ratios than adakites.
Fields for adakite-like rocks from Richards and Kerrich (2007); regional Cretaceous data from Irwin et al. (1988), Vergara et
al. (1995), Cisternas et al. (1999), Parada et al. (1999, 2002), Grocott and Taylor (2002), Morata and Aguirre (2003), Creixell
(2007), Hasler (2007), and Lpez et al. (2014).

rocks (using the criteria of Blevin, 2004). Importantly, there Published Sr-Nd isotope compositions for 53 Cretaceous
is no clear difference in oxidation state between the three igneous rocks from the Coastal Cordillera between 25 and
temporal-tectonomagmatic groups and porphyry- and IOCG- 34S (Supplementary Table S3) are plotted in Figure 8.
related rocks, which all appear to be similarly oxidized. Early Cretaceous rocks have evolved isotopic compositions
 TECTONIC SETTINGS AND S CONTENTS OF MAGMAS ASSOCIATED WITH CRETACEOUS DEPOSITS, CHILE 309

10
Depleted MORB mantle
early Cretaceous
mid-Cretaceous
late Cretaceous

Nd 5

Jurassic igneous rocks

0
Crustal contamination trend

Late Paleozoic
intrusive rocks

-5
0.702 0.703 0.704 0.705 0.706 0.707 0.708 0.709 0.710

(87Sr/86Sr)i
Fig. 8. Nd vs. initial 87Sr/86Sr ratios for Cretaceous igneous rocks from the Coastal Cordillera of Chile between 25 and
34S. Mid-Cretaceous rocks associated with IOCG deposits mostly fall at the primitive end of a range of data reflecting
various degrees of crustal contamination of mantle-derived magmas, whereas early and late Cretaceous rocks associated
with porphyry deposits range to significantly more isotopically evolved compositions. Data from Parada et al. (2005), Hasler
(2007), Morata et al. (2008), and Girardi (2014). Depleted MORB mantle field at ~110 Ma from Pilet et al. (2011). Jurassic
igneous rock field from Parada et al. (1999), Creixell (2007), and Girardi (2014). Paleozoic intrusive rock field from Parada
et al. (1999).

suggesting extensive crustal contamination. In contrast, the
mid- and later Cretaceous rocks cluster at relatively primitive
compositions, albeit still with some crustal contamination.
Apatite Compositions
Electron microprobe analyses of magmatic and hydrothermal
apatite from three samples from the Carmen de Andacollo
porphyry and seven samples from or near IOCG deposits
(Productora, Candelaria, and Casualidad) are listed in Supple-
mentary Table S4, and SO3 analyses of magmatic apatite are
summarized in Table 4 (along with data from the literature).
The results show a clear difference between igneous apatite
from rocks associated with the Carmen de Andacollo porphyry
deposit (0.25 0.17 wt % SO3, n = 69) compared with those
from IOCG deposits (0.04 0.02 wt % SO3, n = 76). A simi-
lar relationship is observed for apatite from porphyry deposits
(0.120.60 wt % SO3) and IOCG deposits (0.070.13 wt %
SO3) reported in the literature (Table 4). Hydrothermal or
late-stage igneous apatite (e.g., edges of apatite micropheno-
crysts; Fig. 2d) showed lower and more variable SO3 contents
(Supplementary Table S4), consistent with observations else-
where in the literature (Streck and Dilles, 1998; Van Hoose
et al., 2013).
The SO3 content of apatite varies as a complex function
of magmatic temperature, oxidation state, and sulfur fugac-
ity (Peng et al., 1997; Parat and Holtz, 2005; Parat et al.,
2011), and an accurate calculation of magmatic sulfur con-
tent from apatite SO3 compositions is not currently possible.
However, the apatite-melt partition coefficient formula of
Peng et al. (1997), which is derived for relatively oxidized
arc magmas, can be used to obtain a semiquantitative esti-
mate of magmatic S content. We have estimated the apatite
saturation temperature of four samples from the Carmen de
Andacollo porphyry, the Candelaria and Casualidad IOCG
deposits, and a sample of regional mid-Cretaceous igneous
rock near Productora (using the equation of Piccoli and Can-
dela, 1994, 2002, which is derived from the data of Harrison
and Watson, 1984) and used this temperature in the equa-
tions of Peng et al. (1997) and Parat et al. (2011) to derive
estimates of magmatic S content. The data reported in Table
5 suggest that the average S content of the magma associ-
ated with the Carmen de Andacollo porphyry deposit was
~0.02 wt %S (up to 0.06 wt % S)significantly higher than
the average values for magma associated with IOCG depos-
its in the region (0.0010.005 wt % S; Table 5). An alterna-
tive method for calculating magmatic sulfur content from
apatite SO3 compositions is provided by Parat et al. (2011),
and these values are also listed in Table 5. The results differ
somewhat in absolute values compared to the results using
the Peng et al. (1997) formula, but not in the relative enrich-
ment in S of the porphyry-related magmas compared to the
IOCG-related magmas.
In order to eliminate the possibility that contrasting mag-
matic oxidation state was responsible for this difference in
apatite SO3 content, we have estimated magmatic fO2 values
for these samples from the average MnO contents of apatite
310 RICHARDS ET AL.

Table 4. Summary of SO3 Compositions of Igneous Apatite from Chilean and Other Porphyry and IOCG Deposits

SO3 (wt %)

Locality Deposit type Minimum Maximum Average s.d. n Source

Carmen de Andacollo Porphyry Cu-Au 0.05 0.81 0.25 0.17 69 This study
Productora Transitional IOCG 0.02 0.07 0.04 0.02 14 This study
Candelaria IOCG 0.02 0.09 0.03 0.02 32 This study
Casualidad IOCG 0.02 0.08 0.03 0.02 30 This study
Yerington Porphyry Cu 0.26 0.99 0.60 0.36 4 Streck and Dilles (1998)
Santo Tomas II (Philex) Porphyry Cu n.a. 0.45 0.30 0.07 n.a. Imai (2002)
Santo Tomas II (Philex) Porphyry Cu n.a. 0.62 0.25 0.07 n.a. Imai (2002)
Clifton Porphyry Cu n.a. 0.76 0.29 0.14 n.a. Imai (2002)
Clifton Porphyry Cu n.a. 0.48 0.27 0.08 n.a. Imai (2002)
Bumolo (Waterhole) Porphyry Cu n.a. 0.59 0.21 0.15 n.a. Imai (2002)
Camp 6 (Black Mountain) Porphyry Cu n.a. 0.48 0.12 0.09 n.a. Imai (2002)
Dizon Porphyry Cu n.a. 0.57 0.17 0.08 n.a. Imai (2002)
Taysan Porphyry Cu n.a. 0.55 0.20 0.11 n.a. Imai (2002)
Duolong Porphyry Cu-Au 0.44 0.82 n.a. n.a. n.a. Li et al. (2012)
Mt. Isa IOCG n.a. n.a. 0.13 0.09 n.a. Piccoli and Candela (2002)
Mt. Isa IOCG n.a. n.a. 0.07 n.a. n.a. Belousova et al. (2002)
Tjrrojkka IOCG 0.02 0.13 0.08 0.03 n.a. Edfelt (2007)
Se-Chahun IOCG (IOA) <0.03 0.11 n.a. n.a. n.a. Bonyadi et al. (2011)

n.a. = data not available, s.d. = standard deviation

using the equation of Miles et al. (2014, Table 5). These data
confirm that all of the rocks are moderately oxidized (DFMQ
0.42.7), although we note that this fO2 calculation relies on
electron microprobe analyses of Mn in apatite at concentra-
tions close to the detection limit, and so cannot be considered
highly accurate. There is also debate about the applicability of
this method to rocks of different magmatic temperature and
composition (Marks et al., 2016; Miles et al., 2016), although
the samples compared here are of broadly similar composi-
tion and likely temperature. Consequently, we consider that
the formula of Peng et al. (1997), derived for oxidized arc
rocks, should be approximately valid, and the calculated abun-
dances of magmatic S should be relatively correct, even if the
absolute values are questionable (cf. Streck and Dilles, 1998).
These data support the hypothesis that the porphyry-forming
magmas were richer in S than the IOCG-related magmas.
Discussion
Igneous geochemistry
Whole-rock geochemical compositions of Cretaceous igneous
rocks from the Coastal Cordillera of Chile between 25 and
34S show minimal differences beyond those expected from
normal fractionation processes (Figs. 35). Rocks associated
with early Cretaceous arc rifting (with minor porphyry Cu-Au
deposits), mid-Cretaceous back-arc transtension (with IOCG
deposits), and later Cretaceous contractional arc magmatism
(with porphyry Cu-Au-(Mo) deposits) have compositions typi-
cal of subduction-related magmatism. On average, however,
later Cretaceous arc rocks are more felsic (Fig. 3), with pro-
nounced listric-shaped REE patterns (Fig. 6) and higher Sr/Y
and La/Yb ratios compared to mid-Cretaceous rocks associ-
ated with IOCG deposits (Fig. 7). There is also a suggestion
that some of the mid-Cretaceous magmas and those associ-
ated with IOCG deposits may have had slightly more mafic,
alkaline compositions (alkali gabbros to syenites).
We interpret these data to indicate that there was little fun-
damental change in the source of magmatism throughout the
Cretaceous, except for a hint of more mafic alkaline magma-
tism during the mid-Cretaceous transtensional rifting phase.
Published Sr and Nd isotope compositions of Cretaceous rocks
from the Coastal Cordillera indicate mixing between depleted,
mantle-derived magmas and isotopically evolved continen-
tal crust, with early Cretaceous magmas showing the highest
degrees of contamination, likely by late Paleozoic lower and
mid-crustal rocks (Fig. 8, Damm et al., 1990; Lucassen et al.,
1999, 2001, 2002). Although the isotopic ranges of mid- and
late Cretaceous rocks overlap, there is a significant clustering
of mid-Cretaceous data at the most primitive end of the range
(eNd 6, 87Sr/86Sri 0.7033). We suggest that back-arc exten-
sional tectonics in the mid-Cretaceous may have facilitated
the greater involvement of primitive, mildly alkaline magmas
derived from partial melting of upwelling mantle astheno-
sphere during crustal extension and thinning (Fig. 9). Never-
theless, a significant amount of crustal processing is evident
for all of these Cretaceous magmas, as is commonly observed
in continental arc rocks (Hildreth and Moorbath, 1988). The
more felsic nature and higher Sr/Y and La/Yb ratios of the later
Cretaceous porphyry-associated magmas (Fig. 7) may reflect
longer residence times in deep crustal magma chambers under
contractional tectonic conditions (Hildreth and Moorbath,
1988; Haschke et al., 2002; Richards and Kerrich, 2007), with
more extensive fractionation of amphibole (Lang and Titley,
1998; Richards and Kerrich, 2007; Richards, 2011a).
We co nclude that it is not possible uniquely to distinguish
between igneous rocks associated with porphyry and IOCG
deposits in the Coastal Cordillera of Chile using their whole-
rock geochemical or isotopic compositions alone, although the
IOCG-associated rocks are, on average, more mafic (locally
alkaline) and isotopically slightly more primitive than the por-
phyry-related rocks, consistent with their back-arc as opposed
to main arc tectonomagmatic setting.


Table 5. Estimates of Magmatic Temperature and Oxidation State from Igneous Apatite and Whole-Rock Compositions

Apatite SO3
Whole- Whole- Apatite (wt %) (n)3 Average Average Maximum Maximum
Deposit Sample rock SiO2 rock P2O5 MnO Estimated Estimated [maximum, magmatic S magmatic S magmatic S magmatic S
(type) no. (wt %)1 (wt %)1 AST2 (wt %) (n)3 log fO24 DFMQ5 minimum] content (wt %)6 content (wt %)7 content (wt %)6 content (wt %)7

Carmen de CDA-2 66.74 0.14 905C n.a. n.a. n.a. 0.23 0.18 (34) 0.0160 0.0088 0.0571 0.1308
Andacollo [0.05, 0.81] 0.0120 0.0230
(porphyry) CDA-88
63.67 0.21 917C 0.12 0.04 (18) 11.8 1.5 0.4 1.7 0.27 0.16 (35) 0.0230 0.0079 0.0513 0.0364
[0.08, 0.61] 0.0137 0.0102

Productora PR-5 64.95 0.13 878C n.a. n.a. n.a. 0.04 (1) 0.0017 0.0010 0.0017 0.0010
(transitional PR-8 57.66 0.19 830C 0.08 0.01 (8) 11.1 0.9 2.7 1.1 0.04 0.02 (13) 0.0009 0.0010 0.0015 0.0012
IOCG) [0.02, 0.07] 0.0003 0.0001

Candelaria CAN-2 58.45 0.45 951C n.a. n.a. n.a. 0.04 0.02 (3) 0.0051 0.0010 0.0077 0.0011
(IOCG) [0.03, 0.06] 0.0022 0.0001
CAN-3 53.36 0.45 880C 0.12 0.06 (6) 11.8 1.9 1.1 2.1 0.03 0.02 (29) 0.0017 0.0010 0.0043 0.0013
[0.02, 0.09] 0.0007 0.0001

Casualidad CAS-4 66.67 0.13 897C n.a. n.a. n.a. 0.06 0.03(3) 0.0030 0.0011 0.0050 0.0013
(IOCG) [0.02, 0.08 ] 0.0015 0.0002
CAS-10 63.65 0.20 911C n.a. n.a. n.a. 0.04 0.02(4) 0.0035 0.0010 0.0046 0.0011
[0.02, 0.06] 0.0020 0.0001
CAS-11 61.56 0.20 886C 0.08 0.03 (10) 11.0 1.2 1.7 1.4 0.03 0.01(23) 0.0016 0.0009 0.0034 0.0012
[0.02, 0.07] 0.0006 0.00007

n.a. = no data available

1Normalized to 100 wt % (Supplementary Table S1)

2 2 5
2Apatite saturation temperature (AST) calculated from whole-rock SiO and P O concentrations using the equation of Piccoli and Candela (1994), recast from the data of Harrison and Watson (1984)
3Average of all igneous apatite analyses (Supplementary Table S4)
4Average log f
O2 calculated from MnO contents of igneous apatite crystals (Supplementary Table S4) using the equation of Miles et al. (2014):
log fO2 = 0.0022 ( 0.0003) Mn (ppm) 9.75 ( 0.46)
5Average log f
O2 value relative to the fayalite-magnetite-quartz (FMQ), where the value of FMQ at different temperatures (provided by the AST estimate) is calculated using the equation of Myers
and Eugster (1983): log fO2 = 24,441.9/T (K) + 8.290 ( 0.167); the FMQ error is the sum of the 0.167 error on FMQ and the uncertainty in the sample log fO2estimate from the previous column
3
6Estimated from apatite SO contents (Supplementary Table S4) using the temperature-dependent apatite-melt partition coefficient formula of Peng et al. (1997):

lnKD = 21,130/T 16.2 (where T is in Kelvin)

3 3 3
7Estimated from apatite SO contents (Supplementary Table S4) using the apatite-melt partition coefficient formula of Parat et al. (2011): SO apatite (wt %) = 0.157 ln[SO ] (melt, wt %) + 0.9834 (r2

= 0.62)
TECTONIC SETTINGS AND S CONTENTS OF MAGMAS ASSOCIATED WITH CRETACEOUS DEPOSITS, CHILE

2 2 5
8SiO and P O compositions for this sample taken from sample CDA-9 (same lithology as CDA-8 but less altered)
311
312 RICHARDS ET AL.

Mild extension
difficult to constrain these parameters due to the widespread
(a) Early Cretaceous
effects of oxidation during hydrothermal alteration in ore-
Small porphyry Volcanic arc
associated rocks and the loss of S (as SO2) from igneous rocks
deposits
Sea level
Minor upper crustal
as they crystallize. Nevertheless, Fe2O3/FeO ratios of igneous
0 km
Oceanic crust Continental
crust
plutonism rocks from these different associations show no clear differ-
Lower crustal
Oceanic mantle
lithosphere
MASH zone ence, and all are moderately to strongly oxidized (acknowl-
Basaltic
underplating SCLM
edging that many of these rocks are hydrothermally altered,
1000C which likely leads to some secondary oxidation). We would
Partial melting of
hydrated mantle 100 km expect the oxidation state of the magma to make a difference
De

wedge
to the behavior of dissolved sulfur only if the rocks were sig-
h yd

nificantly reduced (resulting in S being dominantly present

ra

Asthenosphere
t
io

Asthenosphere
n

as sulfide) compared to oxidized (with S dissolved as sulfate;

10
10

00
00

Carroll and Rutherford, 1985; Jugo et al., 2005). All of the

C
C

200 km
(b) Mid-Cretaceous Sinistral rocks in these suites appear to be at least moderately oxidized,
transtension as expected in arc rocks, so S should have behaved in a similar
Minor volcanism
Upper crustal
batholith and IOCG
way in the magma.
formation
0 km
In order to test the hypothesis that the magmas that formed
S-rich porphyry deposits were more S rich than those form-
ing S-poor IOCG deposits, we analyzed the compositions of
1000C igneous apatite crystals trapped as inclusions in silicate phe-
De

Back-arc
nocryst phases. Our results show that apatite from intrusive
hy

asthenospheric
dra

upwelling
100 km rocks associated with the Carmen de Andacollo porphyry
tio

Cu-Au deposit contains significantly more S (0.25 0.17 wt%

n

Partial-melting in lower crust,

amphibolite (black), or
hydrated lithosphere SO3; Table 4) than that from rocks associated with or near
1000C

Partial-melt flow lines IOCG deposits (Productora, Candelaria, and Casualidad;

Fluid flow lines
0.04 0.02wt % SO3; Table 4). No reliable formula currently
200 km
(c) Late Cretaceous Contraction exists to convert apatite SO3 compositions to magmatic S con-
to Cenozoic tents, but the partition coefficients of Peng et al. (1997) can
Large porphyry
deposits Volcanic arc be used to provide a semiquantitative estimate. The results
Upper crustal 0 km
of these calculations suggest that Carmen de Andacollo por-
Continental
crust
batholith phyry magmas contained ~0.02 wt % S, compared to 0.001 to
Lower crustal
MASH zone 0.005wt% S in the IOCG-associated magmasan order of
De
hy Basaltic
underplating 1000C
magnitude difference (Table 5). This is the opposite to what
dr
at
io
n SCLM would be expected if the difference were simply due to the
of Partial melting of
oc
ea hydrated mantle 100 km felsic versus more mafic nature of the porphyry- versus IOCG-
ni wedge
c
lith
os
related rocks, because S solubility decreases with decreasing
ph
10

Asthenosphere er FeO content of magmas (Wallace and Carmichael, 1992). We

00

e
C

10
00
C
conclude that the IOCG-related magmas were significantly
200 km
S undersaturated compared to the porphyry-forming mag-
mas and, consequently, could only generate S-poor magmatic
Fig. 9. Schematic model illustrating the evolution of the tectonomagmatic hydrothermal fluids and ore deposits.
setting along the margin of northern Chile between 25 and 34S during the
Cretaceous, and its relationship to porphyry and IOCG deposit formation. Metallogenic implications
SCLM = subcontinental lithospheric mantle.
The differences in tectonic setting and S content of magmas
associated with porphyry and IOCG deposits in the Meso-
zoic Coastal Cordillera of Chile suggest contrasting models
Magmatic sulfur content for their formation (Fig. 9). Tectonomagmatic processes that
Porphyry and IOCG deposits are most fundamentally dif- give rise to magmas with the potential to form porphyry Cu
ferentiated by the much greater abundance of sulfur in the Mo Au deposits are well established (Richards, 2003; Cooke
former (predominantly fixed as pyrite in phyllic alteration et al., 2005) and involve the evolution of hydrous, oxidized,
zones) compared to the latter (where Fe oxides, magnetite S-rich, calc-alkaline magmas derived from partial melting
and hematite, predominate). We have hypothesized that this in the metasomatized suprasubduction zone asthenospheric
might reflect a difference in the chemistry of magmas asso- mantle wedge (Fig. 9a, c). A continuous flux of oxidized sulfur
ciated with these contrasting deposit types, but the analysis and water (and other fluid-mobile components such as Cl and
presented above shows that no clear differences can be found LILEs) from the subducting slab supplies the large amount
in their major and trace element compositions, although the of S that is typically present in Phanerozoic arc magmas and
IOCG-related rocks are somewhat more mafic than the por- gives them the potential to form S-rich porphyry deposits.
phyry intrusions. An input of oxidized sulfur is specifically required because
Two other possible explanations are differences in the oxi- reduced sulfur will separate early from the magma as sulfide
dation state or sulfur content of the original magma, but it is liquid and will deplete the magma of chalcophile elements
 TECTONIC SETTINGS AND S CONTENTS OF MAGMAS ASSOCIATED WITH CRETACEOUS DEPOSITS, CHILE 313
prior to their potential segregation into late-exsolving mag-
matic hydrothermal fluids (Hamlyn et al., 1985; Spooner,
1993; Richards, 1995, 2003).
If this supply of oxidized sulfur ceases (e.g., subduction
stops due to arc migration, reversal, or collision) or moves
away from the region of magma production (e.g., subduction
rollback), then derived magmas will be relatively S poor (Wal-
lace and Edmonds, 2011). This may occur in back-arc settings,
where slab rollback and back-arc extension result in the gen-
eration of magmas from upwelling asthenosphere distal to the
subduction zone. These magmas have compositions reflect-
ing more primitive intra-plate characteristics, although they
retain some arc geochemical features (Kimura and Yoshida,
2006; Caulfield et al., 2012; Timm et al., 2012).
We hypothesize that this may have been the case during the
mid-Cretaceous back-arc extensional phase in northern Chile,
and that magmas formed at this time had lower magmatic S
contents than normal arc magmas due to their distance from
the subduction zone. Interaction of these relatively primi-
tive, S-undersaturated asthenospheric magmas with previ-
ously subduction metasomatized upper plate lithosphere
may have resulted in remobilization of metals and volatiles
by dissolution of residual Cu-Aurich sulfides and melting
of hydrous silicates from lower crustal arc cumulates (Keays,
1987; Ackerman et al., 2009; Richards, 2009). Derivative mag-
mas would be compositionally similar to normal arc magmas
(being largely derived from subduction-modified lithosphere)
but would only have the potential to form S-poor magmatic-
hydrothermal ore deposits upon upper crustal emplacement
(Fig. 9b; Core et al., 2006; Richards, 2009; Pettke et al., 2010;
Richards and Mumin, 2013a, b). Deposits formed under such
conditions would share many traits with normal arc porphy-
ries but would be deficient in sulfur and sulfide minerals, and
rich instead in Fe oxides. We refer to these as IOCG deposits
and note that they share many similarities with magnetite-
rich, alkalic-type porphyry Cu-Au deposits formed in back-
arc settings (Harris et al., 2013), suggesting a continuum of
broadly subduction related magmatic-hydrothermal deposit
types, differentiated largely by their sulfur contents and the
sulfur contents of the generative magmas (Richards and
Mumin, 2013b).
Conclusions
By studying an area where porphyry and IOCG deposits occur
in relatively close spatial and temporal proximity, we have
shown that small changes in tectonic conditions can gener-
ate magmas with broadly similar bulk compositions but sub-
stantially different sulfur contents, such that distinctive ore
deposit types are formed. Specifically, porphyry Cu Mo
Au deposits form from relatively S rich arc magmas under
conditions of upper plate contraction or transpression (e.g.,
the late Cretaceous period in Chile) and suboptimally under
extension (early Cretaceous; Tosdal and Richards, 2001). In
contrast, magmas generated in back-arc (extensional) settings
distal to the subduction zone are likely to be relatively S poor
and somewhat more mafic (locally alkaline, and isotopically
primitive) in composition. Where such magmas interact with
previously subduction modified lithosphere during ascent,
they may remobilize metals, leading to the potential forma-
tion of S-poor ore deposits, such as IOCG and alkalic-type
porphyry Cu-Au deposits. Some overlap in space and time
between these deposit styles may result from local mantle and
crustal heterogeneities, as well as delayed magmatic responses
to tectonic changes. We suggest that other deposit types in
the wider IOCG family diverge from this point of intersection
with porphyry systems by the greater involvement of external
fluids and crustal metal fluxing.
Acknowledgments
This paper is based in part on the published findings of
numerous researchers, whose work we hope we have appro-
priately cited. This research was funded by a Discovery
Grant (RGPIN203099) and an Engage Grant (EGP 485693-
15) from the Natural Sciences and Engineering Research
Council of Canada to JPR, and a postdoctoral fellowship
from the University of Alberta to GPL. Claire Chamberlain
and Andrew Davies from Teck Resources Ltd. are particu-
larly thanked for their support of the Engage Grant and for
access to and accommodation at the Carmen de Andacollo
mine. We also thank all the geologists who helped us at the
mine or project sites, particularly Andres Castillo from Teck
Resources Ltd., Cristian Vasquez from Hot Chili Limited,
Osvaldo Beltran from Pucobre, Cristian Leal from the Dos
Amigos Mine, Bernardino Garay and Orlando Rivera from
Codelco Chile, and Jose Armando Rodriguez from Anglo
American. Special thanks go to Brian Townley for lending
us regional maps. Finally, we are also grateful to managers
Jorge Skarmeta (Codelco Chile), Vicente Irarrazabal (Anglo
American), Rodrigo Arce (Anglo American), Wilfredo Tabilo
and Marcelo Bruna (Pucobre), Rodrigo Diaz (Hot Chili), and
Melanie Leighton (Hot Chili) for giving permission to access
their sites and to sample drill core. Jared Geiger is thanked for
his help with sample preparation at the University of Alberta.
Garry Davidson is thanked for his careful review of an ear-
lier version of the manuscript, and Murray Hitzman and John
Dilles are thanked for their editorial contributions, which
have helped to improve its quality.
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APPENDIX
Sources of Data for Figure 1
Tectonostratigraphic time boundaries in Figure 1b (gray lines)
were defined based on correlation of similar formations and
their interpreted tectonic settings, as follows:
i. Punta del Cobre, Arqueros, and Veta Negra formations
(Charrier et al., 2007);
ii. Contact between Punta del Cobre and Bandurrias forma-
tions (Marschik and Fontbot, 2001);
iii. Lower member of Cerrillos Formation (Maksaev et al.,
2009);
iv. Ka1/Ka2 boundary, Arqueros Formation (Morata et al.,
2008);
v. Quebrada Marquesa/Viita formations (Emparan and
Pineda, 2006);
vi. Arqueros Formation (Ferrando et al., 2014);
vii. Quebrada Marquesa Formation (Lpez, 2012);
viii. Las Chilcas Formation (Wall et al., 1999).
Black lines represent the time boundaries of different tec-
tonic settings based on a compilation of kinematics and tim-
ing of movement on structures along the Coastal Cordillera,
as follows:
1. Atacama fault system at 25.5 to 27S (Grocott and Tay-
lor, 2002);
2. Atacama fault system at 25 to 27S (Brown et al., 1993;
Taylor et al., 1998);
3. Atacama fault system at 26 to 27.5S (Dallmeyer et al.,
1996);
4. Atacama fault system at 29S (Arvalo et al., 2003);
5. Dos Amigos fault system (Almonacid, 2007);
6. Bahia Agua Dulce shear zone at 32S (Ring et al., 2012);
7. El Romeral fault at 30S (Emparan and Pineda, 2006);
8. Silla del Gobernador fault at 32S (Arancibia, 2004);
9. Magnetic fabric in Illapel plutonic complex (Ferrando et
al., 2014);
10. Dike swarms at 33S (Creixell et al., 2011);
11. Rapid exhumation of intrusions at 33S (Gana and
Zentilli, 2000).