©2010 Society of Economic Geologists, Inc.

Economic Geology, v. 105, pp. 1243–1270

Petrogenetic Evolution of Arc Magmatism Associated with Late Oligocene

to Late Miocene Porphyry-Related Ore Deposits in Ecuador*
PHILIP SCHÜTTE,1,†,** MASSIMO CHIARADIA,1 AND BERNARDO BEATE2
1Department of Mineralogy, University of Geneva, Rue des Maraîchers 13, 1205 Genève, Switzerland
2Escuela Politécnica Nacional, Quito, Ecuador

Abstract
We present a data set on the geochemical and isotopic composition of mineralized porphyry intrusions, se-
riate intrusions, and arc volcanic formations spatially associated with late Oligocene to late Miocene, porphyry-
related ore deposits in Ecuador. Our aim is to constrain the petrogenetic evolution of these arc magmas, to
evaluate geodynamic and tectonic impact factors on arc magmatism, and to explore the metallogenic signifi-
cance of these parameters.
We distinguish four petrogenetic groups associated with the investigated magmatic centers, indicating dif-
ferent paths of low- and high-pressure crustal magma evolution. Tertiary Ecuadorian arc magmas, which dif-
ferentiated at higher crustal pressures, are commonly characterized by adakite-like compositions related to
fractionation and/or restite equilibration effects of amphibole ± garnet ± titanite, particularly in hydrous silicic
melts without concomitant or subsequent major plagioclase fractionation. Trace element distribution patterns
of arc magmas through time are broadly systematic and indicate that crustal magma differentiation progres-
sively extends to higher pressures from the late Oligocene to the late Miocene, possibly related to crustal thick-
ening. Locally, adakite-like features—possibly related to high melt H2O contents or accessory phase fractiona-
tion—are already observed in the early Miocene in a regional setting otherwise dominated by low-pressure
magma evolution.
Compositional differences between mineralized porphyry intrusions and spatially associated, seriate precur-
sor intrusions in Ecuador mostly reflect regional-scale changes in magma composition through time and are
not observed if the relative emplacement age difference is small. Where porphyry intrusions are associated with
shallow, crustal batholith systems in northern-central Ecuador, their emplacement is commonly late with re-
spect to batholith magmatism. Intrusive compositions indicate that porphyry parental melts mostly evolved at
higher crustal pressures where metallogenically favorable melt preconditioning might possibly occur.

Introduction
PORPHYRY CU deposits and, partly, epithermal high and inter-
mediate sulfidation type deposits—hereafter referred to as
“porphyry-related ore deposits”—form as parts of hydrother-
mal systems related to upper crustal, magmatic fluid exsolu-
tion (Seedorff et al., 2005; Sillitoe, 2010). They can be found
in subduction zone settings worldwide and are regarded as
products of a series of commonplace geologic processes that
have to combine favorably to eventually result in economic
mineralization (Tosdal and Richards, 2001; Richards, 2003,
2005).
Porphyry-related ore deposit distribution and tonnage vary
through time and space (Wilkinson and Kesler, 2009), imply-
ing that certain tectonomagmatic environments may be par-
ticularly prolific for maximizing the potential of porphyry-re-
lated ore deposit formation. Some authors have proposed that
a slab melt component in the petrogenetic evolution of por-
phyry parental melts (indicated by an “adakitic” composition
of porphyry intrusions and facilitated by a special geodynamic
setting) might define such a favorable tectonomagmatic envi-
ronment on the grounds that slab melts are potentially highly
oxidized and that such melt batches may retain their full chal-
cophile element (Au, Cu) budget upon their passage from the
† Corresponding author: e-mail, Ph.Schutte@gmail.com
**Present address: Federal Institute for Geosciences and Natural Re-
sources (BGR), Stilleweg 2, 30655 Hannover, Germany.
* A digital supplement with Appendix and Appendix tables is available at
<http://www.geoscienceworld.org/> or, for subscribers, on the SEG website,
<http://www.segweb.org>.
0361-0128/10/3920/1243-28
mantle wedge to the upper crust (Mungall, 2002). In this con-
text, Thieblémont et al. (1997) empirically observed an asso-
ciation of porphyry-related ore deposits (in some selected,
mostly Tertiary arcs worldwide) with adakitic arc magmatism,
and Oyarzun et al. (2001) noted that Tertiary arc magmatism
of adakitic affinity tends to be associated with higher tonnage
ore deposits than “normal” arc magmas in Chile.
Originally, slab melting has been suggested to contribute to
the petrogenesis of some island-arc magmas based on geody-
namic considerations and a specific magma composition
termed “adakitic,” which is indicative of parental melt equili-
bration with a Y- and heavy, rare earth element-retentive min-
eral phase (garnet) outside of the stability field of plagioclase
(Kay, 1978; Defant and Drummond, 1990). Important com-
positional features characteristic of intermediate-silicic,
adakitic magmas include elevated Sr contents (rarely below
400 ppm), and low Y (≤18 ppm) and Yb (≤1.9 ppm) concen-
trations (Defant and Drummond, 1990; threshold values have
subsequently been modified by some authors; see Richards
and Kerrich, 2007, for a comprehensive summary). However,
more recent studies have shown that a straightforward
adakite-slab melt correlation cannot be unambiguously
demonstrated in continental arc settings where similar geo-
chemical signatures in arc magmas—referred to as “adakite-
like”—are commonly acquired through crustal magma evolu-
tion (Richards and Kerrich, 2007, and references therein).
Thus, the occasionally observed association of adakite-like
magma chemistry and porphyry-related ore deposits does not
necessarily relate to a specific process, such as slab melting in
Submitted: April 5, 2010
1243 Accepted: August 25, 2010
1244 SCHÜTTE ET AL.

the magma source. It may, however, reflect certain petroge-
netic processes of crustal magma evolution—such as progres-
sive volatile enrichment of porphyry parental melts at high
pressures—which are considered as favorable for subsequent
porphyry-related ore deposit formation (e.g., Rohrlach and
Loucks, 2005).
The Ecuadorian arc system located at the northwestern
South American margin hosts a number of moderate-ton-
nage, Oligocene-Miocene, porphyry-related ore deposits
(PRODEMINCA, 2000a, b). These deposits formed on the
background of a complex geodynamic setting. The overall
character of Ecuadorian arc magmatism seems to shift from
dominantly nonadakitic to adakite-like during late Miocene
times; the timing of the change is only loosely constrained at
ca. 9 Ma (Chiaradia et al., 2004a, 2009a). In this context, a
pilot study by Chiaradia et al. (2004a) noted a mutual exclu-
sivity of mainly late Oligocene to mid-Miocene, porphyry-re-
lated ore deposits associated with nonadakitic arc magmatism
and the occurrence of late Miocene or younger, adakite-like
arc magmatism in Ecuador.
The observation of Chiaradia et al. (2004a) is at odds with
the potential association of porphyry-related ore deposits and
adakite-like magmatism, as noted above, and forms the prin-
cipal motivation for the present study. Our contribution pre-
sents new geochemical and isotopic data for a number of
Oligocene-Miocene, mineralized porphyry intrusions, as well
as seriate intrusions and volcanic formations spatially associ-
ated with porphyry-related ore deposits in Ecuador, repre-
senting the most extensive data set to date for Tertiary ig-
neous rocks of the northern Andes. We use geochemical and
isotopic data to investigate the petrogenetic evolution of arc
magmas associated with Ecuadorian porphyry-related ore de-
posits. Our new data, in combination with recently obtained
geochronologic data on Tertiary Ecuadorian arc magmatism
(Schütte et al., 2010), further allow us (1) to inspect the scope
and metallogenic significance of the apparent mutual exclu-
sivity of porphyry-related ore deposits and adakite-like mag-
matism in Ecuador noted by Chiaradia et al. (2004a), and (2)
to discuss the Oligocene-Miocene evolution of Ecuadorian
arc magmatism on the background of the regional geody-
namic setting.
Regional Geology and Geodynamic Setting
The Ecuadorian margin is made up of a foreland basin-
hosting, back-arc region; a major orogen, split into the Eastern
and Western Cordilleras; and a forearc sliver, which undergoes
trench-parallel, dextral strike-slip displacement relative to the
continent as a result of oblique plate convergence between
the Nazca plate and South America (Litherland et al., 1994;
Ego et al., 1996).
While southern Ecuador (south of 2°30' S latitude) is
mostly characterized by subaerial continental arc magmatism
throughout the Tertiary (with the Saraguro Group forming
the most prominent outcrop unit; e.g., Hungerbühler et al.,
2002), early Tertiary magmatism in north-central Ecuador
began as a submarine, volcanic arc system, represented by the
Macuchi unit (Fig. 1). The Paleocene-Eocene Macuchi unit
erupted onto oceanic plateau basement and used to be re-
garded as an allochthonous island-arc system (e.g., Hughes
and Pilatasig, 2002). However, the autochthonous status of
the Macuchi arc system has more recently been demon-
strated, as the oceanic plateau fragments that host the
Macuchi unit had already been accreted to the Ecuadorian
margin by Late Cretaceous times (e.g., Vallejo et al., 2009).
The Macuchi unit is juxtaposed landward against a minor
subaerial Late Cretaceous-Paleocene arc system (Silante unit;
Fig. 1C). The bulk northern Ecuadorian arc system progres-
sively matured during Tertiary times culminating in the pre-
sent-day Northern volcanic zone, where active arc magma-
tism involves substantially thickened, oceanic-continental
crust (50 km, and possibly up to 75 km, crustal thickness; Fig.
1; Guillier et al., 2001; Chiaradia et al., 2009a). Emplacement
of multiple Oligocene-Miocene intrusions along major crustal
structures led to the development of batholith-size intrusive
clusters in northern, central, and southern Ecuador. This em-
placement was accompanied by voluminous arc volcanism
and, partly, porphyry-related ore deposit formation (Fig. 1;
Schütte et al., 2010, and references therein).
A major geodynamic event affected the northern Andean
subduction system with the late Oligocene fragmentation of
the Farallon plate, accompanied by the early Miocene initia-
tion of Cocos-Nazca sea-floor spreading (Barckhausen et al.,
2008). At the Colombian-Ecuadorian trench, this has led to a
progressive, southward-propagating change in subducting
slab properties from relatively old, cool (Farallon) to young,
hot (Nazca) oceanic lithosphere, with the boundary repre-
sented by the offshore Grijalvas scarp (Fig. 1B; Lonsdale,
2005). Late Cretaceous-Tertiary, offshore Galapagos hotspot
magmatism produced seamounts, which were transported to
the northwest and docked onto or partly subducted at the
Panama-Costa Rica margin (Hoernle et al., 2002). A signifi-
cant change in Farallon-Nazca plate motion associated with

FIG 1. (A) Distribution of Northern (NVZ), Central (CVZ), and Southern volcanic zone (SVZ) magmatism resulting from
subduction of the Nazca plate below South America (onshore black bars); offshore gray bars indicate positions of major
seamount chains presently colliding with the central-southern American margin; thick black lines indicate oceanic spreading
centers; and the thin black line corresponds to the trench. (B) Geodynamic configuration of the Panama basin; offshore fea-
tures include seamount chains (dark gray), active parts of the Cocos-Nazca spreading center (thick lines), extinct parts of the
Cocos-Nazca spreading center (thin lines), and transform faults (active = hairlines; inactive = dashed hairlines). The Grijal-
vas scarp, progressively sweeping southward along the margin, separates young (<23 Ma) oceanic crust accreted at the
Cocos-Nazca spreading center to the north from older (>23 Ma) Farallon crust to the south. Onshore features show the An-
dean chain (dark gray), and major strike-slip fault zones (thin lines). (C) Geological map of Tertiary-Quaternary Ecuadorian
arc units and magmatic centers associated with porphyry-related ore deposits investigated in this study. The legend shows
ore deposit type associated with magmatic center (in parentheses: HS = epithermal high sulfidation, IS = epithermal inter-
mediate sulfidation, po. = porphyry). Maps adapted from Litherland et al. (1994), Steinmann (1997), Dunkley and Gaibor
(1997), McCourt et al. (1997), Pratt et al. (1997), Hughes et al. (1998), Meschede and Barckhausen (2001), and Palacios et
al. (2008).

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 PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR 1245

79°W 78°W
Late Tertiary granitoids and volcanic rocks associated with 1°N
porphyry Cu/epithermal ore deposits investigated in this study C Colombia

Western Cordillera granitoids Cangrejos-Zaruma intrusive belt 1

1 - Apuela/Cuellaje (po. Cu-Mo)
2 - Apuela/Junin (po. Cu-Mo)
3 - Telimbela (po. Cu±Mo±Au)
4 - Balsapamba (po. Cu±Mo±Au)
Central Ecuadorian granitoids
5 - Chaucha (po. Cu-Mo±Au)
6 - Gaby (po. Au-Cu)
8 - Cangrejos (po. Au-Cu)
9 - Portovelo (IS Au)
10 - Zaruma (po. Cu-Au?)
Arc volcanic rocks
11 - Saraguro Group at Chaucha 2
12 - Quimsacocha (HS Au-Cu)
13 - Saraguro Group at Tres Chorreras 0°

nte
7 - El Mozo (HS Au) 14 - Saraguro Group at Canicapa

Sila
Quito
15 - Saraguro Group at Portovelo

90°W 85°W 80°W 75°W

lera
10°N

illera
B

Cordil
Panama

n Cord
Macuchi
ge
id

Eastern
sR

5°N
co

Wester
Co

1°S

Colombia
0°
Carnegie Ridge Ecuador
Galapagos
as
hotspot jalv 3
Gri arp
Sc 5°S
Peru
4

2°S
A Caribbean plate

Cocos
plate s
co
Co
12
NVZ 5,11

Carnegie
6
South Cuenca
America 80°W
3°S
13
Sara-
8 guro
a
zc

CVZ 7
Na

10
9,15
Nazca
plate
14

Fernandez LEGEND
Juan-
Late Miocene - recent 4°S
Loja
arc volcanic rocks (NVZ)
SVZ Saca-
Oligocene-Miocene volc. rocks
palca (mainly Saraguro Group)
Paleocene-Eocene volc. rocks
-north: Macuchi (submarine)
Peru Silante (subaerial)
Antarctica -south: Sacapalca (subaerial)
plate
Tertiary granitoids
50 km
5°S

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1246 SCHÜTTE ET AL.
plate fission caused eastward motion of post-late Oligocene,
Galapagos hotspot-derived seamounts. This seamount chain
is referred to as Carnegie Ridge and its late Miocene collision
with, and subsequent subuction at, the Ecuadorian margin
caused minor shallowing of the subducting slab angle, as well
as eastward arc migration and broadening (Fig. 1B; Gutscher
et al., 1999a; Guillier et al., 2001; Barckhausen et al., 2008;
Schütte et al., 2010). Slab flattening, probably in response to
Inca Plateau subduction, began below northern Peru in mid-
to late Miocene times (Gutscher et al., 1999b; James and
Sacks, 1999). Progressive along-arc broadening of the flat slab
segment into southern Ecuador caused cessation of arc mag-
matism in this region; as such, late Miocene or younger, arc
volcanic cover sequences are only rarely observed in southern
Ecuador (Fig. 1C; Schütte et al., 2010).
Tertiary-Quaternary Adakite-like Magmatism in Ecuador
Present-day, Northern volcanic zone magmatism is domi-
nated by, but not restricted to, adakite-like compositions.
Generation of these geochemical features is attributed by
some authors to high-pressure equilibration of arc magmas
at deep to midcrustal levels (e.g., Garrison and Davidson,
2003; Garrison et al., 2006; Chiaradia et al., 2009a), but
mantle wedge contamination by slab melting of the sub-
ducting, young (<24 Ma), hot Nazca slab has alternatively
been proposed to cause adakite-like magmatism in present-
day Ecuadorian arc magmas (e.g., Gutscher et al., 2000;
Bourdon et al., 2003; Samaniego et al., 2005). Bryant et al.
(2006) note the difficulty in unequivocally discriminating
between these two mechanisms and present intramantle
wedge-partial melting processes in the garnet stability field
as an additional petrogenetic option for Northern volcanic
zone magmas. Samaniego et al. (2010) and Schiano et al.
(2010) infer that parental melts of Northern volcanic zone
magmas may partly derive from a mantle wedge metasoma-
tized by slab-derived fluids and partly from a slab melt-
metasomatized wedge with subsequent crustal magma dif-
ferentiation and magma mixing.
The late Miocene collision of the Carnegie Ridge seamount
chain with the northern Ecuadorian margin is considered to
have exerted a major influence on arc magmatism either by
increasing the geothermal gradient along the subducting slab
surface and facilitating slab melting (Samaniego et al., 2005),
or by potentially affecting far-field stress and transcrustal,
magma ascent kinetics (Chiaradia et al., 2009a). Seismic stud-
ies at the Ecuadorian margin demonstrate a continuously
subducting Nazca-Farallon slab, descending at an angle of
25° to 30° down to at least 150 to 200 km in depth; as such,
earlier suggestions proposing slab melting due to slab flatten-
ing in response to Carnegie Ridge subduction can be ex-
cluded (Guillier et al., 2001).
The occurrence of adakite-like magmatic features in the
Ecuadorian subduction system through time is not clearly
understood. Beate et al. (2001), Somers et al. (2005), and
Amórtegui (2007) demonstrate that adakite-like rock compo-
sitions already occur in late Miocene intrusions and volcanic
rocks. Chiaradia et al. (2004a) show that a number of Ter-
tiary, pre-late Miocene intrusions and volcanic formations
lack adakite-like features and note an apparent mutual ex-
clusivity of mainly early to mid-Miocene, porphyry-related
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mineralization and late Miocene to Quaternary, adakite-like
magmatism in Ecuador.
Sampling and Analytical Techniques
Samples for geochemical and isotopic analysis were col-
lected from exploration drill cores or outcrop exposures of
multiple mineralized porphyritic intrusions, seriate intru-
sions, and volcanic formations spatially associated with por-
phyry-related ore deposits (Table 1); sampling localities are il-
lustrated in Figure 1C. Sampling at individual magmatic
centers did not follow a systematic grid pattern, but instead
reflects drill core distribution, outcrop accessibility, and suit-
ability for sampling. Quimsacocha volcanic rock samples are
all related to a single volcanic caldera, whereas sampling lo-
calities for Saraguro Group volcanic rocks show a large geo-
graphic spread (~100 km), covering three main areas in
southern-central Ecuador (Chaucha, Cañicapa, Portovelo;
Fig. 1C) where spatially associated porphyry-related mineral-
ization is observed. Both intrusive centers and Saraguro
Group volcanic rocks may integrate magmatic events of 5 to
15 m.y., corresponding to the time span for batholith con-
struction in southern-central and northern Ecuador (Schütte
et al., 2010).
To ensure compositionally representative geochemical
analysis, sample quantities were typically made up of ~0.5 or
~1 kg of material for fine- or coarse-grained samples, respec-
tively. Lower sample quantities were occasionally obtained
for drill core samples where the amount of material available
for sampling was limited. In most sampled areas, rocks were
affected by porphyry-related hydrothermal alteration; in this
case, careful outcrop selection and drill core quick-logging
ensured sampling of least altered material for a given alter-
ation facies. Intense, feldspar-destructive, phyllic, and argillic
alteration was avoided where possible. Pervasively veined ma-
terial was avoided for sampling, and isolated hydrothermal
veins and vein alteration haloes were removed using a dia-
mond-blade disc saw prior to sample processing.
All sample preparation steps and Sr, Nd, and Pb isotope
mass spectrometric measurements were performed at the
University of Geneva; geochemical measurements (XRF,
ICP-MS) were performed at the University of Lausanne. Ex-
pected 2σ uncertainties from repeated XRF and ICP-MS
standard measurements are 2 to 7 percent for major elements
and up to 10 percent for trace elements. External repro-
ducibility (2σ) for isotope standard measurements is 0.05 per-
cent for 206Pb/204Pb, 0.08 percent for 207Pb/204Pb, 0.10 percent
for 208Pb/204Pb (SRM-981 standard; Todt et al., 1996), 7 ppm
for 87Sr/86Sr (repeated measurements of SRM-987 standard),
and 4 ppm for 143Nd/144Nd (JNdi-1 standard; Tanaka et al.,
2000). Further details for the applied analytical methods are
described in the Appendix.
Results
Combined, whole-rock, XRF and ICP-MS, major and
trace element, Sr, Nd, and Pb isotope compositions of the
complete data set are listed in the Electronic Appendix
(Table A1). Samples are grouped according to localities (in-
trusions) and stratigraphic units (volcanic rocks; Table 1).
Considering the constraints on sampling procedures de-
scribed above, it is important to emphasize that samples
 TABLE 1. Geological Features and Sampling Details of Porphyry-Related Intrusions and Volcanic Rocks Investigated in This Study

No. of
Magmatic center Age1 Associated mineralization2 Sampled main rock units/host rock Sampling sites Alteration3 samples

Apuela/Junin, 15–6 Ma Porphyry Cu-Mo; Nested plutons of hbl- and bt-bearing qtz- Drill cores from Junin and Potassic, 16
Apuela/Cuellaje reserves n/a diorite, granodiorite, and tonalite intruded Cuellaje concessions ±overprinted by
by granodiorite porphyry dikes; hosted by phyllic/propylitic
Rio Cala and Macuchi island-arc units

Balsapamba- 26–16 Ma Porphyry Cu ± Mo ± Au; Hbl- and bt-bearing granodiorite, tonalite, Drill cores from the S’ Telimbela Potassic, propylitic 17

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Telimbela reserves n/a and qtz-diorite plutons; granodiorite porphyry and N’ Balsapamba plutons
dikes hosted by Macuchi unit (volcaniclastic) (El Torneado); road cut exposures
in the central Telimbela batholith

Chaucha 15–10 Ma Porphyry Cu-Mo ± Au; Hbl- and bt-bearing tonalite-granodiorite Southeasternmost part of Chaucha Sodic-calcic, 8
reserves n/a intrusions (batholith); granodiorite porphyry batholith; outcrops along Rio Pita potassic, propylitic,
intrusions at Tunas and Gur-Gur; country rock creek; drill cores from Tunas, ±phyllic
consisting of pelitic metasediments and Naranjos and Gur-Gur sectors
amphibolites, Saraguro lavas

Quimsacocha 9.5–7.1 Ma HS Au-Cu; probable Volcanic caldera complex hosting and Intracaldera dome outcrops and Fresh (partly 13
reserves 1.7 Moz Au surrounded by basal andesite-dacite flows, drill cores weathered and
rhyolitic ignimbrites, and dacitic-rhyolitic oxidized)
intracaldera domes

Gaby 21–20 Ma Porphyry Au-Cu; Hbl tonalite pluton and plag-hbl/hbl-plag Drill cores and outcrops in whole Sodic-calcic, 25
measured and indicated porphyry stocks and dikes; intrusions property area (Gaby and Papa potassic, propylitic
resources 6.2 Moz Au punctured by abundant breccias; hosted by Grande sectors)
oceanic plateau basalts

1247
El Mozo 16 Ma HS Au; inferred Plag-hbl porphyry intrusions hosted by acid Outcrops and drill cores in central Argillic 3
resources 0.3 Moz Au tuffs of uppermost Saraguro Group property area
(La Paz Formation)

Cangrejos 26-24 Ma Porphyry Au-Cu; Nested intrusive complex with px-/bt-bearing Outcrops and drill cores in central Propylitic, 7
reserves n/a qtz-diorite and granodiorite plutons, intruded property area sodic-calcic
by plag-hbl porphyry stocks; abundantly
brecciated; hosted by Mesozoic metasediments

Portovelo-Zaruma 24-20 Ma IS Au ± porphyry Cu;
measured and indicated
resources 1.1 Moz Au
with historic production
>4.5 Moz Au
Hbl-/bt-bearing qtz-diorite, qtz-monzodiorite, Hills N’ Zaruma, drill cores Propylitic 12
and granodiorite intrusions; hbl qtz-diorite between Portovelo and Zaruma,
porphyry dikes underground mines in and
around Portovelo

Saraguro Group
At Tres Chorreras 31 Ma Host unit of mineralization Subvolcanic rock units (associated with Adits and outcrop exposures Argillic 1
diatreme complex)
At Canicapa ~20 Ma “ Dacite flows and tuffs ± subvolcanics Regional outcrop sampling Fresh-propylitic 6
PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR

At Chaucha 29–19 Ma “ Andesite flows Regional drill core sampling Propylitic 3

At Portovelo 24–19 Ma “ Andesite flows Regional drill core sampling Propylitic 11

Abbreviations: bt = biotite, fsp = feldspar, hbl = hornblende, HS = high sulfidation, IS = intermediate sulfidation, plag = plagioclase, px = pyroxene, qtz = quartz,
1Known and/or assumed age range of magmatic centers relevant for sampling (Schütte et al., 2010 , and references therein); still older facies of some batholiths (Apuela, Balsapamba) were not

sampled
2Mineralization type from PRODEMINCA (2000a, 2000b); reserve and/or resource figures from references compiled in Schütte (2010); only NI 43-101-compliant data are reported
3Main alteration type of lithologies sampled for whole-rock geochemistry; other alteration types are present but were avoided for sampling
1247
1248 SCHÜTTE ET AL.
within and between different sample groups are mostly not
considered as cogenetic. Apart from sharing an overall similar
petrogenesis in terms of late Oligocene to late Miocene arc
magmatism, their chemical compositions are, therefore, not
systematically related to each other by a single specific petro-
genetic process (such as magma mixing or AFC—i.e., assimi-
lation and fractional crystallization).
Hydrothermal alteration and the petrogenetic significance of
major and trace elements
Depending on their proximity with respect to centers of
porphyry-related hydrothermal systems, most samples display
variable degrees of high- to low-temperature alteration made
up of potassic, sodic-calcic or calcic-sodic, phyllic, (advanced)
argillic, and propylitic alteration assemblages (Fig. 2). It is
generally accepted that element mobility and redistribution
due to hydrothermal alteration may strongly affect large ion
lithophile elements (LILE) and, to a lesser extent, light rare
earth elements (LREE), whereas high field strength ele-
ments (HFSE) and mid- to heavy rare earth elements
(MREE, HREE) are less affected (e.g., Rollinson, 1993; Kay
et al., 2005).
We tested the compositional scatter caused by hydrother-
mal alteration for a number of magmatic centers where mul-
tiple samples of the same lithology were available by calculat-
ing individual isocons for each sample (Grant, 1986), based
on the least-altered reference samples of each lithologic unit
(Fig. 3; a complete overview table where the relative, isocon-
based compositional changes are quantified can be found in
Table A2 of the electronic Appendix). Isocons are straight
lines through the origin that compare the concentrations of
elements in altered rocks to concentrations in the least-al-
tered reference samples of the same lithology, assuming that
certain elements are immobile during alteration. Isocon
slopes are defined by ratios of equivalent masses before and
after alteration (i.e., immobile element concentrations), and
hence correspond to bulk mass changes associated with alter-
ation processes. Following isocon construction, alteration-in-
duced concentration changes of mobile elements may then
be constrained by deviations of data points from a given iso-
con (Grant, 1986). For our data set, isocon slopes were calcu-
lated using the Al2O3 contents of least-altered references ver-
sus altered samples, as this oxide consistently shows only
minor scatter in concentrations for a given lithology irrespec-
tive of alteration style and intensity.
Compositional scatter between samples of the same lithol-
ogy only becomes statistically significant at relative concen-
tration differences exceeding ~10 percent, corresponding to
the minimum analytical precision of trace element analysis
for our data set. To account for the intense alteration typically
associated with porphyry systems, we doubled this value and
defined 20 percent relative scatter in element concentrations
for the same lithology as acceptable, while regarding elements
showing higher scatter as unreliable indicators of petroge-
netic processes. However, reference protolith heterogeneities
cannot be completely ruled out, such that alteration-induced
compositional scatter of some elements discussed below
might possibly be overestimated.
Using this classification scheme, we find the element be-
havior patterns listed in Table 2, which we tentatively assume
0361-0128/98/000/000-00 $6.00 1248
to be representative for our whole data set. With few excep-
tions, compositional scatter of different chemical groups
(HFSE, LILE, REE) corresponds to the expected behavior
noted above. We emphasize that the observations summa-
rized in Table 2 reflect our sample selection criteria accord-
ing to alteration mineralogy and thus are not necessarily di-
rectly comparable to other data sets using a different
sampling strategy. Throughout this article, we avoid petroge-
netic discussions relying on chemical elements with concen-
trations that are considered to be significantly affected by al-
teration in one of our reference magmatic centers.
Several major elements and HFSE (Zr, Nb, Ta, Y) show
only minor to moderate concentration variations for a given
lithology affected by hydrothermal alteration (Table 2), such
that their concentrations in altered rocks are assumed to ac-
curately reflect petrogenetic processes. Elements of the
LILE group (Cs, Rb, Ba, K) show alteration-induced scatter
beyond acceptable levels (as defined above) and are thus in-
appropriate for constraining petrogenetic processes. Sr,
though part of the LILE group, mostly shows only minor
compositional scatter (Table 2; Fig. 3) and its concentrations
are, therefore, considered to be petrogenetically significant.
The low Sr scatter for most samples is likely an effect of
avoiding intense feldspar, phenocryst-destructive alteration
types for sampling (at macro- and microscopic scales; com-
pare, for example, Fig. 2E and H), although we did not eval-
uate potential alteration effects at the submicroscopic scale in
the porphyry matrix. Biotite constitutes a dominant mineral
in potassic alteration assemblages in Ecuador (e.g., Schütte,
2010); substitution of biotite-hosted, interstitial-site K with
Rb, Cs, and Ba, (but not Sr; Deer et al., 1992) is consistent
with the significant scatter of these elements relative to Sr.
We selected a number of REE to represent LREE (La, Nd),
MREE (Sm, Eu, Gd, Dy), and HREE (Yb) behavior. While
LREE concentrations tend to show scatter outside the 20 per-
cent range, the compositional scatter of most MREE and
HREE is within acceptable limits (Table 2). Single concentra-
tion spikes can be readily identified when evaluated within a
larger group of samples. Frequently observed, chemically cou-
pled behavior of MREE and HREE during alteration makes
MREE/HREE ratios (e.g., Dy/Yb or Sm/Dy) more robust pet-
rogenetic indicators than absolute concentrations.
Petrography
The igneous (unaltered) mineralogical inventory of most
seriate intrusive rocks is made up of plagioclase, hornblende,
quartz, and biotite, with accessory opaque minerals (mostly
magnetite), apatite, and zircon; most highly differentiated
intrusions additionally contain minor alkali-feldspar and ac-
cessory titanite. The majority of these intrusions classify as
granodiorite, quartz-diorite, or tonalite in optically estimated
mineral modes (Fig. 2A, C, F). In decreasing order of abun-
dance, phenocryst modes of porphyry intrusions are mainly
made up of plagioclase, ± hornblende, ± quartz, ± biotite,
with quartz commonly displaying rounded, resorbed grain
margins (Fig. 2B-D). Sampled Quimsacocha andesite lava
flows and dacite domes contain plagioclase and hornblende
phenocrysts (the latter commonly opacitized), frequently em-
bedded in a glassy, nondevitrified matrix (Fig. 2G); clinopy-
roxene occurs as an additional phenocryst phase in andesites.
 PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR 1249

FIG. 2. Macrophotographs (A-B) and microphotographs (C-H) illustrating igneous and alteration features representative
for analyzed samples of Oligocene-Miocene magmatic centers in Ecuador. Scale bar is 1 mm for microphotographs and 2 cm
for macrophotographs; microphotographs are transmitted light with PPL = plane polarized light, or XPL = crossed nicols.
Sample numbers are shown to match mineralogical information with geochemical data (Electronic Appendix Table A1). (A)
Hornblende- and biotite-bearing granodiorite with weak sericite-chlorite alteration (Chaucha batholith; E07001). (B) Horn-
blende granodiorite porphyry with pervasive potassic alteration and sericite alteration haloes surrounding quartz-pyrite vein-
lets (Junin; E07033); note that such veinlets and their haloes were generally removed prior to processing for geochemical
analysis and the present sample was not used for whole-rock geochemistry. (C) Plagioclase-hornblende porphyry with weak
propylitic alteration (XPL; Cangrejos; E05-M4). (D) Hornblende-plagioclase porphyry with sodic-calcic alteration; horn-
blende is replaced by actinolite (XPL; Gaby; E05078). (E) Hornblende quartz-diorite porphyry with potassic alteration (XPL;
Balsapamba; E06131). (F) Hornblende- and biotite-bearing granodiorite with potassic alteration (PPL; Apuela-Cuellaje;
E06202). (G) Plagioclase and hornblende-phyric dacite with fresh, glassy matrix (PPL; Quimsacocha; E06020). (H) Horn-
blende-granodiorite porphyry with pervasive potassic, overprinted by phyllic alteration where feldspar phenocrysts and por-
phyry matrix are partly replaced by sericite (XPL; Junin; E06197); this type of alteration significantly affects whole-rock Sr
contents, rendering results petrogenetically inaccurate, and was used only for a limited number of samples where other sam-
ples were not available.

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1250 SCHÜTTE ET AL.

Gaby plagioclase-hornblende porphyry Balsapamba hornblende quartz-diorite porphyry

15x Nb
E 05088 - K & propyl. E 06131A - K & propyl.
40 E 05083b - Na-Ca 40 E 06132 - K & propyl.
E 05073 - Na-Ca E 06141 - K & propyl.
E 05086 - K & Na-Ca SiO2 /2
[concentration in altered rock]

[concentration in altered rock]

E 06051 - K 4x La SiO2 /2
E 05070 - Na-Ca
E 05090 - Na-Ca & propyl. 65x TiO2
E 05083a - Na-Ca 4x Y
30 50x TiO2 30
E 06048 - Na-Ca 2x Sc
E 06053 - K
Zr /3
2x Y
27x Eu Sr /15 120x P2 O5 Rb
20x K2O
20 20 Sr /13
7x Gd 10x Nb
22x Th 80x Ta
155x Ta 9x Dy
Rb 2x Fe2O3 Zr /3
Ba /30 Sc 10x Hf
85x P2 O5 10x Hf 7x Gd
Al2O 3 Al2O 3
10 Nd 10 Ba /30
2x CaO 10x K2O

3x Na2O 3x Na2O
5x Yb
2x MgO
reference: Sm Nd reference:
La E05078 (Na-Ca) 3x Yb E06135 (K & propyl.)
0 10 20 30 0 10 20 30 40
[concentration in least altered reference lithology] [concentration in least altered reference lithology]
Saraguro Group (Portovelo Unit) andesite Apuela (Cuellaje) hornblende-biotite-bearing tonalite

E 06082 - propyl. E 06206A - K

40 E 06120 - propyl. 40 E 06202 - K & propyl.
10x Nb
[concentration in altered rock]

[concentration in altered rock]

2x Y
60x TiO2
125x Ta 325x P2O 5
SiO2 /2
40x TiO2 30 Sr /20
30
2.5x La
10x Hf
1.5x Nd SiO2 /2
Sc Rb
Al2O 3 Zr /3
Rb /3 5x Th
10x Nb
2x La
20 20
10x Hf
Zr /5
10x K2O
2x Y 120x Ta
3.5x MgO Al2O 3
Ba /30
Nd 3x Na2O
5.5x Dy
10 10x K2O 10 Sc Ba /60
3x Na2O Sr /20
6x Th
Fe 2O 3 5x Yb 5x Yb 10x Eu
2x CaO 50x P2 O5
Gd 1.5x Sm reference: reference:
Dy Fe 2O 3
2x Eu E06081 (propyl.) E06200 (propyl.)
Sm

0 10 20 30 40 0 10 20 30
[concentration in least altered reference lithology] [concentration in least altered reference lithology]
FIG. 3. Isocon plots of selected granitoids and volcanic rocks investigated in this study. Plots constructed after Grant
(1986), assuming constant concentrations of Al2O3 (the least alteration-affected, major element oxide) for altered and least-
altered reference sample. Elemental scatter outside the gray area (±20%) reflects alteration-induced compositional variation
of altered samples beyond (as defined for this study) acceptable means, with respect to a least-altered reference sample of
the same lithology. To some extent, it may also reflect protolith compositional heterogeneity. Note that isocons displayed in
each figure panel correspond to the average composition of compared rock units and serve only for illustrative purposes; to
quantify alteration effects individual isocons were calculated for each sample and considered for relative concentrations
shown in the electronic Appendix (Table A2). Axes refer to concentration units (either ppm or wt %); to obtain visually ho-
mogenous element distributions along the whole length of each axis, elemental concentrations were multiplied and/or di-
vided by arbitrarily chosen factors fitted individually to each plot. These factors serve for illustrative purposes only; individ-
ual isocon slopes, calculated from Al2O3 mass changes, are not affected by these factors, but instead derive from bulk mass
changes (e.g., dehydration-induced mass loss effects). Alteration abbreviation key: K = potassic, Na-Ca = sodic-calcic, propyl.
= propylitic. Feldspar-destructive, phyllic or argillic alteration increases alteration-induced Sr scatter, but was avoided for
most samples. See Seedorff et al. (2005) for definitions of alteration assemblages.

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 PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR 1251

TABLE 2. Hydrothermal Alteration-Influenced Compositional Scatter of Reference Rock Types

Element Remarks

Minor compositional scatter—petrogenetically accurate concentrations1

SiO2, TiO2, Al2O3 Scatter < ±10% for all rock types
CaO, P2O5 Scatter < ±20% for all rock types
Zr, Hf Scatter < ±10% for all rock types
Th Scatter < ±20% for all rock types
Nb, Ta Scatter < ±20% for AC, BA, SA; scatter mostly < ±20% for GA
Sr Scatter < ±10% for AC, GA, BA; scatter < ±20% (with one exception) for SA
Sc Scatter < ±20% for AC, BA, SA; slightly higher scatter (up to 26%) for GA

Moderate compositional scatter—probably petrogenetically accurate concentrations2

Na2O Scatter < ±10% for AC, BA, SA, but highly variable scatter for GA (strong sodic-calcic alteration)
MgO Scatter < ±20% for AC, PO, BA; sometimes higher for GA
Y Scatter < ±20% for GA, PO, BA; higher scatter (up to 35%) for AC due to reference sample low Y content (otherwise
< ±20%)
MREE (Sm, Eu, Gd, Dy) Scatter mostly < ±20%; Sm shows significantly higher scatter at BA; single Gd spikes occur for most rock types
HREE (Yb) Scatter mostly < ±20% with some spikes > ±20% at AC, BA (Dy) and AC, GA (Yb); often chemically correlated behavior
among REE groups such that ratios (e.g., Dy/Yb) may be more accurate than absolute concentrations
REE patterns While single REE may scatter significantly, no systematic disturbance of all REE is detectable such that REE distribution
patterns may be used qualitatively for petrogenetic evaluation (cf. Kay et al., 2005)

Significant compositional scatter—possibly petrogenetically inaccurate concentrations3

K2O Highly variable scatter for all rock types
Fe2O3 Scatter < ±20% for AC, BA, SA, but highly variable scatter for GA (up to 52%)
LILE4 (Cs, Rb, Ba, U) Highly variable scatter for all rock types; at GA correlated with K2O (potassic alteration)
Cr, Ni5 Highly variable scatter for all rock types except for BA
LREE (La, Nd)5 Highly variable scatter for all rock types except for SA

Main alteration types for reference centers where isocons were constructed6
AC Potassic, propylitic
BA Potassic, propylitic
GA Sodic-calcic, potassic, propylitic
SA Propylitic

Abbreviations: AC = Apuela-Cuellaje, BA = Balsapamba, GA = Gaby, SA = Saraguro; details are provided in Table A2 (Electronic Appendix)
1Significant compositional scatter (i.e., >20%) for less than 10% of total reference samples (n = 31); only a single reference center affected
2Significant compositional scatter (i.e., >20%) for 10–20% of total reference samples (n = 31); one or two reference centers affected
3Significant compositional scatter (i.e., >20%) for >20% of total reference samples (n = 31)
4See text for discussion of Sr-LILE decoupling
5In part, the observed scatter might additionally relate to protolith heterogeneities such that element mobility is possibly overestimated in our dataset
6Feldspar phenocryst destructive alteration was generally avoided as much as possible, but is unavoidable for some porphyry intrusions at Junin (and

Chaucha); Sr scatter is expected to increase for these rock types

Saraguro volcanic rocks are made up of andesitic, dacitic, and
rhyolitic flows and subordinate tuffs, where main phenocryst
assemblages are plagioclase, ± hornblende, ± clinopyroxene,
plus quartz with accessory zircon for dacitic-rhyolitic compo-
sitions. All samples classify as andesite, rhyodacite, or rhyolite
in a Winchester and Floyd (1977) silica versus immobile ele-
ment ratio classification plot (Fig. 4). The latter plot type is
preferred in this study, as the accuracy of the more common
total alkali versus silica classification plot is potentially com-
promised by alteration effects.
Major and trace element contents
General fractionation trends: Most samples define broadly
continuous, major element distribution patterns in Harker
diagrams, despite variable elemental scatter due to hydro-
thermal alteration effects. Titanium dioxide, Fe2O3, and CaO
steadily decrease with SiO2—i.e., they show gross compati-
ble behavior (Fig. 5A-C). Al2O3 distribution is constant or
decreases slightly with increasing SiO2, suggesting minor
compatible behavior (Fig. 5D); K2O (significantly influenced
by hydrothermal alteration) and Na2O mainly display incom-
patible behavior or constant values with increasing SiO2 (Fig.
5E-F). The broad similarity of major element trends dis-
played by the whole data set suggests that similar processes of
magma evolution operate in all investigated Oligocene-
Miocene magmatic centers associated with porphyry-related
ore deposits, where trends within individual magmatic suites
are largely mirrored by trends between different suites.
Where appropriate, trace element Harker diagrams (Figs. 6,
7) include the compositional fields of present-day, Northern
volcanic zone main and frontal arc volcanic rocks (Chiaradia
et al., 2009a) and Eocene lavas of the Macuchi unit (Chiara-
dia, 2009) for reference. With the exception of few Saraguro
Group samples, trace elements incompatible in basaltic melts
consistently plot below the Northern volcanic zone main arc,
but tend to overlap with Northern volcanic zone frontal arc
compositions (e.g., Th, U, Zr; Fig. 6A-C). Within a given
Oligocene-Miocene magmatic center, these trace elements
either stay constant or show slightly decreasing contents at
SiO2 >65 wt percent, possibly reflecting fractionation effects

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1252 SCHÜTTE ET AL.
80
rhyolite
70 rhyodacite-
dacite
[wt.%]
60 SYMBOL KEY
andesite
Western Cordillera granitoids
2
SiO
(Apuela, Junin, Telimbela,
Balsapamba)
Central Ecuadorian granitoids
50 (Chaucha, Gaby, Mozo)
Cangrejos-Zaruma intrusive belt
Saraguro Group volcanic rocks
Quimsacocha volcanic rocks
40
0.001 0.01 0.1 1 10
-4
Zr/TiO2 * 10
FIG. 4. Rock classification of Oligocene-Miocene granitoids and volcanic
rocks in Ecuador, based on an SiO2 versus Zr/TiO2 discrimination plot (Win-
chester and Floyd, 1977). The use of the immobile element ratio Zr/TiO2
makes this classification diagram more attractive when classifying altered
rocks than the more commonly used total alkali versus silica diagram; the lat-
ter diagram’s accuracy is potentially compromised by alteration effects re-
sulting from Na and K mobility.
of accessory phases (e.g., zircon, monazite), which only be-
come stabilized in relatively silicic melts (e.g., Hoskins et al.,
2000).
Strontium mostly shows broadly constant concentrations
around 250 to 400 ppm for the 55 to 65 wt percent SiO2 in-
terval and major scatter (100 to ~800 ppm) for more evolved
compositions (Fig. 6D). With the exception of the late
Miocene Quimsacocha volcanic center, Sr contents of
Oligocene-Miocene arc magmas between 55 and 65 wt per-
cent SiO2 overlap with—or slightly exceed—the upper com-
positional range defined by the less-differentiated Macuchi
basalt-andesites. However, Miocene arc magmas consistently
plot below main and frontal arc Northern volcanic zone mag-
mas, although no data for <59 wt percent SiO2 exist for the
latter (Fig. 6D). Less basalt-incompatible elements show
petrologically correlated behavior, in that they mostly plot
above or overlap with frontal (and main) arc Northern vol-
canic zone magmas at similar SiO2 contents; their concentra-
tions broadly decrease with increasing SiO2 (Y, Yb; Fig. 6E-
F).
Adakite-like features: Trace element ratios illustrate the sig-
nificance of the general compositional features listed above
for the development of adakite-like chemical signatures. A
significant portion of Oligocene-Miocene Western Cordillera
granitoids associated with porphyry-related ore deposits qual-
ify as adakite like in an Sr/Y versus Y discrimination plot,
owing to strongly depleted Y contents (<10 ppm) and despite
only moderate (mostly subadakite-like; i.e., <400 ppm) Sr
contents (Fig. 7E). An Sr/Y versus SiO2 plot demonstrates
that most present-day, Northern volcanic zone magmas ac-
quire adakite-like Sr/Y ratios (Sr/Y >40) during relatively early
differentiation stages (at 56 to 65 wt % SiO2; box 1 in Fig. 7A),
0361-0128/98/000/000-00 $6.00
whereas most Oligocene-Miocene magmas (excluding Quim-
sacocha) only display adakite-like Sr/Y ratios for highly differ-
entiated rock compositions (>65 wt % SiO2; box 2 in Fig. 7A).
In contrast to other Oligocene-Miocene magmas, Quim-
sacocha samples tend to overlap with Northern volcanic zone
magmas, although they are overall more differentiated and,
thus, further depleted in Y with respect to Northern volcanic
zone magmas (Figs. 6D-E, 7A, E). The contrasting magma
evolution trends can be bracketed in time between the Quim-
sacocha volcano (7.1–9.5 Ma; Schütte et al., 2010), which had
a compositional trend that resembles some present-day
Northern volcanic zone magmas, and the oldest phases of the
Chaucha batholith in central Ecuador (14.8 Ma; Schütte et
al., 2010). Except for Quimsacocha, Oligocene-Miocene arc
magmas do not qualify as adakite-like in terms of La/Yb ratios
(Fig. 7F), despite significant Yb depletion (virtually all
Oligocene-Miocene samples meet the “adakite” of criteria Yb
≤ 1.9 ppm; as defined by Defant and Drummond, 1990; Fig.
6F).
Rare earth elements: Most chondrite-normalized REE
plots lack negative Eu anomalies (Fig. 8); however, negative
Eu anomalies do characterize a number of mainly southern
Ecuadorian magmatic centers, including Saraguro Group vol-
canic rocks at Chaucha and Portovelo-Zaruma (Fig. 8F), sev-
eral intrusions of the Cangrejos-Zaruma intrusive belt (Fig.
8G), and, partly, the Telimbela batholith in the Western
Cordillera (Fig. 8B). Positive Eu anomalies are displayed by a
fraction of Balsapamba batholith samples (Fig. 8B) and the
Gur-Gur porphyry intrusion at Chaucha (Fig. 8C). Several
studies show that Eu anomalies may be influenced by hy-
drothermal alteration (e.g., Shikazono et al., 2008). In our
data set, isocon reference magmatic centers commonly dis-
play chemically correlated behavior of MREE during alter-
ation (Tables 2, A2; Fig. 3), and feldspar-destructive, phyllic
alteration was avoided for sampling in most cases (Table 1;
Fig. 2), such that potential alteration effects on relative Sm-
Eu-Gd distributions are minimized. While we cannot rule out
potential alteration effects, we do argue that the occurrence
or absence of Eu anomalies in our data set have petrogenetic
significance.
Amphibole and garnet fractionation effects: Several mag-
matic centers associated with porphyry-related ore deposits
are strongly depleted in HREE and display concave-upward
HREE patterns, indicative of amphibole fractionation or flat
to decreasing MREE-HREE slopes, indicative of combined
amphibole-garnet fractionation (Fig. 8A-D). Chondrite-nor-
malized Dy/Yb ratios may be used as petrogenetic finger-
prints for garnet or amphibole fractionation (leading to strongly
increasing or slightly decreasing trends with increasing SiO2,
respectively; Davidson et al., 2007). Individual Northern vol-
canic zone volcanic centers show Dy/Yb and Nb/Ta trends
negatively correlated with SiO2, indicative of amphibole frac-
tionation (Chiaradia et al., 2009a). No such systematic trends
can be clearly discerned for Oligocene-Miocene arc magmas
because most samples do not define cogenetic suites (Fig. 7B,
D); as such, differentiation trends of individual magmatic sys-
tems are not visible, and any long-term bulk distribution trends
might additionally become blurred by the somewhat con-
trasting, superposing fractionation effects of amphibole and
garnet (or other MREE/HREE-fractionating phases) on
1252
 PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR 1253

10
A B
0.8 8

0.6
TiO2 [wt.%]

Fe2O3 [wt.%]
6

0.4 4

0.2 2

C D
12 20

18

Al2O3[wt.%]
8
CaO [wt.%]

16
4

14

E 6 F
6
Na 2O [wt.%]

4
K2O [wt.%]

2
2

50 55 60 65 70 75 50 55 60 65 70 75
SiO 2 [wt.%] SiO 2 [wt.%]

SYMBOL KEY
Western Cordillera granitoids (Apuela, Junin, Telimbela, Balsapamba) Saraguro Group volcanic rocks

Central Ecuadorian granitoids (Chaucha, Gaby, Mozo) Quimsacocha volcanic rocks

Cangrejos-Zaruma intrusive belt

FIG. 5. Harker diagrams for various major elements of investigated samples.

chondrite-normalized MREE-HREE pattern geometries. In
contrast, Sm/Dy ratios increase in response to both amphi-
bole and garnet fractionation; this is evidenced in Figure 7C,
where chondrite-normalized Sm/Dy ratios show an overall
steady increase with SiO2, albeit showing pronounced varia-
tions between different magmatic centers for a given differ-
entiation stage. With few exceptions, Sr/Y and Sm/Dy show
broadly correlated behavior at Sr/Y >40 or pool unsystemati-
cally at Sr/Y <40 (Fig. 7H).
Subduction-related geochemical features: In primitive, man-
tle-normalized, trace element spidergrams, all Oligocene-
Miocene samples display negative Nb-Ta anomalies relative
to LILE (Fig. 8A-G). As all samples consistently display this
feature, irrespective of alteration type and degree, we con-
sider it to be petrogenetically significant, and thus infer a sub-
duction-related, slab fluid-metasomatized mantle wedge as
the magma source (rather than interpreting LILE over
HFSE enrichment as an alteration effect).
Sr, Nd, and Pb isotope composition
Oligocene-Miocene samples define homogeneous groups in
uranogenic and thorogenic Pb isotope plots (Fig. 9C, E) and
combined Sr-Nd, Sr-Pb, and Nd-Pb isotope plots (Fig. 9A, B,
D) for given intrusive and volcanic suites. Western Cordillera
granitoids (Apuela-Junin, Balsapamba-Telimbela) isotopically
overlap with the most primitive, Late Cretaceous-Eocene
Macuchi and Rio Cala volcanic arc units (their immediate
host rocks) and parts of the Caribbean-Colombian Oceanic

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1254 SCHÜTTE ET AL.

12 4
A B
NVZ main arc
3
8 Macuchi Unit

U [ppm]
Th [ppm]

(Eocene)
2

4 NVZ frontal
arc 1

200
C D
800

150
600
Zr [ppm]

Sr [ppm]
100
400

50 200

30 3
E F

20 2
Yb [ppm]
Y [ppm]

10 1

50 55 60 65 70 75 50 55 60 65 70 75
SiO 2 [wt.%] SiO 2 [wt.%]

SYMBOL KEY
Western Cordillera granitoids (Apuela, Junin, Telimbela, Balsapamba) Saraguro Group volcanic rocks

Central Ecuadorian granitoids (Chaucha, Gaby, Mozo) Quimsacocha volcanic rocks

Cangrejos-Zaruma intrusive belt

FIG. 6. Harker diagrams for various trace elements of investigated samples. Macuchi reference field from Chiaradia
(2009); Northern volcanic zone main and frontal arc reference field from Chiaradia et al. (2009a).

FIG. 7. (A-D) Trace element ratios versus SiO2 contents of investigated samples. Reference fields are identical to Figure
6, where applicable. Note that, except for the late Miocene Quimsacocha volcano, most Tertiary magmatic centers develop
toward adakite-like Sr/Y ratios (Sr/Y >40) only at advanced differentiation stages (SiO2 >65 wt %; Fig. 7A, box 2), whereas
Ecuadorian arc volcanoes of the Northern volcanic zone and Quimsacocha magmas acquire adakite-like Sr/Y ratios during
earlier differentiation stages (Fig. 7A, box 1). (E) Sr/Y versus Y diagram with variable boundaries for adakite-like rocks (cor-
responding to Sr/Y > 20 or Sr/Y > 40, respectively, depending on which reference is used; references compiled in Richards
and Kerrich, 2007). The majority of Oligocene-Miocene magmatic centers in Ecuador plot inside, or straddle the border of
the adakite field due to significant Y depletion at Sr contents around or below 400 ppm. Fractionation trends of amphibole,
titanite, zircon, and plagioclase using the partitioning coefficients of Rollinson (1993) for andesitic melts, and Bachmann et
al. (2005) for rhyolitic melts are shown. Tick marks (small white squares) on the andesitic melt-amphibole fractional crystal-
lization trend correspond to 10 percent increments in fractionation values. Fractionation curves for amphibole, titanite, and
zircon in rhyolitic melts overlap and are simplified as one in the diagram; the whole curve range for fractionation effects in
rhyolitic melts corresponds to ~10 percent amphibole and <1 percent titanite and zircon fractional crystallization. Starting
compositions for the modeled trends are 285 ppm Sr and 19 ppm Y (mafic compositions), and 335 ppm Sr and 9 ppm Y (fel-
sic compositions). (F) La/Yb versus Yb diagram with boundary for adakite-like rocks, as depicted in Richards and Kerrich
(2007). (G) Sr/Y versus Sr/Sc plot, showing the effects of combined and separate amphibole and titanite fractionation using
the partitioning coefficients of Bachmann et al. (2005). (H) Chondrite-normalized Sm/Dy versus Sr/Y plot, showing unsys-
tematic pooling of values at Sr/Y <40 and a broad positive correlation for most samples at Sr/Y >40.

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 PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR 1255

150 25
A box 1 box 2 B
125 20

100 NVZ frontal

arc 15

Nb/Ta
Sr/Y

75
NVZ main arc
10
50

5
25

C D
5 2.0
(Sm/Dy) norm.

(Dy/Yb) norm.
4 1.5

3 1.0

2 0.5

50 55 60 65 70 75 50 55 60 65 70 75
SiO 2 [wt.%] SiO 2 [wt.%]
80
E F
150 60 adakite boundary
amphibole, titanite,
zircon FC (La/Yb >20)
Sr/Y

adakite boundary
(rhyolitic melt) (Sr/Y >40)
La/Yb

100 40

adakite boundary
(Sr/Y >20)
50 20
amphibole FC
(andesitic melt)
amph + plag FC
(rhyolitic melt)

0 10 20 30 0 1.0 2.0 3.0

Y [ppm] Yb [ppm]
6
140 G amphibole + titanite FC (95/5) H
5
(Sm/Dy) norm.

100 4
titanite FC
Sr/Y

3
60
2

1
20
amphibole FC

0 40 80 120 0 40 80 120 160 200

Sr/Y
Sr/Sc

SYMBOL KEY
Western Cordillera granitoids Central Ecuadorian granitoids Saraguro Group volcanic rocks
(Apuela, Junin, Telimbela, Balsapamba) (Chaucha, Gaby, Mozo)
Cangrejos-Zaruma intrusive belt Quimsacocha volcanic rocks

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1256 SCHÜTTE ET AL.

100 1000
A

Rock/Primitive Mantle
Rock/Chondrite
100
10
Apuela-Junin
10
Junin porphyry I (4)
1 Junin porphyry II (3)
1 Apuela batholith: Cuellaje (3)
Apuela batholith: Junin (1)
100 1000
B

Rock/Primitive Mantle
Rock/Chondrite

100
Balsapamba-Telimbela
10 10
Balsapamba batholith (3)
Balsapamba porphyry I (3)
1 Balsapamba porphyry II (1?)
Telimbela batholith (1)
Telimbela porphyry (3)
100 1000
C
Rock/Primitive Mantle
Rock/Chondrite

100
10
Chaucha, El Mozo
10
Chaucha: Tunas porphyry (3)
1 Chaucha: Gur-Gur porphyry (3)
1
Chaucha: batholith (2?)
El Mozo porphyry (1)
1000 1000
D
Rock/Primitive Mantle
Rock/Chondrite

100
100

10
10 Quimsacocha
1
andesite (4)
dacite (4)
100 100
E
Rock/Primitive Mantle
Rock/Chondrite

10 10 Gaby-Papa Grande
Gaby porphyry (2)
Papa Grande porphyry (2)
seriate tonalite (2)
100 1000
F
Rock/Primitive Mantle
Rock/Chondrite

100
Saraguro Group
10
Chaucha (1)
10 Tres Chorreras (2)
Portovelo-Zaruma (1)
Canicapa (2)
100 1000
G
Rock/Primitive Mantle
Rock/Chondrite

100
Cangrejos-Zaruma
10
Cangrejos seriate intrusions (2)
10 Cangrejos porphyry (1)
Portovelo porphyry (2)
Zaruma seriate intrusions (1)
1 1
La Pr Sm Gd Dy Er Yb Rb Th Nb La Pb Sr Zr Sm Gd Dy Ho Tm Lu
Ce Nd Eu Tb Ho Tm Lu Ba U Ta Ce Pr Nd Hf Eu Tb Y Er Yb

FIG. 8. C1 chondrite-normalized REE diagrams and primitive, mantle-normalized spidergrams of investigated samples.
Numbers in parentheses assigned to each lithology in individual plot legends refer to petrogenetic groups as listed in Table 3. 1
= significant shallow crustal magma evolution (plagioclase fractionation); 2 = no significant shallow crustal plagioclase fraction-
ation and no significant hornblende, garnet, or titanite fractionation; 3 = significant amphibole ±titanite fractionation (higher
pressure differentiation and/or H2O-rich melts); 4 = similar to group 3, but at higher pressure where garnet influence becomes
more significant. Note variable scaling at the logarithmic axis. Normalization values from Sun and McDonough (1989).

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 PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR 1257

12 0.708 towards Raspas metapelites

A B

bulk Earth
Raspas Complex ultramafics (El Oro) Western Cordillera shallow
and Eastern Cordillera (Loja)
basement
Rio Cala 0.707
towards Raspas
8 Complex metapelites Cretaceous-Paleogene
intrusions

87Sr/ 86 Sr
Macuchi
Western Cordillera 0.706 Western Cordillera
x
shallow basement granulites/amphibolites
ε Nd init

Western Cordillera
Alao
4 oceanic plateau units 0.705 Rio Cala (Eastern Cordillera)
(CCOP)
Macuchi
x
0.704
0 bulk Earth

Western Cordillera 0.703

granulites/amphibolites Raspas Complex ultramafics (El Oro) Western Cordillera oceanic
plateau units (CCOP)

0.702 0.703 0.704 0.705 0.706 0.707 0.708 18.50 18.75 19.00 19.25 19.50
87Sr/ 86 Sr 206 Pb/ 204 Pb
15.75 12
C Loja Amotape incl. Raspas Complex Cretaceous-Paleogene intrusions
(Eastern Cordillera) Raspas Complex ultramafics Western Cordillera oceanic D
plateau units (CCOP)
15.70
8
207 Pb/ 204 Pb

Alao
15.65 (Eastern Cordillera)
Rio Cala x Macuchi

ε Nd init
x
15.60 4
Macuchi
Western Cordillera
15.55 granulites/amphibolites
Rio Cala Western Cordillera
oceanic plateau 0
15.50 units (CCOP)
Western Cordillera Western Cordillera
Western Cordillera shallow basement granulites/amphibolites shallow basement towards Raspas metapelites
18.50 18.75 19.00 19.25 19.50 18.50 18.75 19.00 19.25 19.50
206 Pb/ 204 Pb 206 Pb/ 204 Pb
39.2 Alao (Eastern
E Amotape incl. Raspas Complex Cordillera) SYMBOL KEY
Cretaceous-Paleogene intrusions
Western Cordillera granitoids
39.0 Western Cordillera (Apuela, Junin, Telimbela, Balsapamba)
208 Pb/ 204 Pb

shallow basement
Central Ecuadorian granitoids
38.8 Chaucha
Loja
x
(Eastern
Gaby
38.6 Cordillera) Mozo
Macuchi Western Cordillera Cangrejos-Zaruma intrusive belt
oceanic plateau
38.4 Western Cordillera units (CCOP) Saraguro Group volcanics
granulites/amphibolites
Quimsacocha volcanics
Rio Cala
x Most primitive sample compositions of
18.50 18.75 19.00 19.25 19.50 Chiaradia (2009) and Chiaradia et al. (2009a)
206 Pb/ 204 Pb

FIG. 9. Sr, Nd, and Pb isotope compositions of investigated samples. “Central Ecuadorian granitoids” are differentiated into
individual magmatic centers (Chaucha, Gaby, Mozo) in the legend to allow discussion of different basement rock units in across-
arc dimension. The “X” in the white box serves as a proxy for the isotopic composition of least-differentiated melts formed in
the Ecuadorian mantle wedge, corresponding to the isotopic composition of the most primitive Tertiary-Quaternary samples
identified by Chiaradia (2009) and Chiaradia et al. (2009a). The Sr-Nd isotope composition of Western Cordillera granitoids
(Fig. 9A) relative to these least-differentiated samples indicates that assimilation of primitive oceanic plateau or island-arc base-
ment units caused granitoid parental melts to become isotopically more primitive (i.e., less radiogenic in 87Sr/86Sr and more ra-
diogenic in initial εNd) during crustal magma differentiation. Isotopic reference fields of potential crustal assimilants make up
Western Cordillera outcrops of the Caribbean-Colombian Oceanic Plateau (Mamberti et al., 2003); the Rio Cala and Macuchi
volcanic arc units of the Western Cordillera (Chiaradia, 2009); the Raspas Complex at the western end of the Cangrejos-Zaruma
intrusive belt (Bosch et al., 2002); Western Cordillera shallow basement units (mica schist of Amórtegui, 2007; single Pichincha
xenolith of Chiaradia et al., 2009a); Western Cordillera amphibolites and/or granulites (amphibolites of Amórtegui, 2007; Pich-
incha granulite xenoliths of Chiaradia et al., 2009a); metasediments and igneous units of the Amotape terrane (southern
Ecuador), and the Loja and Alao tectonostratigraphic units of the Eastern Cordillera (Pb isotopes only; Chiaradia et al., 2004b);
Cretaceous-Paleogene intrusions in southern Ecuador (Sr and Pb isotopes only; Chiaradia et al., 2004a). Error bars for Pb iso-
topes (± 2σ) are shown in the lower right corner of plot panels C and E; Sr and Nd isotope error bars are below symbol size.

Plateau (the regional basement unit at depth; Fig. 9A-E). In- Central Ecuadorian magmatic centers (Chaucha, Quim-
trusions of the Caribbean-Colombian Oceanic Plateau basalt- sacocha, Saraguro Group at Cañicapa) define broadly homo-
hosted Gaby porphyry Au-Cu system at the southern end of geneous Sr, Nd, and Pb isotope groups (Fig. 9A-E). Intrusions
the Western Cordillera show slightly more radiogenic Sr and associated with the El Mozo epithermal, high-sulfidation
Pb, and less radiogenic Nd isotope compositions than West- type deposit—situated at the limit between the Loja and
ern Cordillera granitoids to the north (Fig. 9A, B, D). Alao terranes of Litherland et al. (1994), and Saraguro Group

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1258 SCHÜTTE ET AL.
volcanic rocks at Tres Chorreras—mostly overlap with this
group in Nd and Pb isotope compositions (Fig. 9D), but are
characterized by a slightly more radiogenic Sr composition,
though they are still more primitive than the bulk earth (e.g.,
Fig. 9A). A significant contribution of Loja (highly radiogenic
Sr and Pb) or Alao (highly radiogenic Pb) Eastern Cordillera
basement units is thus unlikely for parental melts of the El
Mozo intrusions.
Oligocene-Miocene intrusions and volcanic rocks of the
Cangrejos-Zaruma intrusive belt are characterized by more
variably radiogenic Sr and Pb, and less radiogenic Nd isotope
compositions than magmatic centers further north (Fig. 9A,
B, D). They partly overlap with the isotopic composition of
Cretaceous-Paleogene intrusions in southern Ecuador and
consistently plot between potential, assimilant end-member
isotope compositions (Caribbean-Colombian Oceanic Plateau,
Eastern Cordillera, or Amotape basement; Fig. 9B, C, E).
Petrogenetic Constraints from
Rare Earth Element Distribution Patterns
Four major groups of variable REE distribution patterns
can be distinguished for Oligocene-Miocene intrusions and
volcanic rocks associated with porphyry-related ore deposits
in Ecuador (Fig. 8; Table 3). These groups mainly differ in
HREE fractionation and in the occurrence or absence of neg-
ative Eu anomalies. They can be correlated with distinct,
trace element compositions (as discussed further below). The
facts that (1) no Ce anomalies are observed, and (2) the main
variability in the REE pattern shape lies in the MREE and
HREE instead of the LREE (Fig. 8) have been used else-
where to argue for the petrogenetic significance of REE pat-
terns of altered rocks (Kay et al., 2005).
Group 1: REE patterns characterized by negative
Eu anomalies and without strong HREE depletion
This group is mainly made up of volcanic rocks and seriate
and porphyritic intrusions in southern Ecuador (parts of the
Cangrejos-Zaruma intrusive belt and the Saraguro Group;
Fig. 8F, G), but also includes a minor number of Western
Cordillera granitoids (Fig. 8A-C). Samples of this group uni-
formly display minor to moderate, negative Eu anomalies in
their REE patterns and make up a wide range of SiO2 con-
tents (53–70 wt %). For the most part, these plutonic and vol-
canic rocks show relatively flat MREE-HREE patterns, with
HREE concentrations ≥10 times chondrite; slightly fraction-
ated or U-shaped HREE patterns are rare. All intrusions are
characterized by high modal proportions of plagioclase and
their REE distribution patterns suggest that their parental
melts fractionated plagioclase. Although amphibole (horn-
blende) is present in significant modal proportions in several
intrusions, significant amphibole fractionation did not take
place. In H2O-saturated experimental runs of basaltic-andesitic,
bulk compositions with fO2 buffered at NNO (Ni-NiO2), pla-
gioclase appears earlier on the liquidus than amphibole only
at pressures <0.4 GPa (Grove et al., 2003). This suggests that
parental melts of intrusions and volcanic rocks of this group
underwent a significant step in evolution at shallow crustal
levels. Prior to their shallow crustal evolution, parental melt
evolution in a hot zone at deeper crustal levels (Annen et al.,
2006) mostly did not involve significant amphibole (or garnet)
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fractionation. The latter condition might apply for primitive
melt evolution in a hot zone at the base of a relatively thin
crust (or a midcrustal hot zone in a thicker crust), where H2O-
undersaturated parental melts would mainly crystallize
clinopyroxene instead of amphibole (Müntener et al., 2001).
Group 2: REE patterns without negative
Eu anomalies or strong HREE depletion
This group is made up of variably differentiated (52–71 wt %
SiO2) intrusions and volcanic rocks mainly located in southern
Ecuador (parts of the Cangrejos-Zaruma intrusive belt, the
Gaby porphyry Au-Cu deposit, and parts of the Saraguro
Group), which do not show significant negative Eu anomalies
or strongly depleted HREE contents (Fig. 8E-G; Table 3).
Parental melts of this group probably share a similar deep- to
midcrustal evolutionary history with the previous group, al-
though it might have included minor amphibole fractionation
in some cases where more hydrous melts were involved. In
contrast to the previous group, the absence of negative Eu
anomalies indicates that significant plagioclase fractionation
did not take place, suggesting a limited shallow crustal open-
system magma evolution. Alternatively (or in addition), pla-
gioclase fractionation occurred in highly oxidized melts where
Eu incompatibility for plagioclase increases in such a way that
the formation of negative Eu anomalies was suppressed
(Rollinson, 1993).
Group 3: REE patterns with strong HREE depletion and
concave-upward to flat HREE distribution
Significant HREE depletion (<10 × chondritic values)
combined with mostly concave-upward or minor relatively
flat HREE patterns is observed for a significant portion of
mineralized porphyry intrusions and spatially associated seri-
ate intrusions of the Western Cordillera (Apuela-Junin, Bal-
sapamba-Telimbela, and Chaucha; Fig. 8A-C; Table 3). All
intrusive rocks of this group are highly differentiated (64–73
wt % SiO2). In several cases, strong HREE fractionation coin-
cides with the development of a minor-moderate positive Eu
anomaly (Fig. 8B, C). The latter samples are characterized by
moderate Sr contents (300–400 ppm), and petrographic in-
vestigations indicate that they do not represent plagioclase
cumulates, although modal proportions of plagioclase are rel-
atively high.
The strong HREE depletion displayed by samples of this
group (and, possibly, their positive Eu anomalies) is indicative
of amphibole and/or titanite fractionation (or equilibration
with a restite bearing these minerals; Davidson et al., 2007;
Glazner et al., 2008). Given the highly differentiated sample
compositions, liquid-amphibole HREE partitioning coeffi-
cients will be fairly high (Bachmann et al., 2005); thus, small
amounts of amphibole fractionation, or trace amounts of ti-
tanite fractionation both succeed in explaining strong HREE
depletion.
Group 4: REE patterns with strong HREE depletion
and a negative HREE slope
This group, made up of the Quimsacocha volcanic center
and few a Junin porphyry intrusions, is characterized by sig-
nificant HREE depletion and steadily decreasing MREE/
HREE ratios (Fig. 8A, D; Table 3). Negative Eu anomalies
 TABLE 3. Summary of Petrogenetic Indicators for Crustal Magma Differentiation Depth/Pressure and Adakite-Like Features of Late Oligocene-Late Miocene Ecuadorian Arc Magmas

SiO2 Sr Y
Magmatic center Age1 (wt %) (ppm) (ppm) Sr/Y Sr/Sc (Dy/Yb)n Eu anomaly MREE-REE geometry Group2

Apuela-Junin/Cuellaje
Biotite-bearing granodiorite at Junin (batholith) 15 Ma 64–70 246–331 14 18–24 23 1.1 Minor negative Flat 1
Hornblende-biotite-bearing tonalite at Cuellaje 13 Ma 66–68 489–577 6–8 66–95 60–71 1.0–1.4 None Flat to slightly concave-upwards 3
(batholith)
Junin hornblende granodiorite porphyry I 6–9 Ma 67–71 210–3363 3.9–6.1 34–86 46–71 1.1–2.0 None Moderately decreasing slope 4
Junin hornblende granodiorite porphyry II 6–9 Ma 69–70 87–1293 2.4 36–54 27–52 0.7–1.3 None Concave-upwards 3

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Telimbela
Hornblende-bearing tonalite (batholith) 26 Ma 65 309–349 17–18 17–21 14–26 1.1 Minor negative Flat 1
Hornblende-bearing quartz-diorite (batholith) 20 Ma? 53–57 321–400 13–15 21–31 14–20 1.2 Minor negative Flat 1
Hornblende-bearing tonalite porphyry 20 Ma? 64 393 7.4 53 37 1.3 Minor positive Flat 3
Balsapamba
Hornblende-biotite-bearing tonalite I (batholith) 22 Ma 66–68 355–402 6.5–8.6 41–62 52–53 1.1–1.3 None Concave-upwards 3
Hornblende-biotite-bearing tonalite II (batholith) 22 Ma 68 393–395 1.4–3.5 112–282 37 1.2 Moderate positive Concave-upwards 3
Hornblende quartz-diorite porphyry I 21 Ma 66 333–348 8–11 31–44 25–29 0.8–1.3 Minor positive–none Concave-upwards 3
Hornblende quartz-diorite porphyry II 21 Ma? 58 344 11 32 24 1.6 Minor negative Steeply decreasing slope 1?
Gaby
Plagioclase-hornblende porphyry & seriate 20 Ma 60–65 254–310 12–17 17–25 14–20 0.8–1.2 None Flat to slightly concave-upwards 2
tonalite
Saraguro Group volcanic rocks
Andesite at Chaucha 25 Ma? 57–66 270–395 19–20 15–20 12–20 1.1 Moderately negative Flat to slightly concave-upwards 1
Dacite at Canicapa 20 Ma 69–71 289–417 12–15 19–35 63–81 1.0–1.1 None Concave-upwards 2
Andesite at Canicapa 20 Ma 62 424 15 29 37 1.3 Slightly negative Slightly decreasing slope 1

1259
Andesite at Portovelo >24 Ma 55–59 256–350 15–21 13–24 12–17 1.1–1.3 Moderately negative Flat 1
Granodiorite subvolcanic at Tres Chorreras 31 Ma? 60 210 10 21 22 1.0 None Flat 2
Chaucha
Biotite tonalite (batholith) 15 Ma 64–69 336–416 8–13 27–53 30–50 1.1–1.3 Minor negative–none Flat 2?
Granodiorite porphyry at Tunas 10 Ma 64–68 492–611 7.2–8.3 68–74 40–70 1.0–1.4 None Concave-upwards or 3
moderately decreasing
Granodiorite porphyry at Gur-Gur 10 Ma 73 307–3293 1.7–4.6 72–181 60–68 0.5–1.0 Moderate– Concave-upwards 3
major positive
El Mozo
Biotite-bearing granodiorite porphyry 16 Ma 61–62 316–459 16–25 12–18 13–30 1.0–1.2 Minor negative Flat to slightly concave-upwards 1
Quimsacocha volcanic rocks
Andesite 9.5 Ma 62–63 578–696 7–11 62–79 53–57 1.2–2.0 None Steeply decreasing slope 4
Dacite 7.1 Ma 67–70 448–858 4.1–5.7 86–168 96–128 1.4–1.9 None Moderately decreasing slope 4
Cangrejos
Biotite-bearing quartz-diorite 26 Ma 52–62 229–302 14–18 13–17 5–19 1.2–1.5 None Flat 2
Plagioclase-hornblende porphyry 24 Ma 62–65 285–317 17–23 14–17 16–20 1.1–1.4 Moderately negative Flat to slightly decreasing slope 1
Zaruma-Portovelo
PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR

Multiple porphyry intrusions around Portovelo 24 Ma 63–66 201–313 12–14 15–25 21–28 1.1–1.2 None–minor negative Flat to slightly concave-upwards 2
Multiple seriate intrusions north of Zaruma 21 Ma 55–66 228–372 14–19 13–26 14–18 1.0–1.3 Moderately negative Flat 1

1Age references in Schütte et al. (2010), and references therein; lithologies where no direct age constraint is available are marked with a question mark
2Group key: 1 = significant shallow crustal magma evolution (plagioclase fractionation); 2 = no significant shallow crustal plagioclase fractionation; no significant hornblende, garnet, or titanite frac-
tionation; 3 = significant amphibole ± titanite fractionation (higher pressure differentiation and/or H2O-rich melts); 4 = as group 3, but at higher pressure where garnet influence becomes more sig-
nificant
3Potentially petrogenetically inaccurate (depleted due to hydrothermal alteration)
1259
1260 SCHÜTTE ET AL.
are not observed. The strongly fractionated intra-HREE pat-
terns, combined with moderate-strong LREE/HREE frac-
tionation (Quimsacocha samples are fresh and their LREE
concentrations are, therefore, petrogenetically significant)
observed in this group, resemble some Quaternary Ecuado-
rian arc volcanoes, which have parental melts that are in-
ferred to evolve through combined amphibole, clinopyrox-
ene, and garnet fractionation/restite equilibration (Chiaradia
et al., 2009a). These minerals may be stabilized in variably
H2O-rich melts processed in deeper crustal hot zones
(Alonso-Perez et al., 2009). The similarities in REE charac-
teristics between some present-day Northern volcanic zone
magmas and the late Miocene Quimsacocha and some Junin
porphyry magmas indicate that they might share a similar pet-
rogenesis in terms of crustal magma evolution. In the latter
case, slab melting (Beate et al., 2001) would not be required
to explain intra-HREE fractionation (and other adakite-like
geochemical features) of the Quimsacocha volcanic center.
Crustal Magma Evolution and Adakite-like Features
of Oligocene-Miocene Intrusions and
Arc Volcanic Rocks in Ecuador
As indicated in the previous sections, Oligocene-Miocene
arc magmas associated with porphyry-related ore deposits in
Ecuador partly derive from hydrous melt equilibration with
mainly amphibole-bearing residues (with additional garnet
fractionation significant since late Miocene times). This re-
sults in Y and HREE depletion, driving an increase in Sr/Y ra-
tios (toward adakite-like compositions) at broadly constant Sr
contents. In the following section, we inspect the spatiotem-
poral distribution of these characteristic features and discuss
their petrogenetic context.
Strontium contents of arc magmas
Whole-rock Sr contents of most Oligocene-Miocene intru-
sions and volcanic rocks are relatively low (<410 ppm, avg an-
desite of Gill, 1981). Except for Quimsacocha, most samples
plot below Northern volcanic zone values at a given SiO2 con-
tent (Fig. 6D). These low Sr contents might reflect source
and/or a crustal magma differentiation effects. Considering
the former, the highly variable, Oligocene-Miocene geody-
namic regime at the northern Andean margin makes source
controls on the Sr budget of arc magmas by processes operat-
ing in the mantle wedge a possible option (e.g., variable de-
grees of mantle wedge contamination and/or metasomatism
or partial melting due to differences in the properties of sub-
ducting Farallon-Nazca lithosphere, or variable rates of sub-
duction erosion). These effects cannot be evaluated with our
data set, however, as it is mainly made up of intermediate to
highly differentiated samples. We focus, therefore, on inves-
tigating the features of crustal magma evolution, which might
contribute to Sr depletion of Oligocene-Miocene arc magmas
compared to late Miocene Quimsacocha and present-day
Northern volcanic zone magmas. The following considera-
tions apply in this context:
1. Miocene intrusions and volcanic rocks (group 1 in Table
3) characterized by negative Eu anomalies, which are indica-
tive of plagioclase fractionation, may become depleted in Sr
during shallow crustal magma differentiation.
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2. Plutonic rocks tend to be slightly depleted in incompati-
ble elements with respect to cogenetic volcanic rocks (Bach-
mann et al., 2007), such that the difference in Sr contents
between Oligocene-Miocene granitoids and Quaternary
Northern volcanic zone magmas might partly relate to the
plutonic versus volcanic nature of the samples. However, this
effect should be pronounced for more incompatible elements
such as Th (compared to Sr incompatibility), opposite of what
is observed; Northern volcanic zone frontal-arc magmas and
Oligocene-Miocene intrusions tend to overlap in Th, but dif-
fer systematically in their Sr contents (Fig. 6A, D). Moreover,
Miocene volcanic rocks of the Saraguro Group have similar,
low Sr contents as coeval intrusive rocks (Fig. 6D); as such, a
systematic compositional difference between volcanic and
plutonic rocks is an unlikely cause for the observed variations
in Sr contents.
3. Hot zone melt extraction and equilibration with basal
crustal rock units at high pressures result in elevated melt Sr
contents and leave plagioclase-diminished crustal residues
behind (Hildreth and Moorbath, 1988). Bulk Sr concentra-
tions of Oligocene-Miocene arc magmas increase through
time (Fig. 10A). The overall crustal thickness in Ecuador dur-
ing Oligocene-Miocene times was lower than at the present
day (Jaillard et al., 2005), such that the bulk increase in Sr
concentrations from Tertiary to Quaternary arc magmas
might reflect incremental or progressive crustal thickening,
and/or a deeper-seated magma source within a given, lower,
crustal hot zone.
4. Significant late Miocene eastward arc broadening likely
added further rock units as potential assimilants at depth and
caused arc magmatism to migrate toward the region of maxi-
mum crustal thickness in an across-arc dimension (Guillier et
al., 2001; Jaillard et al., 2005; Schütte et al., 2010).
Yttrium, MREE, and HREE contents of arc magmas
Maximum and minimum Y contents of late Oligocene to
late Miocene arc magmas decrease progressively through
time (Fig. 10C) and are correlated with an increase in Sm/Dy
ratios (Fig. 10B). Extreme Y depletion (<10 ppm) can be ob-
served for most Western Cordillera granitoids and at
Chaucha; this includes both seriate and porphyritic, intrusive
rock facies, and correlates with strong HREE depletion
(Table 3; groups 3 and 4). Furthermore, strong Y and HREE
depletion affects the late Miocene Quimsacocha volcanic
center. Yttrium depletion in arc magmas has been correlated
with increasing, high-pressure, crustal magma evolution be-
cause said evolution favors the stability of Y- and HREE-com-
patible minerals, which also fractionate Sm/Dy (Hildreth and
Moorbath, 1988).
Fractionation effects causing increasing
(adakite-like) Sr/Y ratios
Excluding the late Miocene Quimsacocha andesites, all
samples characterized by Y < 10 ppm represent silicic intru-
sions (SiO2 > 64 wt %; Fig. 6E). Mineral phases with a sta-
bility that is favored in silicic melts, and which are highly
compatible for Y, are made up of amphibole, zircon, and ti-
tanite, all of which have been observed as major or accessory
phases in at least some of the late Oligocene to late Miocene
intrusions. Zircon and titanite are unlikely to saturate in bulk
 PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR 1261

6
800
A B
increasing increasing

(Sm/Dy) norm.
600 high pressure high pressure
Sr [ppm]

differentiation 4 differentiation

400

200 2

alteration?
C 140 D
30
increasing
high pressure
100
differentiation
Y depletion at

Sr/Y
20 ± constant Sr
Y [ppm]

60

amphibole/titanite fract.
10 crystallization producing 20
extreme Y depletion

0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
age [Ma] age [Ma]

SYMBOL KEY
Western Cordillera granitoids Saraguro Group volcanic rocks
(Apuela, Cuellaje, Junin, Telimbela, Balsapamba)
Quimsacocha volcanic rocks
Central Ecuadorian granitoids (Chaucha, Gaby, Mozo) NVZ main arc
Chiaradia et al. (2009a)
Cangrejos-Zaruma intrusive belt NVZ frontal arc

FIG. 10. Trace element and trace element ratio versus emplacement and/or eruption age diagrams for investigated late
Oligocene to late Miocene magmatic centers. Maximum values for Sr (Fig. 10A), chondrite-normalized Sm/Dy (Fig. 10B),
and Sr/Y (Fig. 10D) of arc magmas increase systematically through time, while Y concentrations (Fig. 10C) decrease (trends
marked by black arrows), suggesting progressively increasing, high-pressure crustal magma differentiation. The latter might
be caused by the downward migration of crustal hot zones associated with episodes of crustal thickening (Mamani et al.,
2010). Extreme Y and HREE depletion of Western Cordillera granitoids at Balsapamba (21 Ma; Fig. 10C) is a local, anom-
alous phenomenon, and produces elevated (adakite-like) Sr/Y and Sm/Dy ratios in the early Miocene (Fig. 10B, D). Stron-
tium depletion of some Junin porphyry intrusions in the Western Cordillera (~9 Ma; Fig. 10A) is probably an effect of hy-
drothermal alteration and is thus petrogenetically insignificant. Reference ages for Tertiary magmatic centers are presented
in Schütte et al. (2010).

andesitic melts (although they might saturate in local melt
pockets; Hoskin et al., 2000). While amphibole is stable in
H2O-rich mafic melts and may, in concert with garnet, drive
Y depletion in mafic-intermediate melts at deep to midcrustal
levels, its partitioning coefficient for Y is highly sensitive to
melt composition and sharply increases in silicic melts (Bach-
mann et al., 2005). Thus, fractionation (or restite equilibra-
tion) of these minerals succeeds in explaining the observed
restriction of strong Y (and HREE) depletion to highly dif-
ferentiated compositions.
To test the petrogenetic significance of amphibole, zircon,
and titanite fractionation, some illustrative fractionation trends
are included in Figure 7. While progressive amphibole frac-
tionation using an amphibole-andesitic melt partitioning coef-
ficient (Rollinson, 1993) could describe the gross Sr/Y versus
Y distribution trend of our samples, it requires unrealistically
high fractionation values (up to 70%) to explain extremely
fractionated Sr/Y ratios. However, starting from a position
corresponding to a more silicic rock composition in our data
set (as a proxy for an evolved, intrusive parental melt) and
using a dacitic-rhyolitic melt partitioning coefficient (Bach-
mann et al., 2005), fractional crystallization of small amounts
(<10%) of amphibole—or trace amounts (<1%) of either zir-
con or titanite—reproduces the observed, extreme Y deple-
tion (Fig. 7E).
While amphibole, zircon, and titanite fractionation in silicic
melts affects Sr/Y versus Y distribution trends in similar ways,
their potential individual contributions can be discerned
when other trace elements are considered. Fractionating only
trace amounts (<1%) of zircon from a dacitic-rhyolitic melt
results in extreme Zr depletion of derivative liquids, which is
not observed in our data set (Fig. 6C). Although compatible
in both minerals, titanite is characterized by a much lower
partitioning coefficient for Sc than amphibole in silicic melts

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1262 SCHÜTTE ET AL.
(Bachmann et al., 2005). Therefore, if Sr/Y fractionation was
mainly driven by amphibole fractionation, it should be ac-
companied by a proportionally higher increase in Sr/Sc. In
contrast, titanite-dominated fractionation changes in Sr/Y
should have a minor effect on Sr/Sc ratios. Figure 7G shows
that small amounts (<5%) of combined amphibole-titanite
fractionation (in 95:5 proportions) closely reproduce the com-
positional Sr/Y versus Sr/Sc range of most silicic intrusions, al-
though a higher proportion of titanite with respect to amphi-
bole might be required for some intrusions. Several Saraguro
Group volcanic samples are characterized by high Sr/Sc ratios
without a concomitant strong increase in Sr/Y, suggesting
Sr/Sc fractionation there was mainly driven by amphibole (or
clinopyroxene) fractionation. The latter is in agreement with
the scarcely reported occurrence of titanite in volcanic rocks
(Hoskin et al., 2000).
Sr/Y ratios as indicators for the pressure of
crustal magma evolution
Adakite-like geochemical features of modern Northern vol-
canic zone magmas in Ecuador are mostly considered to be
the result of crustal magma evolution (e.g., Chiaradia et al.,
2009a). Elevated Sr/Y ratios commonly signal high-pressure
magma differentiation, whereas low Sr/Y ratios indicate
upper crustal magmatism at low pressures (e.g., Tulloch and
Kimbrough, 2003; Bachmann et al., 2005). This is supported
by our observations that high Sr/Y ratios (with a threshold
value of ~30–40) in our data set are associated with parental
melt evolution without significant plagioclase fractionation at
shallow crustal levels, as inferred from REE distribution pat-
terns (Table 3), and show a broad positive correlation with
Sm/Dy, thus indicating amphibole or garnet fractionation
and/or restite equilibration (Fig. 7H). Consequently, pro-
nounced magma evolution (compositional modification) at
shallow crustal levels, where plagioclase is stable closer to the
liquidus than amphibole (at <0.4 GPa; Grove et al., 2003), is
unlikely. Deep crustal, H2O-rich magma evolution potentially
involves significant garnet fractionation (at 1.2 GPa; Alonso-
Perez et al., 2009) and is not observed in our data set except
for late Miocene or younger magmas. Thus, parental melts of
most Miocene intrusions, characterized by elevated Sr/Y ra-
tios and associated with porphyry-related ore deposits in the
Western Cordillera of Ecuador, seem to have evolved at pres-
sures of ca. 0.4 to 0.8 GPa, where amphibole is expected to be
a dominant liquidus phase (Alonso-Perez et al., 2009).
The distribution of adakite-like magmatism through time
Oligocene-Miocene arc magmas sampled by Chiaradia et
al. (2004a) are mostly made up of selected intrusions and vol-
canic rocks in southern Ecuador; robust geochronologic con-
trol on sampled rock units available at that time was rather
poor. Consequently, Chiaradia et al. (2004a) inferred the
presence of two distinct temporal and compositional groups
of Tertiary-Quaternary arc magmas (adakite-like, high-pres-
sure late Miocene and Northern volcanic zone magmas ver-
sus nonadakitic, low-pressure, pre-late Miocene magmas).
Our new data allow an update of this model—Figure 10
demonstrates that broadly systematic, progressive trace ele-
ment trends through time dominate the overall late Oligocene
to late Miocene magmatic evolution, which includes different
0361-0128/98/000/000-00 $6.00 1262
petrogenetic groups including both high- and low-pressure
crustal magma differentiation. The broad correlations of Sr, Y,
and Sm/Dy distribution trends through time (Fig. 10A-C) are
in agreement with overall, progressively increasing, high-
pressure, crustal magma evolution and a higher likelihood for
the occurrence of adakite-like magmatism in Ecuador with
decreasing age (Fig. 10D).
Additional factors may be superposed on this general pat-
tern, as exemplified by strongly Y-depleted intrusions (and
thus, adakite-like Sr/Y ratios) at Balsapamba-Telimbela (~21
Ma; Schütte et al., 2010). A possible explanation for these
compositional anomalies is a more prominent role of acces-
sory phase fractionation, as discussed above. Alternatively, the
irregular geochemical signature of Balsapamba-Telimbela
might relate to anomalies in the subducting lithosphere, such
as oceanic fracture zones. The latter may lead to a locally in-
creased, volatile flux into the mantle wedge, giving rise to un-
usually H2O-rich arc magmas where amphibole and garnet
stability is increased (Rodriguez et al., 2007). While Kay et al.
(2005) note that local peaks in mantle wedge contamination by
subduction erosion may also, in part, explain the irregular oc-
currence of adakite-like arc magmas, this is rather unlikely for
Balsapamba-Telimbela because elevated Sr concentrations
(in addition to Y and HREE depletion) are not observed (Fig.
10A). Variations in the regional stress field may also represent
an additional influence factor on crustal magma differentia-
tion pressure due to their potential bearing on crustal magma
ascent and stagnation levels (e.g., Richards, 2003, 2005).
These variations have been explicitly noted to influence the
petrogenetic evolution at individual Quaternary Northern
volcanic zone volcanoes in Ecuador (Chiaradia et al., 2009a).
Variable degrees of differentiation of
adakite-like magmas through time
Increasing magma differentiation pressure results in in-
creasing proportions of garnet in an amphibole-garnet liq-
uidus assemblage for H2O-rich andesitic melts (Alonso-Perez
et al., 2009). This mainly applies to the late Miocene Quim-
sacocha volcanic center, which shares some compositional
features with several Northern volcanic zone magmas, in-
cluding a prominent garnet signature in REE patterns (Fig.
8D). In consideration of variable, melt composition-depen-
dent partition coefficients, extreme Y depletion by amphibole
fractionation only applies to relatively silicic melt composi-
tions. Garnet fractionation, on the other hand, may already
produce strong Y depletion in mafic to intermediate melts
(Rollinson, 1993). Late Miocene (Quimsacocha) or younger
arc magmas evolving by combined amphibole-garnet frac-
tionation and/or restite equilibration may, therefore, develop
toward elevated (adakite-like) Sr/Y ratios at less silicic com-
positions—i.e., during earlier differentiation stages than pre-
late Miocene arc magmas (box 1 versus box 2 in Fig. 7A).
Isotopic Constraints on Shallow versus
Deep Crustal Magma Evolution
The broad overlap observed in 87Sr/86Sr versus εNd (Fig. 9A)
—or uranogenic and thorogenic Pb (Fig. 9C, E)—isotope di-
agrams for different groups of intermediate-silicic Oligocene-
Miocene arc magmas with similar locations and variable ages
(e.g., Quimsacocha volcanic rocks, Chaucha, and El Mozo
 PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR 1263

intrusions, covering an age range of 16–7 Ma; Western
Cordillera granitoids with ages ranging from 21–9 Ma;
Schütte et al., 2010) suggests that first-order variations in
these isotopic ratios are mainly caused by differing crustal
contamination effects, rather than by significant variations in
the isotopic composition of the Ecuadorian mantle wedge
through time. Mamani et al. (2010) conclude the same for
magmas of mainly Tertiary age in the Central Andes of Peru.
Crustal contamination of arc magmas is a function of the in-
tegrated, crustal magma evolution path, and is thus controlled
by the isotopic composition and leverage of basement units,
which are potentially heterogeneous in three dimensions, as
well as crustal thickness (Hildreth and Moorbath, 1988; Dun-
gan and Davidson, 2004; Mamani et al., 2010).
Figure 11 shows plots of several radiogenic isotope ratios
versus Sr/Y and SiO2 ratios, documenting crustal magma
evolution where isotopic differences of assimilants occur both
vertically in a given crustal column and in an across-arc di-
mension. Magmatic centers of the Western Cordillera and in
central-southern Ecuador define sublinear, diverging arrays
in the 87Sr/86Sr versus SiO2 space, suggesting that open-sys-
tem, crustal magma evolution involves the assimilation of iso-
topically heterogeneous basement units (Fig. 11A). This is
further documented by distinct, Sr/Y >30, subparallel, iso-
topic arrays in Sr, Nd, and Pb isotope versus Sr/Y plots at Sr/Y
> 30 (Fig. 11B-D).
The neighboring outcrop areas of the Saraguro Group and
Quimsacocha volcanic rocks, as well as most central Ecuado-
rian granitoids (Chaucha, Mozo) and the Cangrejos-Zaruma
intrusive belt, cover a close latitudinal range (3°–4°S; Fig. 1).
Isotopic differences displayed by these magmatic centers
(Figs. 9, 11) should then mainly reflect vertical assimilant

0.708 0.708
A B
0.707 0.707
shallow to mid-crustal AFC
0.706 AFC with variable 0.706
Sr
Sr

basement units
86
86

mid- to deep crustal AFC

Sr/
Sr/

0.705 0.705
87
87

0.704 0.704

0.703 0.703
50 55 60 65 70 75 0 40 80 120
SiO 2 [wt.%] Sr/Y
8 15.70
C D

15.66
4
mid- to deep crustal AFC
init

Pb
ε Nd

204

15.62
Pb/

0
207

shallow to
mid-crustal AFC 15.58

-4
0 40 80 120 0 40 80 120
Sr/Y Sr/Y

SYMBOL KEY
Western Cordillera granitoids (Apuela, Junin, Telimbela, Balsapamba) Saraguro Group volcanic rocks

Central Ecuadorian granitoids (Chaucha, Gaby, Mozo) Quimsacocha volcanic rocks

Cangrejos-Zaruma intrusive belt

FIG. 11. Sr, Nd, and Pb isotope composition versus SiO2 and Sr/Y distribution of late Oligocene-late Miocene granitoids
and volcanic rocks. (A) 87Sr/86Sr versus SiO2 plot illustrating assimilation and fractional crystallization (AFC) trends involving
variable crustal basement rock units, as evidenced by diverging isotopic arrays with SiO2. (B) 87Sr/86Sr versus Sr/Y plot show-
ing distinct, subparallel isotopic distributions with increasing Sr/Y. As discussed in the text, the Sr/Y ratio serves as a proxy to
discriminate lower versus upper crust-dominated magma evolution (with a threshold value of ~30–40 for our data set). Major
isotopic variability is thus acquired by upper crustal magma differentiation, whereas deep crustal AFC processes produce
only limited scatter in Sr isotope compositions. (C) Initial εNd versus Sr/Y plot mirroring the trends as discussed for 87Sr/86Sr.
(D) 207Pb/204Pb versus Sr/Y plot showing that upper versus lower crustal magma differentiation is not clearly distinguishable
by Pb isotopes, suggesting greater transcrustal heterogeneity in Pb isotope compositions.

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1264 SCHÜTTE ET AL.
heterogeneities in a given crustal column. Dungan and
Davidson (2004) show that crustal contamination of arc mag-
mas may produce only subtle changes in the isotopic compo-
sition of derivative liquids if evolving arc magmas mainly con-
sume arc intrusive roots. In contrast, upper crustal assimilants
are often characterized by more mature isotopic compositions
(Hildreth and Moorbath, 1988). As discussed above, Sr/Y ra-
tios in our data set may, to some extent, qualitatively discrim-
inate between integrated crustal magma evolution at low
(usually Sr/Y <30–40; groups 1 and 2 in Table 3) versus high
pressures (Sr/Y >30–40; groups 3 and 4 in Table 3). Radi-
ogenic 87Sr/86Sr and initial εNd values of southern-central
Ecuadorian magmatic centers show major differences for
Sr/Y >30 and <30, respectively (Fig. 11B, C), indicating that
variations in crustal magma differentiation depth may signifi-
cantly influence the isotopic composition of arc magmas (see
also Chiaradia et al., 2009a).
In detail, low 87Sr/86Sr and high initial εNd values at Sr/Y >
30 in southern-central Ecuador (Chaucha, Quimsacocha) in-
dicate assimilation of arc intrusive roots or, isotopically, rela-
tively primitive oceanic plateau (Caribbean-Colombian
Oceanic Plateau) material at lower crustal levels (Fig. 11B,
C). Slightly increasing 87Sr/86Sr ratios with SiO2 (Fig. 11A)
demonstrate that high-pressure magma differentiation in
these magmatic centers is not a closed-system process. While
the adakite-like affinities of late Miocene Quimsacocha mag-
mas have been used to infer a slab melt contribution to the
petrogenetic evolution of Quimsacocha parental melts (Beate
et al., 2001) we note that lower crustal magma differentiation,
as evidenced by our geochemical and isotopic data, outline an
alternative environment compatible with the formation of
adakite-like features.
Magmas with an inferred, significant, low-pressure crustal
differentiation step (i.e., Sr/Y <30; mainly the Cangrejos-
Zaruma intrusive belt and Saraguro Group volcanic rocks) scat-
ter significantly toward higher 87Sr/86Sr and lower initial εNd
values. This is in agreement with a greater isotopic hetero-
geneity of upper crustal rock units, including the occurrence
of mature, continental, crust-like isotopic composition of po-
tential upper-crustal assimilants (Figs. 9, 11B-D). Isotope-
based discrimination between upper and lower crustal magma
evolution becomes slightly more blurred for 207Pb/204Pb (Fig.
11D), suggesting that hot zone-hosting units at lower crustal
levels have a higher variability in Pb isotope compositions.
Geodynamic Impacts on Crustal Magma Evolution
Crustal thickening
First-order variations in trace element compositions of arc
magmas associated with porphyry-related ore deposits in
Ecuador through the last ~30 Ma (Fig. 10) are broadly sys-
tematic, suggesting that progressive processes (or systematic
episodes) dominantly influenced the bulk geochemical char-
acter of arc magmatism. Similar observations for Oligocene-
Miocene arc magmas in the Central Andes have been attrib-
uted to the progressive downward migration of crustal hot
zone magmatism associated with episodes of crustal thicken-
ing (Mamani et al., 2010). Significant crustal thickening by
contraction probably affected the central Andes (southern
Peru and northern Chile) from late Oligocene times onward,
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while it initiated in northern Peru in late Miocene times (Pi-
card et al., 2008; Mamani et al., 2010). In the northern Andes
of Ecuador, pre-late Miocene crustal thickening might also
have been associated with the regional underthrusting of ac-
creted oceanic plateau fragments that, until late Miocene
times, mainly affected the forearc and frontal arc region (in-
cluding the foothills of the Western Cordillera where several
porphyry Cu systems and granitoids investigated in this study
are located; Jaillard et al., 2005).
Local effects are superposed on systematic temporal pat-
terns of Oligocene-Miocene arc magma compositions in
Ecuador, as evidenced by the trace element composition of
parts of the early Miocene, Balsapamba-Telimbela intrusive
cluster. These effects might relate to the influence of acces-
sory phase fractionation in silicic magmas, or to the influence
of oceanic fracture zone subduction and increased melt H2O
contents (see above; Rodriguez et al., 2007). Whereas
episodes of crustal thickening can be considered as a system-
atic, regional-scale effect, variations in melt H2O contents
also apply at a more local scale.
The spatiotemporal distribution of arc magmatism
Previously addressed trace element concentrations and ra-
tios used as proxies for increasing high-pressure magma dif-
ferentiation (further modulated by melt composition and dif-
ferentiation effects) show a north-south division of associated
magmatic centers: low-pressure differentiation is mainly in-
ferred for southern Ecuador (Cangrejos-Zaruma intrusive
belt, Saraguro Group), whereas high-pressure differentiation
mostly applies for northern-central Ecuador (Quimsacocha,
Western Cordillera granitoids). We suggest that this is mainly
an effect of the spatiotemporal distribution of arc magmatism
in Ecuador (Fig. 1). Mid- to late Miocene arc magmatism in
southern Ecuador migrated northward in response to the pro-
gressive along-arc broadening of a flat slab segment (Beate et
al., 2001; Schütte et al., 2010). Consequently, the lack of
younger volcanic cover sequences in southern Ecuador re-
sults in the preferential exposure of older arc magmatic units,
which were processed in an overall thinner crust (Jaillard et
al., 2005). However, regional along-arc differences might ad-
ditionally apply, as the potential for tectonic crustal thicken-
ing may be higher in northern-central Ecuador, where the pa-
leocontinental margin is buttressed against the allochthonous
oceanic plateau block (see above; Jaillard et al., 2005).
Stress regime
The petrogenetic evolution of late Miocene arc magmas
(associated with parts of the Junin porphyry Cu-Mo system
and the Quimsacocha epithermal, high sulfidation-type de-
posit) resembles several Northern volcanic zone volcanic cen-
ters, where Chiaradia et al. (2009a) propose that episodes of
bulk arc compression cause their parental melts to evolve at
deep levels of a thick crust. Several authors (e.g., Richards,
2003, 2005) note that a compressive setting favors magma evo-
lution and stagnation in deeper, crustal hot (MASH) zones,
whereas rapid magma ascent to upper crustal levels preferen-
tially occurs upon stress relaxation.
The onset of Quimsacocha magmatism (~9.5–7.1 Ma;
Schütte et al., 2010) and early porphyry intrusion emplace-
ment at Junin (~9 Ma; Schütte et al., 2010) correlate in time
 PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR
with widespread basin inversion in southern-central Ecuador,
indicating a pulse of regional compression at ~9 Ma (Hunger-
bühler et al., 2002). These arc magmas are characterized by
elevated, adakite-like Sr/Y ratios, indicating high-pressure
magma differentiation, and might support this indication of
regional compression. However, while Chiaradia et al.
(2009a) propose collision of the Carnegie Ridge seamount
chain with the northern-central Ecuadorian margin as the
cause for bulk margin compression, the latter, if applicable,
could only be relevant for arc magmas <8 Ma, the maximum
age accepted by most recent studies for the inception of
Carnegie Ridge collision in northern Ecuador (e.g., Gutscher
et al., 1999a; Michaud et al., 2009; Schütte, 2010). As such, al-
ternative causes for an overall compressional stress field at
the Ecuadorian margin—possibly associated with high-pres-
sure magma differentiation giving rise to adakite-like magma-
tism—need to be invoked.
Slab melting
The late Oligocene to mid-Miocene geodynamic setting at
the Ecuadorian margin is incompatible with slab melting, as
relatively old (ca. >40 Ma) Farallon crust was subducted at
normal angles at the Ecuadorian trench at that time (e.g.,
Lonsdale, 2005; Schütte et al., 2010). Gutscher et al. (2000)
suggest that slab flattening may facilitate slab melting and
adakitic magmatism. Slab flattening, probably in response to
subduction of buoyant, oceanic plateau-hosting lithosphere
(the Inca plateau), occurred in northern Peru and southern
Ecuador during mid- to late Miocene times, with the flat slab
segment progressively broadening in an along-arc dimension
(Gutscher et al., 1999b; Schütte et al., 2010).
While slab flattening mostly postdates arc magmatism asso-
ciated with porphyry-related ore deposits in southern
Ecuador, it broadly coincides in space and time with late
Miocene magmatism at the Quimsacocha volcanic center,
which is characterized by adakite-like features. This
prompted Beate et al. (2001) to infer a slab melt contribution
to Quimsacocha parental melts. However, we note that the Ni
and Cr contents of Quimsacocha andesites and dacites (com-
monly <10 ppm and <20 ppm, respectively; Table A1; Beate
et al., 2001) are significantly below threshold values defined
for adakites in the narrowest sense (Ni ≥20 ppm and Cr ≥30
ppm; Richards and Kerrich, 2007). As shown in the present
study, other geochemical and isotopic features of the Quim-
sacocha volcanic center are in agreement with lower crustal
magma differentiation, similar to what has been inferred for
several Quaternary Northern volcanic zone volcanoes
(Chiaradia et al., 2009a).
Significance of Adakite-like Features for
Late Oligocene to Late Miocene Porphyry-Related
Ore Deposits in Ecuador
A spatiotemporal association of porphyry-related ore de-
posits and adakite-like magmatism related to a specific path
of crustal magma evolution has been observed in a number of
studies, with amphibole commonly playing an important role
in controlling the formation of adakite-like signatures during
high-pressure differentiation of hydrous arc magmas (e.g.,
Baldwin and Pearce, 1982; Richards et al., 2001; Rohrlach
and Loucks, 2005; Richards and Kerrich, 2007; Chiaradia et
0361-0128/98/000/000-00 $6.00
1265
al., 2009b). To test the significance of this association for
Oligocene-Miocene Ecuadorian porphyry systems, we plot-
ted the compositions of mineralized porphyry intrusions and
spatially associated, seriate precursor intrusions in Sr/Y versus
Y diagrams for the five porphyry Cu systems investigated in
this study (Junin, Balsapamba-Telimbela, Chaucha, Gaby,
Cangrejos; Fig. 12). Furthermore, Figure 12 shows Sr/Y ver-
sus SiO2 diagrams to illustrate potential differentiation ef-
fects. Volcanic rocks and intrusions associated with epi-
thermal, high or intermediate sulfidation-type Au (-Cu)
deposits (Quimsacocha, Zaruma-Portovelo, El Mozo) are not
discussed, as genetic relationships between these units and
potential parental melts associated with the porphyry-epi-
thermal hydrothermal systems are not completely understood
at the moment.
Chiaradia et al. (2004a) already noted that the mutual ex-
clusivity of adakite-like magmatism and porphyry-related ore
deposits in Ecuador (as observed by these authors) might be
misleading, as it may be caused by regional outcrop and ex-
posure parameters. The present study shows that magmatism
associated with porphyry-related Oligocene-Miocene ore de-
posits in Ecuador may be of both adakite-like and nonadakitic
affinity. Porphyry stocks and dikes at Junin, Balsapamba-Te-
limbela, and Chaucha are characterized by adakite-like signa-
tures (Fig. 12A-C), whereas porphyry intrusions at Gaby and
Cangrejos are not (Fig. 12D-E). At the scale of individual de-
posits, the occurrence of adakite-like magmatism seems to be
broadly time-controlled; there is a shift toward adakite-like
magma compositions at Junin (>15 to 13–6 Ma; note that Sr
contents of Junin porphyries might have been lowered by hy-
drothermal alteration in such a way that these intrusions
would originally plot at higher Sr/Y ratios; Fig. 12A), at Te-
limbela (~26–20 Ma; Fig. 12B), and at Chaucha (15–10 Ma;
Fig. 12C). In contrast, no systematic shifts are recorded at
Gaby and Cangrejos (always low Sr/Y; Fig. 12D-E) and Bal-
sapamba (always high Sr/Y; Fig. 12B), where the intrusive
evolution spans a relatively short time range of less than 2
m.y. (Balsapamba batholith growth covers a significantly
longer time span, but geochemical data for older intrusive
pulses are not available). Silica contents of samples with vari-
able Sr/Y ratios are approximately constant at Junin (Fig. 12A)
and Chaucha (Fig. 12C), indicating that temporal changes,
rather than differences in the degree of differentiation (which
is constantly high), form the main control on Sr/Y ratios in
these magmatic centers.
The following two observations can be made, both of which
correlate among the various porphyry systems:
1. Excluding the occurrence of elevated Sr/Y ratios at Bal-
sapamba-Telimbela, Sr/Y ratios tend to become higher with
decreasing intrusive age on a regional scale. The age trend co-
incides with a south-north spatial distribution trend that re-
flects general, arc magmatic migration patterns (as discussed
above). Thus, the spatiotemporal distribution of adakite-like
magmatism for these Ecuadorian porphyry Cu systems
largely reflects regionally controlled trends in arc magma geo-
chemistry. Consequently, mineralized Oligocene-Miocene
porphyry intrusions do not seem to be exclusively associated
with a specific geochemical signature or a specific path of
crustal magma evolution in Ecuador, supporting the general
1265
1266 SCHÜTTE ET AL.

200 porphyry intrusions

Apuela batholith (at Junin)
Junin A
0°19’N
Apuela batholith (at Cuellaje)
150

200
Sr/Y

100 ~13 Ma adakite boundary

(Sr/Y >40)

Sr/Y
100
50
adakite boundary
6-9 Ma (Sr/Y >20)
>15 Ma
200
porphyry intrusions (Bals.) Balsapamba B
Balsapamba batholith Telimbela
150 porphyry intrusions (Teli.) 1°40’S
Telimbela batholith
Sr/Y

200
100

19-22 Ma
50 Sr/Y 100 FIG. 12. Sr/Y versus Y dia-
grams differentiating mineralized
porphyry intrusions and spatially
26 Ma? associated, seriate, precursor in-
trusive units for individual late
porphyry intrusions
Chaucha batholith
Chaucha C Oligocene to late Miocene por-
2°56’S phyry Cu deposits in Ecuador.
150 Also shown are Sr/Y versus SiO2
diagrams, which allow direct
evaluation of differentiation ef-
Sr/Y

200 fects. Overall, the occurrence of

100 adakite-like features in all intru-
~10 Ma
sions (porphyritic and seriate)
tends to follow the regional com-
Sr/Y

50 100 positional characteristics of arc

~15 Ma magmatism at a given time. If
present, trace element composi-
tional differences between por-
200 phyry intrusions and spatially as-
porphyry intrusions
seriate tonalite
Gaby D sociated seriate intrusions relate
to different emplacement ages
3°03’S
intrusions and petrogenetic trends through
150
time. Junin (Fig. 12A) and
Chaucha (Fig. 12C) Sr/Y ratios of
intrusive rocks vary for rocks of
Sr/Y

200
100 similar SiO2 contents, demon-
strating that the observed varia-
tions in Sr/Y are, to a first order,
Sr/Y

50 100 controlled by temporal trends

rather than simply representing
differences in the degree of dif-
21-20 Ma ferentiation. Amphibole ± titan-
200 ite ± garnet fractionation and/or
porphyry intrusions restite equilibration at deep to
Cangrejos E midcrustal levels drives hydrous
seriate (qtz-) diorite 3°30’S
intrusions melt evolution toward adakite-
150 like compositions. This magmatic
evolution step might represent a
200 metallogenically favorable pre-
Sr/Y

100 conditioning stage for porphyry

parental melts (e.g., Rohrlach
and Loucks, 2005), whereas—as
Sr/Y

100 discussed in the text—intense,

50
shallow crustal magmatism dur-
~26 Ma ~24 Ma ing peak batholith assembly may
be less favorable to form and pre-
serves porphyry-related mineral-
0 5 10 15 20 25 50 60 70 ization. Emplacement ages are
Y (ppm) SiO 2 [w t.%] from Schütte et al. (2010).

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 PETROGENETIC EVOLUTION ASSOCIATED WITH PORPHYRY-RELATED ORE DEPOSITS IN ECUADOR
notion that any arc magma of a sufficient volume may poten-
tially contribute to the formation of an average-tonnage por-
phyry Cu deposit, as long as the relevant tectonomagmatic
processes combine favorably (Cline and Bodnar, 1991;
Richards, 2005).
2. Except for Cangrejos, porphyry intrusions lack negative
Eu anomalies, indicating the absence of significant shallow
crustal plagioclase fractionation or/and relatively oxidized
parental magmas. Where porphyry intrusions are associated
with batholith-scale intrusive clusters (Junin, Balsapamba, Te-
limbela, Chaucha), porphyry intrusion emplacement is mostly
late with respect to batholith magmatism (Fig. 12A-C; Schütte
et al., 2010). Batholith construction peaks during arc mag-
matic flare-ups are commonly associated with high magma
supply rates, where large shallow crustal magma chambers in-
volving major plagioclase fractionation might be established
(e.g., Bachmann et al., 2005, 2007; de Silva and Gosnold,
2007). The underrepresentation of major, shallow crustal mag-
matic systems temporally associated with Oligocene-Miocene
porphyry intrusion emplacement in Ecuador might relate to
the following: (1) Lower H2O solubilities of melts, evolving at
lower pressures; on the other hand, petrogenetic precondi-
tioning of porphyry parental melts by progressive, volatile en-
richment due to magma evolution at higher pressures favor-
ably influences the fluid exsolution kinetics of subsequently
ascending melt batches with respect to porphyry-related min-
eralization, and also increases the pressure-sensitive Cl melt-
fluid partition coefficient (potentially implying a fluid richer in
Cl-complexed Cu; Rohrlach and Loucks, 2005). (2) Uncon-
trolled volatile loss to the surface and fluid dissipation instead
of focused exsolution, due to a higher probability for cata-
strophic ignimbrite eruption associated with shallow crustal,
batholith construction peaks (de Silva and Gosnold, 2007;
Bachmann et al., 2007; Sillitoe, 2010). (3) A higher probability
for internal deposit dilution by frequent, postmineral intrusive
pulses, which are associated with the high magma flux during
peak shallow crustal batholith construction.
As demonstrated above, melt evolution at deep to mid-
crustal levels may result in adakite-like geochemical composi-
tions of Tertiary Ecuadorian arc magmas if pressure, melt
composition, and melt H2O contents are suitable to stabilize
amphibole (and other phases such as garnet) in the evolving
magma; as such, adakite-like signatures might indicate a
tectonomagmatic environment where favorable petrogenetic
preconditioning of porphyry parental melts at depth for sub-
sequent porphyry-related mineralization may occur (Rohrlach
and Loucks, 2005; Chiaradia et al., 2009b; see also Richards,
2003, 2005). Thermal constraints dictate that a sizeable melt
reservoir, a key variable for the metal budget of a given por-
phyry-related ore deposit, may be sustained at mid- to deep
crustal levels for a significant amount of time (e.g., Annen et
al., 2006) without sharing the metallogenically negative im-
pacts potentially associated with periods of peak batholith
magmatism at shallow crustal levels as pointed out in the pre-
vious paragraph.
Oyarzun et al. (2001) note that adakite-like features may be
particularly relevant for the tonnage of a given porphyry-re-
lated ore deposit. In this context, we note that the significance
of magma chemistry (such as adakite-like or nonadakitic
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1267
composition) for the total tonnage of a given ore deposit
in Ecuador cannot be accurately evaluated because the
Oligocene-Miocene porphyry systems are variably deeply
eroded in such a way that their current tonnage, which is
mostly poorly constrained at the moment, does not necessar-
ily reflect the initial deposit size (PRODEMINCA, 2000a).
However, Oligocene-Miocene porphyry-related ore deposits
in Ecuador included in this study do not seem to be of giant
size, in contrast to a number of Tertiary ore deposits else-
where in South America. The significance of specific geo-
chemical compositions for giant porphyry-related ore de-
posits, possibly associated with a specific geodynamic
environment, thus warrants further study (e.g., Baldwin and
Pearce, 1982; Cooke et al., 2005).
Conclusions
We present a data set on the geochemical and isotopic com-
position of arc magmas associated with late Oligocene to late
Miocene porphyry-related ore deposits in Ecuador. Our data
allow us to investigate the petrogenetic evolution of these arc
magmas, evaluate geodynamic and tectonic impact factors on
arc magmatism, and explore the association of various paths
of crustal magma evolution with porphyry-related ore de-
posits. In this context, we investigate the tectonomagmatic
environment and metallogenic significance of Oligocene-
Miocene, adakite-like magmatism in Ecuador.
Late Oligocene to late Miocene mineralized porphyry in-
trusions—as well as seriate intrusions and volcanic rocks spa-
tially associated with porphyry-related ore deposits in
Ecuador—compositionally define four major petrogenetic
groups indicative of distinct crustal magmatic evolution paths
(Table 3). With the exception of early Miocene, adakite-like
magmatism at the Balsapamba-Telimbela batholith (and the
associated porphyry Cu systems), trace element distribution
patterns of these groups through time are broadly systematic
and indicate crustal magma differentiation at progressively
higher pressures from the late Oligocene to the late Miocene.
The integrated vertical (transcrustal) magma evolution of
these different groups is clearly recognizable in terms of radi-
ogenic isotope compositions and Sr/Y ratios.
Magmatic centers with adakite-like features (Sr/Y >40)
occur throughout the Miocene and are mainly hosted by the
Western Cordillera in northern-central Ecuador. High Sr/Y
magmatism mostly results from strong Y and HREE deple-
tion at broadly constant Sr contents. This is related to crustal
magma differentiation, including fractionation and/or restite
equilibration effects of amphibole, garnet, and titanite. Shal-
low crustal plagioclase fractionation affected some, but not
all, late Oligocene and younger arc magmas associated with
porphyry-related ore deposits in southern Ecuador; it is of
minor petrogenetic significance for Miocene intrusions asso-
ciated with porphyry Cu deposits in the Western Cordillera of
northern-central Ecuador. As the petrogenetic importance of
high-pressure crustal magma differentiation increases from
the late Oligocene to the late Miocene—perhaps related to an
overall trend of crustal thickening—the influence of amphi-
bole and garnet fractionation and/or restite equilibration is
progressively extended in such a way that the likelihood for
Y/HREE depletion and elevated (adakite-like) Sr/Y ratios in-
creases with decreasing magmatic age.
1268 SCHÜTTE ET AL.
Compositional differences between mineralized porphyry
intrusions and spatially associated seriate intrusions mostly
relate to regional-scale magmatic evolutionary trends in
Ecuador, such that changes in their respective geochemical
compositions are broadly controlled by relative emplacement
age differences. Compositional differences are not recorded
if the time difference between the respective emplacement
events is small (<2 m.y.). In this case, magmas may be both of
adakite-like or nonadakitic affinity. For late Oligocene to late
Miocene porphyry Cu deposits where multi-m.y., precursor
batholith magmatism occurs at the same site and porphyry in-
trusion emplacement represents a late (or the last) magmatic
event, we note a tendency of porphyry intrusive parental
melts to evolve toward adakite-like compositions. While this
observation integrates into the regional-scale magmatic evo-
lution trend noted above, it also indicates that porphyry Cu
deposit formation was associated with magmatism at greater,
mid to deep crustal depth at a given location. This tectono-
magmatic framework, allowing prolonged evolution and
volatile enrichment of porphyry parental melts, may be more
favorable for porphyry-related ore deposit formation than
peak, shallow, crustal batholith magmatism.
Acknowledgments
We thank Fabio Capponi, Alexey Ulianov, Denis Fontignie,
and Jean-Marie Boccard for analytical support and technical
assistance. Comments by Kalin Kouzmanov and Othmar Mün-
tener on an early version of the manuscript as part of the senior
author’s Ph.D. thesis were appreciated. The manuscript bene-
fited from the thoughtful reviews of Jon Davidson and Jeremy
Richards, and from the careful editorial handling by Larry
Meinert. This project was funded by the Swiss National Sci-
ence Foundation (grants 200021-109636 and 200020-117617).
Logistic field support was generously provided by Ascendant
Copper, International Minerals Corporation, Dynasty Metals
and Mining, Iamgold, AtlasMoly, Channel Resources, and
Ecuagold. P.S. benefited from travel grants from the Augustin
Lombard Foundation of the Geneva SPHN Society and the
Ecole Doctorale en Sciences des Minéraux (EDSM).
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