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Distinctive composition of copper ore forming arc magmas

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Australian Journal of Earth Sciences (2014)

61, 5–16, http://dx.doi.org/10.1080/08120099.2013.865676

Distinctive composition of copper-ore-forming

arc magmas
R.R. LOUCKS*

Centre for Exploration Targeting, School of Earth and Environment, University of Western Australia, Crawley, WA
6009, Australia.

Magmatic fertility to generate porphyry- and high-sulfidation copper ore deposits generally develops,
not at the scale of individual igneous complexes, but rather at the scale of petrochemical provinces
spanning hundreds of kilometres of arc length, and containing many igneous complexes. The extent
and duration of copper metallogenic provinces and epochs are apparently controlled by
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geodynamically imposed compressive stress that commonly lasts ca 5–20 Ma and fosters entrapment
of mantle-derived basaltic magmas in chambers near the Moho where they cool very slowly and are
likely to last long enough to experience intermittent replenishment during fractional crystallisation of
layered ultramafic–mafic cumulate complexes on the chamber floor. Accumulation of dissolved H2O
through multiple cycles of replenishment and crystallisation in high-pressure magma chambers can
explain the distinguishing chemical features of copper-ore-forming calc-alkalic arc magmas. The
distinguishing features include unusually high contents of Sr and V, and unusually low contents of Sc
and Y. The distinction from ordinary andesitic, dacitic and rhyolitic arc magmas can be enhanced by
using ratios of enriched elements to depleted elements. The ratios Sr/Y and V/Sc are shown here to be
effective in discriminating least-altered samples of ore-forming intrusions from ordinary,
metallogenically unproductive arc magmas.
KEYWORDS: porphyry copper, high sulfidation, metallogeny, arc magmatism, exploration, magma
fertility, adakite.

INTRODUCTION magmas. These two themes are the principal topics of

It is enigmatic that large segments of some arcs become
richly mineralised during a brief epoch, but preceding
and succeeding igneous activity in the same region pro-
duced little or no copper ore. Striking examples include:
the rich porphyry copper provinces that developed ca
66–54 Ma in the southwestern USA and northern Mexico;
the string of porphyry-copper deposits that formed ca 42–
31 Ma in northern Chile; the many gold-rich magmatic-
hydrothermal deposits that formed during the Miocene
epoch in northern Chile; and the swarm of copper and
gold deposits that developed between 5 and 1 Ma in arcs
bordering the western margin of the Philippine Sea
Plate and along the New Guinea–Solomons–Fiji interval
of the southwestern Pacific Plate (Sillitoe 2010, and refer-
ences therein).
Any model that purports to explain the origins of
magmatic fertility for generating magmatic-hydrother-
mal copper ore deposits along convergent plate margins
must account for: (1) the tendency of deposits to cluster
in metallogenic belts and epochs that are transient in
space and time within much more extensive and longer-
lived convergent-margin magmatic belts; and (2) the dis-
tinctive lithophile-element chemical characteristics of
copper-ore-forming arc magmas relative to ordinary arc
this paper.
FIRST-ORDER CONTROLS ON COPPER FERTILITY
OF ARC MAGMAS
Figure 1 shows the distribution of late Paleogene copper
(
gold
silver
molybdenum)-bearing magmatic-
hydrothermal ore deposits in the central Andes. The
take-away messages from this time–space distribution of
ore deposits are that: (1) the controls on metallogenic fer-
tility operate not at the at the scale of individual mag-
matic centres, but rather over hundreds of kilometres of
arc length including many magmatic centres; and (2) the
ability of certain arc segments to turn on and shut off
metallogenic activity and migrate fore and aft while
remaining magmatically active implies that copper met-
allogenic fertility is not due to recycling pre-existing Cu
enrichments within the lithosphere, such as often
appears to be the case for tin, molybdenum, uranium
and fluorine ore provinces. It is evident from its tran-
sient provinciality that magmatic fertility for copper
metallogeny cannot be explained by serendipitous
crustal contamination scenarios, such as assimilation of
limestone, redbeds, coal or sulfidic black shales. Neither

*Robert.Loucks@uwa.edu.au
Ó 2014 Geological Society of Australia
 TAJE_A_865676.3d (TAJE) 18-02-2014 17:23

6 R. R. Loucks
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Figure 1 Distribution of Cenozoic magmatic-hydrothermal porphyry copper (–gold–silver–molybdenum) and copper-bearing

gold-rich epithermal and porphyry deposits in the central Andes. Green symbols represent deposits of Paleogene age, mainly
late Eocene and earliest Oligocene. Red symbols represent deposits of Neogene age. Squares are gold-rich intermediate- and
high-sulfidation epithermal deposits and porphyry gold (–copper) deposits; circles are porphyry copper (
gold
molybde-
num) deposits. It is striking that the latitude interval 19–26 S that was richly productive of giant porphyry coppers in the late
Eocene has continued to be magmatically active up to the present time, but has been metallogenically unproductive for the
past 25 Ma, whereas the latitude interval 29–34 S that was magmatically active but metallogenically unproductive in the Paleo-
gene became richly productive of copper and gold–copper deposits in the Neogene. In the interval 17–19 S, the metallogeny
switched from copper-dominant in the Eocene to gold-dominant in the Neogene, and migrated inland. South of El Teniente,
the Southern Volcanic Zone in the latitude interval 35–47 S has been magmatically active but metallogenically unproductive
for copper throughout the Cenozoic. The two Neogene ore provinces along the west side of the Neogene–Quaternary Altiplano
uplift and along the west side of the Sierras Pampeanas Neogene thrust and fold belt are coincident in time and space with lat-
itude intervals of strong orogenic deformation by agents illustrated in blue. Depth contours on Wadati-Benioff zone (Cahill &
Isacks 1992) flare eastward where the Nazca plate is buoyed up by the thick crust of the Nazca Ridge (top of map) and by the
young, warm Juan Fernandez Ridge (8.5 Ma at east end; < 1 Ma near the current location of the Juan Fernandez hotspot
(Farley et al. 1993; Flueh et al. 1998). Shaded areas on the seafloor are shallower than 4 km depth (von Huene et al. 1997). The
oldest ocean floor at the trench is Chron 23 (58 Ma) at the Peru–Chile bend (Arica orocline), where the slab dip is relatively
steep at 34 (Cahill & Isacks 1992). The relative-motion vectors of the Nazca and South America plates (78–81 mm/yr) are
from DeMets et al. (1990). The plate-convergence vector is decomposed into vector components perpendicular to (dashed light
blue arrows) and parallel to (dashed dark blue arrows) the trench on the north and south sides of the Arica bend at the Peru–
Chile border. North and south of Arica, the trench-parallel components of the plate-convergence vectors have opposing direc-
tions that converge to produce compression that has caused crustal thickening and uplift of the Altiplano region (Dewey &
Lamb 1992) and oroclinal bending by more than 30 during the past 20 Ma (MacFadden et al. 1995). Grey triangles schemati-
cally represent the distribution of Quaternary volcanic cones (Isacks 1988), which are absent above the flattest parts of the
slab in central Peru and in Chile at 29–33 S, where the South American Plate has over-ridden the buoyant Nazca Ridge and
Juan Fernandez Ridge.
 TAJE_A_865676.3d (TAJE) 18-02-2014 17:23
can it be explained by serendipitous subduction of local
compositional anomalies in the oceanic lithosphere
such as volcanogenic massive sulfide deposits or serpen-
tinised fracture zones. Explanations of copper metallo-
genic provinces must invoke processes that transcend
chemical heterogeneity in local environments.
Sillitoe (1998) noted that crustal thickening associated
with compressive tectonism was synchronous with the
formation of giant porphyry copper systems in central
and northern Chile, southwest Arizona, Irian Jaya and
Iran. The late Eocene–early Oligocene ore belt (Figure 1)
developed during waning stages of a period of Cordille-
ran orogeny that appears to be related to the collision of
Africa-Arabia with Eurasia, which closed the western
Tethys, stalled the Afro-Arabian plate, and caused the
full spreading rate on the mid-Atlantic Ridge to be trans-
mitted as accelerated westward migration of the Ameri-
cas, causing them to over-ride their Pacific-margin
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subduction zones and induce a period of low-angle sub-
duction and Eocene orogenic deformation at latitudes
from Montana to central Chile (Silver et al. 1998). The
two Neogene metallogenic belts represented by red sym-
bols on Figure 1 are coincident in time and space with
latitude intervals of Neogene strong orogenic deforma-
tion by stress-focusing into indentations in the over-rid-
ing plate, and by buoyant features (bathymetric highs)
in the subducting plate that drag along the base of the
over-riding plate, as described in the caption. It is there-
fore likely that the transient provinciality of copper met-
allogeny along convergent plate margins is due to
geodynamically imposed variations of tectonic stress,
which in turn affect the depth at which magmas are
trapped and chemically differentiate by fractional crys-
tallisation (Loucks 2000; Loucks & Ballard 2002; Rohrlach
2002; Rohrlach & Loucks 2005).
ARE COPPER-ORE-FORMING MAGMAS
UNUSUALLY WATER-RICH?
A clue to the origin of magmatic fertility for copper ore
genesis is given by the distribution of hornblende along
the southern and central Andes. My survey of the exten-
sive literature on petrology of late Cenozoic igneous
centres in the unmineralised Southern Volcanic Zone of
Chile finds that the latitude interval 35–45 S contains a
larger proportion of basalts, and corroborates the report
by Hildreth & Moorbath (1988) that its andesites and
dacites are nearly all pyroxene-rich and hornblende-
poor or -absent. During metallogenic epochs in the ore
belts farther north, hornblende usually arrived in the
crystallisation sequence at a basaltic andesite or mafic
andesite (54–59 wt% SiO2) stage of magmatic differentia-
tion, and pyroxene-bearing dacites and rhyolites are
apparently absent.
Andesitic to rhyolitic magmas containing more than
about 1–1.5 wt% dissolved H2O have more H2O than can
be accommodated in hydroxyl sites of igneous minerals,
so the rest migrates to country rocks or to the atmo-
sphere during crystallisation. The H2Oþ or loss-on-igni-
tion in a whole-rock chemical analysis does not
represent the water content of hydrous magmas from
which the rock crystallised, so the hydration state of
Copper-ore-forming arc magmas 7
magmas must be assessed from thermodynamic analysis
of mineral–melt equilibria, such as the plagioclase/melt
hygrometer (Housh & Luhr 1991; Rohrlach & Loucks
2000; Lange et al. 2009) or inferred qualitatively from
whole-rock element ratios. Rohrlach & Loucks (2005)
used the plagioclase/melt geohygrometer calibration of
Rohrlach & Loucks (2000) to demonstrate that ore-stage
dacitic magmas that produced the giant Tampakan high-
sulfidation and porphyry Cu (–Au) deposits in southern
Mindanao had accumulated 8 wt% dissolved H2O by
inheritance through several cycles of magma-chamber
replenishment and fractional crystallisation.
It is useful to exploration geologists to be able to infer
the hydration state of arc magmas from commonly
reported major and trace elements in published whole-
rock analyses. Formulation of whole-rock element-ratio
proxies for the hydration state of magmas can be
assisted by reference to experimental studies that show
how varying the hydration state of a magma affects the
crystallisation sequence of minerals and hence the rela-
tive rates of depletion or enrichment of major and trace
elements in the residual melt during cooling and crystal-
lisation at any given pressure.
Figure 2 illustrates how increasing the content of dis-
solved H2O in a silicate melt affects the crystallisation
sequence of minerals. The effect of dissolving the first
few percent H2O is to hydroxylate the bridging oxygens
Figure 2 Varying the wt% H2O dissolved in the silicate melt
strongly affects the order of mineral crystallisation from the
melt—and consequently the relative rates of depletion or
accumulation of various trace elements in the melt—as illus-
trated by this map of phase assemblages in a series of experi-
ments on a basaltic-andesite arc magma of the composition
shown in the inset. Each black dot represents an experiment
in which the crystallising mineral assemblage was identi-
fied by Moore & Carmichael (1998), and the melt’s content of
dissolved H2O (dotted grey contours) was determined from
the composition of the quenced glass according to the
method of Moore et al. (1998). At PH2O ¼ 0 (dry), the crystalli-
sation order of silicates from the cooling melt is plagioclase
first, followed by olivine, orthopyroxene and then augite. At
PH2O > 350 MPa and > 6.5 wt% H2O dissolved in the melt, pla-
gioclase is the last of those silicates to crystallise, and horn-
blende is first. Saturation curves for magnetite and
orthopyroxene in the hydrous melts are based on lower-tem-
perature experiments by Blatter & Carmichael (1998).
 TAJE_A_865676.3d (TAJE) 18-02-2014 17:23
8 R. R. Loucks
that bind Si–O–Al tetrahera together to constitute the
polymerised framework of the silicate melt (Burnham
1979; Stolper 1982). Hydroxylation breaks the polymeris-
ing bonds. Depolymerisation of the melt makes it more
difficult for minerals such as feldspars and pyroxenes to
assemble their crystal structures, so their saturation
temperatures decrease with increasing OH content of
the melt. Orthosilicates such as olivine and zircon that
use only silica monomers should rise in saturation tem-
perature owing to increasing supply of monomers upon
addition of the first few percent H2O to dry melt (cf. oliv-
ine-in curve in Figure 2), but further increase in dis-
solved H2O dilutes the concentrations of all other
chemical components of the melt and thereby depresses
the saturation temperatures of all anhydrous minerals,
including oxides such as chromite and titanomagnetite,
as shown in Figure 2. Hydroxyl-bearing minerals such
as hornblende and biotite rise in saturation temperature
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during dissolution of the first 5–6 wt% H2O in the melt,
but with further additions of dissolved H2O, the dilution
effect takes over, and saturation temperatures of
hydroxyl-bearing minerals decline too (Holloway 1973;
Foden & Green 1992).
Changes in the crystallisation order of these miner-
als, equivalent to those shown in Figure 2, have been
demonstrated in experiments with varied H2O contents
on bulk compositions ranging from tholeiitic basalt (Hol-
loway & Burnham 1972; Feig et al. 2006; Pichavant & Mac-
Donald 2007), high-alumina basalt (Baker & Eggler 1983;
Foden & Green 1992), low-alumina andesite (Blatter &
Carmichael 1998), siliceous andesite (Green 1972; Martel
et al. 1999), dacite (Rutherford & Devine 1988; Johnson &
Rutherford 1989; Scaillet & Evans 1999; Costa et al. 2004),
to high-silica rhyolite (Scaillet et al. 1995). In all cases,
the saturation temperatures of feldspars and quartz are
depressed more by increasing H2O than are saturation
temperatures of ferromagnesian silicates. As shown by
the dotted grey contours in Figure 2, the melt’s H2O dis-
solution capacity is very sensitive to decompression, but
not very sensitive to cooling. All the experiments show
that crystallisation of hornblende from basaltic and
basaltic-andesitic melt compositions above  980 C
requires > 5 wt% dissolved H2O in the melt (e.g. Feig
et al. 2006); dacitic melts at 800–850 C require > 4 wt%
H2O for hornblende crystallisation (Costa et al. 2004).
The melt’s inability to dissolve that much H2O at low
pressure destabilises hornblende.
The conclusion from Figure 2 is that whole-rock ele-
ment ratios that reflect the modal ratio of plagioclase/
hornblende segregated from the magma during differ-
entiation up to the stage sampled should reflect the
hydration state of the magma. Elements such as Al and
Sr that partition strongly into plagioclase, but weakly
into hornblende, should accumulate in residual melts
until plagioclase eventually saturates. Elements that
partition strongly into hornblende, but not into plagio-
clase, should undergo strong depletions from residual
melt as hornblende crystallises, e.g. Ti, Sc and Y. Thus,
in more hydrous mafic-to-felsic magmatic differentia-
tion series, the ratios Al2O3/TiO2 and Sr/Y in whole-
rock analyses may be expected to rise more strongly
with rising SiO2, whereas these ratios may be expected
to remain flat or decline with rising SiO2 in weakly
hydrous or dry mafic-to-felsic differentiation series
(Loucks 2000).
At high contents of dissolved H2O in the melt, horn-
blende can saturate before titanomagnetite (Figure 2)
and can deplete the melt of Fe3þ as well as Fe2þ and
thereby delay and suppress production of magnetite. V4þ
has a very high magnetite/melt partition coefficient on
the order of 10 times larger than the hornblende/melt
partition coefficient (Luhr & Carmichael 1984; La
Tourette et al. 1991), so to the degree that hornblende
supplants titanomagnetite as a sink for Fe3þ in very
hydrous melts, vanadium can avoid much of the deple-
tion from the melt that occurs in drier magmatic differ-
entiation series. So, the ratio V/Sc can be expected to
rise with rising SiO2 in very hydrous mafic-to-felsic dif-
ferentiation series (Loucks 2000). These expectations
will be tested for relevance to copper-ore-forming arc
magmas in a following section.
EFFECT OF PRESSURE ON MAGMATIC
DIFFERENTIATION TREND
Calculations by Loucks (2000), Loucks & Ballard (2002),
Rohrlach (2002), and Rohrlach & Loucks (2005) indicate
that magmas ascending from the asthenospheric mantle
wedge into a lithospheric regime of horizontal compres-
sive stress during orogeny, have difficulty propagating
dykes to the upper crust and are likely to stall at or near
the Moho, where basaltic magmas lose much of their
buoyancy at the density discontinuity between dense
mantle peridotite and less-dense lower-crustal mafic
granulites or gabbros. Where the roots of arcs are
exposed at various localities around the world, lower-
crustal layered ultramafic–mafic cumulate complexes
provide evidence of arc magmas stalling and crystallis-
ing at high pressure for long periods (e.g. Garuti et al.
1980; DeBari & Coleman 1989; Miller et al. 1991). Cognate
xenoliths of high-pressure cumulates in volcanic and
hypabyssal calc-alkalic rocks provide corroborative evi-
dence (e.g. DeLong et al. 1975; Arculus & Wills 1980; Con-
rad & Kay 1984; DeBari et al. 1987; Lee et al. 2007).
Figure 3 illustrates the experimentally determined
effect of pressure variation on the crystallisation
sequence of minerals at constant bulk composition
(including constant bulk H2O content) during solidifica-
tion of a magnesium-rich tholeiitic basaltic parental
melt at any given depth. There are several important fea-
tures to note. (1) At 0.1 GPa (upper blue horizontal band),
plagioclase is the second silicate to begin crystallising,
whereas at 1.3 GPa (lower blue horizontal band), plagio-
clase is among the last; residual felsic liquid of dacitic
composition can precipitate ultramafic cumulates on
the magma chamber floor. (2) Hornblende precipitation
begins at higher temperatures at lower-crustal depths
than at upper-crustal depths. (3) Hornblende’s advance
in the crystallisation sequence with increasing pressure
occurs at the expense of titanomagnetite (as well as
pyroxenes and plagioclase), because high-pressure horn-
blende can accommodate most of the Ti and all the Fe3þ
in a normal calc-alkalic composition (at ƒO2 around the
nickel metal þ nickel-oxide buffer, in these experiments).
 TAJE_A_865676.3d (TAJE) 18-02-2014 17:23

Copper-ore-forming arc magmas 9

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Figure 3 Experimentally determined liquidus phase relations of picritic tholeiite dyke RC158c from the Adamello igneous
complex, Italian Alps (Ulmer 1989; Ka € gi et al. 2005) and of similar magnesian tholeiite compositions, combined with lower-tem-
perature phase-relations in less primitive basaltic and andesitic bulk compositions having initial H2O contents and composi-
tions that lie on the chemical evolution trajectory of a picritic parent initially containing 2.5–3 wt% H2O. Shaded sectors in
the hexagons indicate the presence of the respective mineral in the quenched experiment, keyed to the enlarged, labelled
hexagon in the lower-left. Late-crystallising and accessory minerals are not represented in the hexagons. Mineral saturation
curves labelled ‘Olivine-in’ etc. represent the apparent temperature of first appearance of the respective mineral during cool-
ing and crystallisation at any particular depth. Some minerals stop crystallising (e.g. ‘Olivine-out’ curve) when their chemical
components in the melt are consumed by other, recently arrived minerals, such as hornblende. The 2.5–3 wt% H2O in the start-
ing composition exceeds the magma’s water solubility limit at depths less than  3.5 km (1 kbar), so the upper parts of the min-
eral saturation curves show a kink and rise in temperature as H2O exsolves with decreasing pressure. Mismatch of starting
bulk compositions causes minor discrepancies of mineral stability fields among the various experimental studies represented
by different colours on the diagrams. Mafic magmas with more than 1 wt% H2O finish crystallising at the wet solidus. The
mineral paragenetic sequence in a magma crystallising at any particular depth corresponds to the succession of saturation
curves crossed by horizontal paths extending from the liquidus on the right to the solidus on the left. The crystallisation
sequences during cooling along the light blue horizontal bands illustrate the contrast in mineral assemblage and crystallisa-
tion sequence in magma chambers at 1 kbar (3.5 km depth) and at 13 kbar (40 km depth, appropriate to the crust/mantle
boundary in continent-margin orogenic belts).

So, it is apparent that increasing pressure up to about
1 GPa has essentially the same effect on the relative sta-
bilities of plagioclase, hornblende and titanomagnetite
as the effect of increasing the content of dissolved H2O in
the melt. In the following sections, tests are made
whether the element ratios Al2O3/TiO2, Sr/Y and V/Sc
are effective in discriminating copper-ore-forming intru-
sions from ordinary arc magmas in apparently unminer-
alised arc segments. For the purpose of mineral
exploration, it is not necessary to discriminate the com-
ponent of the chemical signal owing to elevated H2O con-
tent from the component of the signal owing to elevated
pressure and orogenic compressive stress.
STRATEGY AND METHODS
Formulation and testing of petrogenetic hypotheses,
regarding linkages between tectonic and petrochemical
controls on magmatic-hydrothermal ore-forming pro-
cesses, may be done more efficiently by thorough compi-
lation and imaginative analysis of the vast amount of
extant petrochemical analytical data in published litera-
ture and student theses, than by embarking on a field-
based mapping and sampling and chemical analysis pro-
gram of necessarily modest regional scope and duration.
For this study chemical analyses have been compiled
(major and trace elements) of petrographically fresh or
weakly altered intrusive rocks that are deemed by the
respective authors to represent the magmatic source of
exsolved hydrothermal fluids that supplied most of the
essential chemical components for formation of 135 por-
phyry-type, or high-sulfidation epithermal type, or exog-
enous skarn and manto replacement-type ore bodies of
mined or minable economic significance in which cop-
per is a principal metal of value. Because unaltered sam-
ples of ore-forming intrusions are in short supply in
most studies of most districts (mainly from satellite
 TAJE_A_865676.3d (TAJE) 18-02-2014 17:23

10 R. R. Loucks

dykes emanating from ore-stage stocks), most deposits in

the compilation are represented by only one, two or
three ‘least-altered’ samples that retain nearly fresh pla-
gioclase. Igneous (not hydrothermal-alteration-induced)
chemical features of those ore-productive intrusions are
compared with chemical features of large and composi-
tionally diverse arc igneous suites from regions that are
relatively thoroughly explored and believed to have no
association with economically significant magmatic-
hydrothermal copper mineralisation. The barren suites
selected for comparison comprise 473 samples of Neo-
gene and Quaternary volcanics and shallow intrusions
in the latitude interval 21.2–25.7 S of the Chilean Central
Volcanic Zone (CVZ), 893 samples of Neogene and Qua-
ternary volcanics and shallow intrusions throughout
the latitude interval 35–46 S of the Chilean Southern Vol-
canic Zone (SVZ), and 1094 samples of Pliocene and Qua-
ternary volcanic rocks and epizonal intrusions
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throughout the Kurile-Hokkaido and North Honshu

(Toyoha) arcs. Theoretically formulated chemical
parameters are tested for their efficacy in sorting analy-
ses of ore-productive intrusions from the unmineralised
rock suites in the CVZ, SVZ and Kurile-Hokkaido-Hon-
shu barren reference suites.
Selection criteria for compiled analyses
Selection criteria for acceptable analyses are:
(1) Loss on ignition (LOI) or individually analysed H2O
þ CO2 þ S sum to < 3.5 wt%.
(2) Analytical totals in the 97.5–101.5 wt% range (vola-
tile-free basis).
(3) Absence of significant plagioclase-destructive hydro-
thermal alteration according to the authors’ petro-
graphic descriptions (in thin-section, plagioclase is
often cloudy, but with visible polysynthetic
twinning).
(4) None of the utilised analyses represents crystal
cumulates to a conspicuous degree; in particular, no
whole-rock analyses have positive europium anoma-
lies Eu/Eu > 1.3, and none have > 20 wt% Al2O3—
features characteristic of plagioclase cumulates.
(5) All analyses belong to the tholeiitic or the low-K to
high-K calc-alkalic magma series, as defined by
Irvine & Baragar (1971) and by Peccerillo & Taylor
(1976).
(6) None of the compiled analyses corresponds to feld-
spathoid-normative alkalic rocks, nor to the ortho-
pyroxene-normative, strongly potassic-alkalic
absarokite–shoshonite–banakite series as defined by
Peccerillo & Taylor (1976).
RESULTS OF COMPARISONS
In Figure 4, the whole-rock Al2O3/TiO2 of fresh or weakly
altered samples (as described in the preceding section on
‘selection criteria’) of ore-forming porphyry intrusions
parental to 135 major Phanerozoic copper ore deposits at
convergent plate margins are compared with all avail-
able analyses of unaltered Neogene–Quaternary volca-
nic and hypabyssal rocks in two latitude intervals of the
Figure 4 Red symbols are least-altered samples of intrusions
parental to major copper (
molybdenum) ore deposits;
inverted pink triangles are least-altered samples of intru-
sions that exsolved hydrothermal fluids that produced
major gold-rich porphyry and high-sulfidation and skarn
deposits of Phanerozoic age worldwide. These ore-forming
suites are compared with all available analyses of volcanic
and hypabyssal intrusions in two latitude intervals of the
Chilean Andes that lack known significant copper ore depos-
its in the 23–0 Ma time frame. Blue squares represent aver-
age continental-margin arc basalt, basaltic andesite,
andesite, dacite and rhyolite from my compilations for Neo-
gene and Quaternary suites from the Andes, southern
Alaska, Kamchatka, Japan, Ryukyu arc, Sunda arc and New
Guinea. The data have been compiled from many published
sources.
Chilean Andes that lack known significant copper min-
eralisation in the age range 23–0 Ma.
Feiss (1978) presented empirical evidence that por-
phyry-Cu-productive intrusions in the southwestern
USA and Greater Antilles typically have higher values of
the alumina saturation index (i.e. Al2O3/
(CaOþNa2OþK2O) on a molar basis) than regionally
associated, penecontemporaneous barren intrusions.
Mason & Feiss (1979) extended that observation to New
Guinea and the Solomon Islands. Figure 4 shows that the
igneous differentiation trend leading to magmatic-
hydrothermal Cu-ore-forming intrusions extends to
compositions that are significantly more aluminous
than the unproductive arc reference suites, and more
aluminous than average basalts, basaltic andesites,
andesites, dacites and rhyolites of continent-margin
arcs. As illustrated in Figures 2 and 3, higher dissolved
H2O contents and/or higher total pressure tend to shift
the relative positions of plagioclase and titanomagnetite
and hornblende in the crystallisation sequence, and
thereby tend to delay and diminish plagioclase produc-
tion and to advance and enhance hornblende production
at the expense of plagioclase, because hornblende con-
sumes plagioclase-forming components of the melt.
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Copper-ore-forming arc magmas 11

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Figure 5 On a plot of whole-rock Sr/Y vs wt% SiO2, seemingly barren intra-oceanic and epi-continental Neogene and Quater-
nary volcanic and hypabyssal tholeiitic and calc-alkalic arc suites (Aleutian arc, northern Japan, central and southern Chile)
are compared with fresh or least-altered samples of intrusions parental to major Cu and Cu–Au deposits of Phanerozoic age
worldwide. Nearly all Au-poor giant porphyry Cu deposits (e.g. Chuquicamata, Rio Blanco, Escondida, El Abra, El Salvador
and Yulong) plot at Sr/Y ratios > 40 (mostly >70) and have SiO2 > 60 wt%. Most samples of most giant Au-rich porphyry Cu
deposits (Panguna, Bingham Canyon, Ok Tedi, Grasberg, Batu Hijau, Alumbrera) are less siliceous at 58–68 wt% SiO2, and
plot at Sr/Y > 35, tending to cluster in the lower half of the range for ore-productive intrusions. The Au-poor, low-grade subeco-
nomic Cu prospects (not shown) plot mainly or entirely at Sr/Y < 40. Barren arc suites plot at even lower Sr/Y in the SiO2
range > 55 wt%. The trends of large black symbols that represent average circum-Pacific arc basalt, basaltic andesite, andes-
ite, dacite and rhyolite do not significantly overlap the Sr/Y range of magmas that produced any giant porphyry Cu deposits.
For prospectivity assessments of igneous complexes, sites having Sr/Y > 35 at SiO2 > 57 wt% can be regarded as Cu-fertile.

These relations cause initially tholeiitic, mantle-derived
basaltic magmas to differentiate by crystal-liquid segre-
gation along a more strongly calc-alkalic differentiation
trend, which corresponds to a trend of more strongly
increasing Al2O3/TiO2 in the melt as magmatic differen-
tiation proceeds. Copper-ore-forming arc magmas are
the most extreme representatives of the calc-alkalic dif-
ferentiation trend.
Figure 5 shows that the ratio of Sr/Y in 291 least-
altered samples of ore-stage intrusions, parental to 135
major Phanerozoic porphyry copper (–gold) ore deposits,
is usefully effective in discriminating copper-ore-forming
magmas from ordinary andesites, dacites and rhyolites in
apparently unmineralised arc segments around the
Pacific margin. Thie blemont et al. (1997) compiled chemi-
cal analyses of intrusions related to 28 porphyry copper
 TAJE_A_865676.3d (TAJE) 18-02-2014 17:23
12 R. R. Loucks
deposits worldwide and reported that most of them are
associated with ‘adakites,’ which are calc-alkalic rocks of
andesitic to dacitic composition that have high Sr/Y as
one of their distinguishing characteristics. Thie blemont
et al. (1997) followed the interpretation of Defant & Drum-
mond (1990) in attributing their genesis to partial fusion
of mafic protoliths at high pressure in the eclogite or gar-
net-granulite facies. Loucks (2000) and Loucks & Ballard
(2002) showed that more than 80 porphyry copper deposits
worldwide are genetically related to felsic intrusions hav-
ing Sr/Y > 35, and they attributed the genesis of those
magmas to fractional crystallisation of ordinary arc-basal-
tic magmas at high pressure in slow-cooling, long-lived,
Moho-level magma chambers in which intermittent
chamber replenishments during continuous fractional
crystallisation led to accumulation of exceptional con-
tents of dissolved H2O in residual melts after several crys-
tallisation-and-replenishment cycles. Detailed petrological
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study of the long-lived (ca 8 Ma) Tampakan igneous com-
plex in Mindanao, Philippines, field-tested and validated
this petrogenetic model (Rohrlach & Loucks 2005). Cham-
befort et al. (2008) reported that the Cu–Au high-sulfida-
tion epithermal and porphyry deposits at Yanacocha,
Peru, developed late in the history of a long-lived (ca
6 Myr) igneous complex from very hydrous hornblende-
phyric magmas that had undergone magmatic differentia-
tion at 6–9 kbar before migrating to subvolcanic ore-
forming depths. Least-altered samples of ore-stage horn-
blende-andesite at Yanacocha were reported by Turner
(1997) and Longo et al. (2010) to have Sr/Y > 50. Chiaradia
et al. (2012) have updated the literature survey of ore-
related igneous suites having elevated Sr/Y, and they
describe evidence at Pilavo volcano, Ecuador, for exsolu-
tion of Cu-rich hydrothermal fluid from ascending H2O-
rich magma at 15 km depth.
The plagioclase/melt partition coefficient of Sr is
around 3–5 in calc-alkalic hydrous melts of andesitic and
dacitic composition (Blundy & Wood 1991), whereas the
hornblende/melt partition coefficient of Y is around 2–
6 in melts of andesitic and dacitic composition (Ewart &
Griffin 1994; Sisson 1994) and is substantially higher
than that of augite/melt. So, the trend to high Sr/Y in
copper-ore-forming arc magmas is readily accounted for
by early and prolific crystallisation of hornblende and
by delayed and diminished production of plagioclase,
both in response to elevated contents of dissolved H2O in
the melt and lower-crustal pressure on the order of 0.6–
1.2 GPa, as illustrated in Figures 2 and 3.
In Figure 6 the ratio V/Sc in the same suite of least-
altered whole-rock samples of porphyry-copper-ore-
forming intrusions effectively discriminates most of
them from average, ordinary volcanic and hypabyssal
andesites, dacites and rhyolites in apparently unminer-
alised segments of circum-Pacific Neogene–Quaternary
arcs. The distinction in V/Sc ratio is accounted for by
the effects of elevated content of dissolved H2O in the
melt (Figure 2) and/or elevated pressure (Figure 3) in
causing hornblende to advance in the crystallisation
sequence relative to titanomagnetite. At melt redox
states ranging from about 6 log units of ƒO2 below to 2
log units above the fayalite–magnetite–quartz reference
buffer, vanadium is predominantly in the V4þ valence
state and follows Ti4þ into titanomagnetite (Toplis &
Corgne 2002). But to the degree that hornblende takes
over from titanomagnetite as a sink for Fe3þ, as shown
in Figures 2 and 3, more vanadium can remain in resid-
ual melt, while scandium continues to be efficiently
extracted from the melt into hornblende.
High magmatic K2O destabilises hornblende
Experimental evidence shows that at a specified pres-
sure and H2O content in calc-alkalic magma of nominally
constant composition, increasing the melt’s Na2O con-
tent or Na2O/K2O ratio causes hornblende to saturate at
higher temperature, earlier in the crystallisation
sequence (Cawthorn 1976; Sisson & Grove 1993). The Na-
bearing pargasitic–hastingsitic hornblende is stable to
substantially higher temperatures and pressures than
alkali-poor amphiboles (Holloway 1973; Thomas 1982).
Although some marginally shoshonitic magma com-
positions are shown in Figures 5 and 6 (e.g. from Goo-
numbla, Cadia, Grasberg-Ertsberg, Bingham Canyon,
etc.), the reason for excluding more strongly potassic-
alkalic arc magma series from the compilations shown
in Figures 5 and 6 is that highly potassic magma series
tend to crystallise biotite þ pyroxenes
titanomagnetite
in lieu of hornblende over a greater interval of the differ-
entiation sequence. In strongly potassic members of the
orthopyroxene-normative absarokite–shoshonite–bana-
kite clan and in feldspathoid-normative leucite tephrites
and leucite phonolites etc., hornblende is commonly
absent throughout the differentiation sequence. The
effect of elevated activity of an orthoclase (or leucite or
kalsilite) molecular component in the melt is to destabi-
lise molecular components of hornblende by reactions of
the following types:
pargasite melt

NaCa2 ðMg4 AlÞðAl2 Si6 ÞO22 ðOHÞ2 þ SiO2 þ
melt

plagioclase plagioclase augite
KAlSi3 O8 ! CaAl2 Si2 O8 þ NaAlSi3 O8 þ CaMgSi2 O6
biotite
þ KMg3 ðAlSi3 ÞO10 ðOHÞ2
and
ferri-pargasite melt

NaCa2 ðFe2þ 3þ
4 Fe ÞðAl2 Si6 ÞO22 ðOHÞ2 þ 0:5 Fe2 Si2 O6
melt plagioclase

þ KAlSi3 O8 ! 0:5 CaAl2 Si2 O8
plagioclase magnetite augite
þ NaAlSi3 O8 þ 0:5 Fe2þ Fe3þ
2 O4 þ 1:5 CaFeSi2 O6
biotite
þ KFe2þ
3 ðAlSi3 ÞO10 ðOHÞ2
Whereas elevated Na2O activity as NaAlSi3O8 or NaAl-
SiO4 molecular components of the melt would cause
reactions of this type to run to the left, producing parga-
sitic hornblende at the expense of pyroxenes and plagio-
clase, reactions (1) and (2) show that at constant
hydration state of the magma (no water molecules con-
sumed or liberated in these reactions), increasing the
K2O content of the melt—as orthoclase or leucite or kalsi-
lite molecular components of the melt—tends to convert
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Copper-ore-forming arc magmas 13

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Figure 6 Whole-rock V/Sc is highly selective for Cu, not Au, ore-forming fertility. The ratio V/Sc is available for fewer samples
of fewer deposits than the ratio Sr/Y shown in Figure 5. The V/Sc has a different mineralogical basis than Sr/Y, and is rela-
tively resistant to disturbance by moderate hydrothermal alteration, so it can provide independent corroboration of the Cu
prospectivity of igneous suites. Average basalt, basaltic andesite, andesite, dacite and rhyolite in late Cenozoic circum-Pacific
arcs (heavy grey squares and circles) represent the usual magmatic-differentiation trend of igneous suites that are unprospec-
tive for Cu-dominant ore deposits. Magmas parental to gold-dominant deposits (not shown) generally plot at higher V/Sc
ratios than average unproductive arc magmas, but within the range of scatter of the unproductive suites that are plotted for
comparison. Many intrusions parental to major Au–Cu deposits (dark pink triangles) also plot within the field of scatter of
unproductive igneous suites. However, all of the Au-poor giant porphyry Cu deposits (Chuquicamata, El Abra, Escondida), as
well as some of the giant Au–Cu deposits (Bingham, Batu Hijau, Ertsberg, Bajo de la Alumbrera), are characterised by V/Sc >
10, which does not significantly overlap the scatter range of unproductive arcs or arc segments. All intrusive felsic porphyry
suites having V/Sc > 10 are unambiguously prospective (magmatically fertile) for large Cu (
Au) deposits. The cutoff can be
defined by the sloping line V/Sc ¼ 32.5–0.385  wt% SiO2.

pargasite, tschermakite, edenite, hastingsite, kaersutite
and related molecular components of hornblende solid
solution into plagioclase þ augite
magnetite. Biotite
may crystallise synchronously with plagioclase, augite
and magnetite, or ‘biotite’ can be retained in the melt as
a latent molecular component until it saturates after
plagioclase and augite began to crystallise, depending on
pressure, temperature and K2O content of the melt, etc.
Owing to suppressed hornblende crystallisation by ele-
vated K2O content in the melt, highly potassic-alkalic
arc magmas characteristically have undepleted yttrium
but experience greater magnetite-induced vanadium
 TAJE_A_865676.3d (TAJE) 18-02-2014 17:23
14 R. R. Loucks
depletion as magmatic differentiation proceeds at mod-
erate oxygen fugacity, typically in arc magmas around 1–
3 log units above the fayalite–magnetite–quartz refer-
ence buffer. Consequently, in strongly potassic magma
series, the V/Sc ratio evolves to low values with increas-
ing SiO2, just as in tholeiitic magmas that are too H2O
poor to crystallise early and abundant hornblende. The
exception to this generalisation is at very high ƒO2s,
which are rather common in strongly alkalic arc mag-
mas (such as those parental to the Emperor and Ladolam
and Cripple Creek gold deposits), wherein an appreci-
able fraction of the V in the melt occurs as V5þ (Toplis &
Corgne 2002), which accumulates in residual melts and
is partitioned into exsolving hydrothermal fluids to gen-
erate vanadian mica (roscoelite) and vanadian sulfides
(colusite, vanadian enargite, etc).
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CONCLUSIONS
Values of Sr/Y > 35 and V/Sc > 32.5–0.385  wt% SiO2 at
58–70 wt% SiO2 are typical of arc magmas parental to
magmatic-hydrothermal copper ore deposits at conver-
gent plate margins throughout Phanerozoic time, accord-
ing to my compilation of compositions of ore-forming
intrusions in 135 deposits. These ratios may be used to
screen whole-rock chemical analyses to identify igneous
complexes that may contain undiscovered copper ore.
Magmatic fertility, as represented by these chemical
features, is a necessary, but not sufficient, condition for
an igneous complex to produce a major porphyry or
high-sulfidation magmatic-hydrothermal copper
deposit. Most, if not all, major porphyry Cu–Mo deposits
are composite ore bodies produced by overlap of several
pulses of mineralisation from a succession of juxtaposed
stocks. Tectonic disturbance may disrupt the magmatic
plumbing system, causing volcanic vents and subvol-
canic apophyses to relocate, with the result that succes-
sive mineralisation pulses do not superpose to generate
a large composite ore deposit. If volcanoes undergo sec-
tor collapse that redistributes the load on the underlying
magma chamber, successive stocks and their mineralisa-
tion shells may not be juxtaposed. If the subvolcanic
‘batholithic’ magma body is relatively flat-topped and
lacks major apophyses, then flow of the more buoyant,
felsic, hydrous residual melt fractions along the roof
may lack focus, with the result that only widely distrib-
uted, subeconomic mineralisation is produced.
Chemical screening of whole-rock analyses to identify
arc segments, individual igneous complexes within
them, and stages in the evolution of long-lived magmatic
centres that match the chemical features of copper-ore-
forming arc magmas, is one of two principal criteria
that exploration geologists should apply to selection of
geologically favourable target regions. The second crite-
rion is targeting arc intervals that have experienced
recent compressive orogenic deformation in the lead-up
to the magmatic activity being assessed.
ACKNOWLEDGEMENTS
I am grateful to journal reviewers Massimo Chiaradia,
Anthony Crawford and David Cooke for substantially
improving the clarity of presentation. The material has
also been honed by discussions with exploration staff of
many companies that sponsored much of this research
and with academic audiences at many presentations.
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Received 8 July 2013; accepted 8 November 2013