Miner Deposita (2015) 50:493–515
DOI 10.1007/s00126-014-0539-y
ARTICLE
Geochemistry of magnetite from porphyry Cu and skarn deposits
in the southwestern United States
Patrick Nadoll & Jeffrey L. Mauk & Richard A. Leveille &
Alan E. Koenig
Received: 21 January 2013 / Accepted: 9 April 2014 / Published online: 23 August 2014
# Springer-Verlag Berlin Heidelberg (outside the USA) 2014
Abstract A combination of petrographic observations, laser
ablation inductively coupled plasma mass spectrometry (LA-
ICP-MS), and statistical data exploration was used in this
study to determine compositional variations in hydrothermal
and igneous magnetite from five porphyry Cu–Mo and skarn
deposits in the southwestern United States, and igneous mag-
netite from the unmineralized, granodioritic Inner Zone
Batholith, Japan. The most important overall discriminators
for the minor and trace element chemistry of magnetite from
the investigated porphyry and skarn deposits are Mg, Al, Ti,
V, Mn, Co, Zn, and Ga—of these the elements with the highest
variance for (I) igneous magnetite are Mg, Al, Ti, V, Mn, Zn,
for (II) hydrothermal porphyry magnetite are Mg, Ti, V, Mn,
Editorial handling: R.P. Xavier and G. Beaudoin
Electronic supplementary material The online version of this article
(doi:10.1007/s00126-014-0539-y) contains supplementary material,
which is available to authorized users.
P. Nadoll : J. L. Mauk
School of Geography, Geology and Environmental Science,
The University of Auckland, Private Bag 92019,
Auckland, New Zealand
R. A. Leveille
Freeport McMoRan Copper & Gold Inc., Phoenix, 333 N.
Central Ave., Phoenix, AZ 85004, USA
A. E. Koenig
U.S. Geological Survey, MS-964 Denver Federal Center,
PO Box 25046, Denver, CO 80225-0046, USA
Present Address:
P. Nadoll (*)
CSIRO-ARRC, 26 Dick Perry Avenue, 6151 Kensington,
WA, Australia
e-mail: pnadoll@gmail.com
Present Address:
J. L. Mauk
U.S. Geological Survey, MS-964 Denver Federal Center,
PO Box 25046, Denver, CO 80225-0046, USA
Co, Zn, and for (III) hydrothermal skarn magnetite are Mg, Ti,
Mn, Zn, and Ga. Nickel could only be detected at levels above
the limit of reporting (LOR) in two igneous magnetites.
Equally, Cr could only be detected in one igneous occurrence.
Copper, As, Mo, Ag, Au, and Pb have been reported in
magnetite by other authors but could not be detected at levels
greater than their respective LORs in our samples.
Comparison with the chemical signature of igneous magnetite
from the barren Inner Zone Batholith, Japan, suggests that V,
Mn, Co, and Ga concentrations are relatively depleted in
magnetite from the porphyry and skarn deposits. Higher for-
mation conditions in combination with distinct differences
between melt and hydrothermal fluid compositions are
reflected in Al, Ti, V, and Ga concentrations that are, on
average, higher in igneous magnetite than in hydrothermal
magnetite (including porphyry and skarn magnetite). Low Ti
and V concentrations in combination with high Mn concen-
trations are characteristic features of magnetite from skarn
deposits. High Mg concentrations (<1,000 ppm) are charac-
teristic for magnetite from magnesian skarn and likely reflect
extensive fluid/rock interaction. In porphyry deposits, hydro-
thermal magnetite from different vein types can be distin-
guished by varying Ti, V, Mn, and Zn contents. Titanium
and V concentrations are highly variable among hydrothermal
and igneous magnetites, but Ti concentrations above
3,560 ppm could only be detected in igneous magnetite, and
V concentrations are on average lower in hydrothermal mag-
netite. The highest Ti concentrations are present in igneous
magnetite from gabbro and monzonite. The lowest Ti concen-
trations were recorded in igneous magnetite from granodiorite
and granodiorite breccia and largely overlap with Ti concen-
trations found in hydrothermal porphyry magnetite.
Magnesium and Mn concentrations vary between magnetite
from different skarn deposits but are generally greater than in
hydrothermal magnetite from the porphyry deposits. High
Mg, and low Ti and V concentrations characterize hydrother-
mal magnetite from magnesian skarn deposits and follow a
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trend that indicates that magnetite from skarn (calcic and
magnesian) commonly has low Ti and V concentrations.
Keywords Magnetite . Hydrothermal . Porphyry . Skarn .
Minor and trace elements
Introduction
Magnetite (Fe3O4) is one of the most abundant oxide minerals
in the continental crust, and a common accessory mineral in
igneous, metamorphic, and sedimentary rocks; it is also a
common mineral in porphyry Cu and skarn deposits.
Magnetite crystallizes over a wide range of geologic condi-
tions and can incorporate a large number of minor and trace
elements (Buddington and Lindsley 1964; Dupuis and
Beaudoin 2011; Ghiorso and Sack 1991a; Haggerty 1991;
Nadoll et al. 2014; Powell and Powell 1977). The chemistry
of magnetite is governed by a number of controlling factors
such as temperature, fO2, fS2, cooling rate, matrix/melt ratio,
and fluid compositions (Buddington and Lindsley 1964; Frost
and Lindsley 1991; Ghiorso and Sack 1991b; Haggerty 1991;
Mollo et al. 2013; Whalen and Chappel 1988). These attri-
butes make magnetite a useful petrogenetic indicator and a
useful pathfinder mineral for geochemical studies (Barnes and
Roeder 2001; Dare et al. 2012; Dupuis and Beaudoin 2011;
Nadoll et al. 2012, 2014; Reguir et al. 2008; Righter et al.
2006a; Ryabchikov and Kogarko 2006). Insights into compo-
sitional variations between magnetite of igneous and hydro-
thermal origin, in combination with a thorough petrographic
understanding and statistical analysis can be used to discrim-
inate barren from mineralized areas and hence, can be
employed as a tool to fingerprint ore deposits (Carew et al.
2006; Dupuis and Beaudoin 2011; Kamvong et al. 2007;
McQueen and Cross 1998; Nadoll and Koenig 2011; Nadoll
et al. 2012, 2014; Rusk et al. 2010; Singoyi et al. 2006). The
characterization of igneous and hydrothermal magnetite has
been facilitated by the development and improvement of
analytical techniques such as laser ablation inductively
coupled plasma mass spectrometry (LA-ICP-MS) and elec-
tron probe microanalysis (EPMA) that allow in situ measure-
ments with increasingly lower detection limits (Dare et al.
2012; Dupuis and Beaudoin 2011; Longerich et al. 1996;
Nadoll and Koenig 2011; Nadoll et al. 2014).
Iron, Al, Ti, Mg, Mn, Zn, Cr, V, Ni, Co, and Ga are
elements that typically substitute primary cations in spinel
group minerals such as magnetite and are therefore the most
useful indicator elements for discriminating magnetite from
different sources (Barnes and Roeder 2001; Carew et al. 2006;
Dupuis and Beaudoin 2011; Klemm et al. 1985; Lindsley
1976; Nadoll et al. 2012, 2014; Rusk et al. 2009). Although
magnetite has been used as an indicator mineral for petroge-
netic and provenance studies for over 60 years (Buddington
Miner Deposita (2015) 50:493–515
and Lindsley 1964; Frietsch 1970; Hutton 1950; Mitcham
1952; Rumble 1976; Shcheka et al. 1980, 1982), only more
recent studies have shown systematic compositional patterns
in hydrothermal magnetite that promote its use as an indicator
mineral for exploration. For example, Dupuis and Beaudoin
(2011) employ Ni/(Cr+Mn) vs. Ti+V and Ca+Al+Mn vs.
Ti+V diagrams to differentiate hydrothermal magnetite from
porphyry Cu, skarn, and other mineral deposits. McQueen and
Cross (1998) demonstrate how variations in trace element
concentrations in hydrothermal magnetite from contact meta-
somatic skarn deposits can help to target magnetite-bearing
ore deposits. Rusk et al. (2010) show that high Mn/Ti ratios in
magnetite from iron oxide–copper–gold (IOCG) deposits con-
trast with Mn/Ti ratios found in magnetite from unmineralized
breccia bodies in the Cloncurry region.
Here, we demonstrate that hydrothermal orebodies such as
porphyry Cu and skarn deposits, and their associated host
rocks, can be characterized and discriminated based on com-
positional variations in magnetite. We present minor and trace
element data for hydrothermal and igneous magnetite from
five well-studied porphyry Cu and skarn deposits in the south-
western United States (Fig. 1) and compare those with igneous
magnetite from an unmineralized magnetite-series granodio-
rite of the Inner Zone Batholith in southwest Japan (Ishihara
1977; Spong 1998).
Porphyry and skarn deposits are characterized by multiple
mineralization stages, primary and secondary alteration, and,
in most cases, a diverse suite of plutonic, volcanic, and (meta)-
sedimentary host rocks (Lowell and Guilbert 1970; Seedorff
et al. 2005; Sillitoe 2010). Skarn deposits can form where
porphyry systems intrude carbonate rocks (e.g., Beane and
Titley 1981; Einaudi 1981; Einaudi et al. 1981; Meinert et al.
2005). Magnetite of hydrothermal and igneous origin is a
ubiquitous accessory mineral in these magmatic-
hydrothermal environments. Hydrothermal magnetite occurs
in veins of varying assemblages. The vein style in porphyry-
type deposits commonly evolves from early simple magnetite
to later more complex magnetite–pyrite–chalcopyrite–quartz–
epidote veins (Arancibia and Clark 1996; Gustafson and Hunt
1975; Sillitoe 2010). Hydrothermal magnetite can also occur
disseminated, associated with large-scale potassic alteration.
In skarn, hydrothermal magnetite can be an abundant mineral,
Fig. 1 Location of sampled porphyry Cu–Mo+skarn deposits in the„
western United States. a Simplified geological map of the Chino (Santa
Rita), Hanover-Fierro, and Copper Flat deposits (after Hernon et al.
1964). b The Chino (Santa Rita) porphyry Cu deposit and the
associated calcic and magnesian Cu-Fe skarn (after Hernon et al. 1964).
c Simplified geological map of the Morenci porphyry Cu deposit and the
associated structurally controlled Cu-Fe-Zn skarn (after Richard et al.
2000). d The Safford mining district showing the locations of the four
porphyry Cu deposits–Dos Pobres, Lone Star, San Juan, and Sanchez
(after Langton and Williams 1982; Richard et al. 2000)
Miner Deposita (2015) 50:493–515 495
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occurring as massive replacement mineralization from Fe-rich
fluids (Einaudi 1981; Meinert et al. 2005).
We used petrographic examination, EPMA, LA-ICP-MS,
and statistical data analysis to determine major, minor, and trace
element variations in hydrothermal and igneous magnetite from
five porphyry Cu and skarn deposits within the Late Cretaceous
to early Tertiary (Laramide) magmatic arc in the southwestern
United States (Creasey 1980; English and Johnston 2004;
Sillitoe 2010) (Fig. 1): (1) Chino (Santa Rita), (2) Hanover-
Fierro, (3) Copper Flat, (4) Morenci, and (5) Safford.
Methods
We collected a suite of 177 samples representing the variety of
host rocks, veins, and alteration types associated with the five
porphyry Cu and skarn deposits. Samples, thin and polished
sections were studied petrographically to document the miner-
al assemblages and to help discriminate hydrothermal from
igneous magnetite. Hydrothermal and igneous magnetite sep-
arates were prepared by crushing whole rock samples that were
then magnetically separated. Magnetite grains were mounted
in epoxy resin pucks and analyzed using EPMA and LA-ICP-
MS. The limit of reporting (LOR=10 times standard deviation)
is used here because it is a more robust and reliable lower limit
of element concentrations (Shrivastava and Gupta 2011).
One of the crucial prerequisites for obtaining meaningful
compositional data is the discrimination of igneous and
hydrothermal magnetite based on careful petrographic
examination. McQueen and Cross (1998) report that textures
or crystal habits may reflect the origin of magnetite grains.
Magnetite of igneous and hydrothermal origin can be discrim-
inated based on a number of features: (1) area of occurrence—
vein vs. disseminated in host rock, (2) habit—euhedral vs.
massive, (3) associated minerals—mafic minerals vs. second-
ary hydrothermal minerals, and (4) the occurrence and type of
exsolutions and mineral inclusions. Unless otherwise noted
(ESM 2), igneous magnetite from the five examined deposits
has been collected from fresh (unweathered) rocks.
Laser ablation inductively coupled plasma mass spectrometry
and electron probe microanalysis
LA-ICP-MS analyses were carried out at the U.S. Geological
Survey (USGS) in Denver using a New Wave Research UP-
193 FX LA system (193 nm, 4 ns excimer, ArF) that was
coupled to a PerkinElmer DRC-e ICP mass spectrometer
(carrier gas He) using the methods described in Nadoll and
Koenig (2011). The laser was operated at 4 Hz pulse frequen-
cy with an energy density of ∼5 J/cm2. The acquisition time
for each analysis was 120 s. The background was analyzed for
45–60 s. Iron concentrations, determined by EPMA with a
15 kV standard energy dispersive spectroscopy (EDS) signal
Miner Deposita (2015) 50:493–515
(800 pA beam current, 2 μm beam size, and 100 s count time),
were used as an internal standard for calibration of LA-ICP-
MS data. The EPMA was undertaken at the University of
Auckland, New Zealand. Microprobe results were accepted
only if the compound weight percent total was between 98.5
and 101.5 %. The ferric iron content of each analysis was
calculated based on the assumption of a stoichiometric AB2O4
formula. EPMA and subsequent LA-ICP-MS analyses
targeted the same locations within the magnetite grains. This
provides the best possible calibration of LA-ICP-MS data.
Signals were calibrated using NIST 610 silicate glass (spot
size 50 μm) and USGS GSE-1G basaltic glass (spot sizes 10,
15, 25 μm). The reference materials were analyzed five times
at the beginning of the analytical session and monitored
throughout the session for potential drift. The Th/ThO+ratio
was optimized to be less than 0.2 %. Concentrations were
determined using off-line calculations following the protocol
of Longerich et al. (1996) using GeoPro (CETAC
Technologies) software (Nadoll and Koenig 2011). Table 1
shows the average LORs for LA-ICP-MS analyses. Thirty-
two elements were included in the analyses: Na, Mg, Al, Si, S,
Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Sr, Y, Nb,
Mo, Ag, In, Sn, Ba, Ce, Au, Tl, Pb, and Th. This list includes a
number of non-spinel elements, such as Si, Ca, and the REEs,
that can be helpful for data screening and the identification of
analyses that are affected by inclusions. Close to 400 single
LA-ICP-MS spot analyses were carried out and, after screen-
ing for contamination, a total of 339 analyses were used for
further data processing.
As shown in Table 1 different laser ablation spot sizes
translate to different LORs. Median values for groups of anal-
yses often include data collected from a range of spot sizes. If
the calculated median value for element (y) for a group of
analyses is below the LOR for the largest spot size (x) that
did not detect the respective element (y) then the median value
is set to y=<LOR(x). This also applies if more than 50 % of the
data for a group of analyses are below the LOR.
Geology
Porphyry and skarn deposits are key targets for mineral ex-
ploration due to their size and mineral endowment. Magmatic-
hydrothermal processes involved in their formation have been
the focus of many studies (e.g., Audetat et al. 2008; Einaudi
1981; Guilbert and Lowell 1974; Seedorff et al. 2005; Sillitoe
2010; Titley 1981; Titley and Beane 1981). Igneous and
hydrothermal magnetite are ubiquitous accessory minerals in
porphyry Cu–(Au)–(Mo) and associated skarn deposits
(Arancibia and Clark 1996; Beane and Titley 1981; Einaudi
1981; Gustafson and Hunt 1975; McQueen and Cross 1998;
Meinert et al. 2005; Sillitoe 2000, 2010; Titley and Beane
1981). The Late Cretaceous to early Tertiary (Laramide) arc in
Miner Deposita (2015) 50:493–515 497

Table 1 Average LA-ICP-MS reporting limits (LOR, ×10 standard which is North America’s largest producer of copper and
deviation of the blank) in parts per million
one of the largest porphyry open pit mines in the world; and
Spot size (5) the Safford district, with its four porphyry Cu deposits.
ESM 1 lists the samples that were selected for LA-ICP-MS
50 μm 25 μm 15 μm 10 μm analyses, information about the deposits, host rock compo-
Na 14 48 148 394
sition, magnetite type, types of alteration, and, if applicable,
the drill hole number. Detailed sample descriptions are
Mg 10 48 166 452
listed in ESM 2.
Al 60 219 561 1,240
Si 2,790 8,550 25,400 47,800
Chino (Santa Rita)
S 215 234 342 873
Ca 10,100 26,900 64,400 145,000
The Chino porphyry Cu deposit and the associated calcic and
Ti 15 75 160 330
magnesian Cu-Fe skarn are located 24 km east of Silver City
V 14 35 70 170
in the Pinos Altos Ranges, New Mexico. The deposit has been
Cr 36 120 920 2,460
described by Rose and Baltosser (1966) and Nielsen (1968).
Mn 2 10 29 70
Copper mineralization is associated with the Paleocene Santa
Co 2 8 20 50
Rita Granodiorite Porphyry (Fig. 1a, b), which is cut by
Ni 12 47 133 330
quartz–monzonite and latite dikes that preferably formed
Cu 3 11 30 70
along existing structural features that were important path-
Zn 14 60 190 370
ways for hydrothermal fluid flow (Turner and Bowman 1993).
Ga 1 6 15 32
These dikes intrude a variety of host rocks that include
Ge 4 15 56 130 Mesozoic quartz –d i o r i t e , C r e t a c e o u s l i m e s t o n e ,
As 10 34 106 320 Pennsylvanian clastic metasedimentary rocks (Syrena, Abo,
Se 108 224 1,720 505 and Oswaldo Formations), and Tertiary volcanic rocks
Sr 1 2 9 19 (Nielsen 1968; Rose and Baltosser 1966). Hypogene alter-
Y 1 2 7 17 ation at the Santa Rita stock is characterized by abundant
Nb 0.5 2 7 15 pyrite. Shaly limestones and calcerous shales of the Syrena
Mo 2 8 22 57 Formation have been largely metamorphosed to hornfels
Ag 2 8 23 50 (Rose and Baltosser 1966). Sericitic alteration with a typical
In 0.4 1 4 11 quartz, sericite, and pyrite assemblage is abundant and wide-
Sn 2 7 23 51 spread, and potassic alteration occurs locally (Fig. 2a).
Sb 2 6 19 46 Supergene processes formed a well-developed leached cap
Ba 1 3 8 18 and a high-grade supergene chalcocite enrichment zone.
Ce 0.5 2 6 19 Mississippian and Pennsylvanian limestones of the Lake
Au 1 5 107 63 Valley Limestone and Oswaldo Formation, and the
Tl 1 5 56 53 Fusselman and Montoya Dolostones have been extensively
Pb 2 5 19 35 altered to Fe–Cu skarn near the Santa Rita stock (Einaudi and
Th 1 3 9 22 Burt 1982; Nielsen 1970). These Paleozoic calcic and mag-
nesian (dolomitic) skarns have a chlorite–actinolite–epidote–
The LA-ICP-MS LORs vary depending on the employed analytical spot
garnet–diopside–magnetite alteration assemblage with abun-
size
dant pyrite veinlets.

the southwestern United States has been ascribed to subduction Magnetite

processes (Schmitt 1968; Titley 1981) and has one of the highest
concentrations of porphyry Cu and skarn deposits in the world
(e.g., Sillitoe 2010; Titley and Beane 1981; Titley 2001).
We focused our investigations on five porphyry Cu and
skarn deposits within the Laramide magmatic arc in the
southwestern United States (Fig. 1): (1) Chino (Santa
Rita) porphyry Cu and Cu skarn deposit, which was one
of the world’s first low-grade open pit copper mines; (2)
Hanover-Fierro, a porphyry Cu and Cu–Fe skarn north of
Chino; (3) Copper Flat, a Cu–Pb–Zn skarn; (4) Morenci,
We collected a total of 50 samples from Chino, and 12 were
selected for LA-ICP-MS analyses (ESM 1). Hydrothermal
magnetite in granodiorite, quartzite, and in both calcic and
magnesian skarns occurs in veins associated with pyrite and
chalcopyrite (Fig. 2a, b) or as massive replacement minerali-
zation. Micrometer- to millimeter-scale sulfide inclusions are
common in magnetite where sulfide minerals are part of the
mineral assemblage. Magnetite is also locally replaced by
pyrite and chalcopyrite, a secondary alteration event that
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Fig. 2 Photomicrographs illustrating the minerals associated with igne-
ous and hydrothermal magnetite from Cu–Mo–porphyry and skarn de-
posits in the southwestern USA. a Magnetite–sulfide vein in skarn from
Chino. The magnetite (mt) displays martitization (hematite—hm) along
spinel planes, rims, and fissures. Pyrite (py) and chalcopyrite (cpy) are
commonly associated with magnetite in veins and massive zones in skarn.
b Hydrothermal magnetite in skarn from Chino. Secondary quartz has
replaced the primary mineralogy. A small chlorite–biotite veinlet runs
from the upper left to lower right corner. The hydrothermal magnetite
occurs in and along the veins and shows comparatively smaller grains
than igneous magnetite. c Igneous magnetite hosted in the quartz-rich
Santa Rita (Chino) granodiorite, which shows potassic alteration with
reflects a shift in fO2/fS2 conditions and fluid composition. In
the supergene enrichment zone, secondary magnetite occurs
with actinolite, secondary Cu-sulfides, and abundant hematite.
Igneous magnetite generally occurs as disseminated subhedral
to euhedral grains or as irregular grains in contact with mafic
minerals in the granodioritic Santa Rita stock (Fig. 2c), the
hydrothermal granodiorite breccia, and later post-ore
monzonitic intrusions.
Miner Deposita (2015) 50:493–515
reaction rims of biotite. d Hanover-Fierro skarn sample with millimeter-
size calcite (ca) crystals and a large garnet (grt) porphyroblast. Hydro-
thermal magnetite is abundant and often associated with pyrite (py), but
also occurs as disseminated euhedral grains ≤500 μm. e Hydrothermal
magnetite in calcic skarn from Copper Flat associated with extensive fine-
grained recrystallized quartz (qz) and calcite (ca) veins with quartz rims.
Magnetite occurs as small grains and aggregates associated with minor
sulfides (mostly pyrite (py)). f Relict of a euhedral igneous magnetite
grain in gabbro. The mineral assemblage includes plagioclase (plag), a
fine grained mix of alteration products (K-feldspar, sericite—ser, chlo-
rite—chl, and plagioclase), and quartz. The magnetite in this sample
shows extensive corrosion that is preferential along spinel planes
Hanover-Fierro (Cobre mine)
The Hanover Granodiorite Porphyry Cu and Cu–Zn–Fe skarn
deposit is located approximately 4 km north of Chino near the
town Hanover (Fig. 1a, b). The Hanover Granodiorite
Porphyry intruded Paleozoic and Mesozoic sedimentary rocks
during the late Tertiary (55.9 ± 1.7 Ma) (McDowell 1971;
Turner and Bowman 1993). The granitic porphyry stock
Miner Deposita (2015) 50:493–515
mainly intrudes sedimentary rocks of the Lower Mississippian
Lake Valley and Cretaceous Beartooth and Colorado
(Mancos) Formations, the Pennsylvanian Syrena Formation,
and the Silurian Fusselman Dolostone and Permian Abo
Formation. Most of the Cu reserves are in the skarn mineral-
ization associated with the Syrena Formation and Lake Valley
Limestone at the southern lobe of the Hanover-Fierro pluton
(Turner and Bowman 1993). Chalcopyrite, Fe-rich sphalerite,
and magnetite are the dominant ore minerals (Turner and
Bowman 1993; U.S. Geological Survey 1997). Large
centimeter-size crystals of red and green garnet (Fig. 2d),
pyroxene, and sphalerite are widespread. Epidote and horn-
blende are also common in the skarn.
Magnetite
Three samples of magnetite were selected for LA-ICP-MS
analyses from 14 samples that were collected from Hanover-
Fierro. Hydrothermal magnetite in skarn occurs in veins and
as massive aggregates commonly associated with red and
green garnet. The granitic stock hosts disseminated sub-
euhedral igneous magnetite, whereas hydrothermal massive
and disseminated magnetite is abundant in hornfels.
Copper flat
Copper Flat (Graham County) is a barren Upper Cretaceous to
lower Tertiary stock and sill complex with an associated
adjacent Zn skarn about 3 km northwest of Chino (Fig. 1a).
Historic mining activities were focused on extracting Zn from
the altered limestone of the Pennsylvanian Oswaldo
Formation (Mullen and Storms 1948).
Magnetite
Magnetite is a widespread accessory mineral at Copper Flat
but is particularly abundant in the associated calcic Zn skarn.
Magnetite occurs with secondary carbonates in veinlets, as
widespread disseminated grains and as massive replacement
bodies (Fig. 2e). Laser ablation ICP-MS analysis was carried
out on one magnetite sample from the calcic skarn (ESM 1).
Morenci
Morenci is located about 35 km northeast of Safford, close to
the historic mining town of Clifton (Fig. 1c). The Precambrian
basement in the area comprises schist, quartzite, granite, and
granodiorite (Moolick and Durek 1966; Reber 1916). The
Morenci porphyry Cu deposit and the associated structurally
controlled Cu-Fe-Zn skarn formed at about 55 Ma
(McCandless and Ruiz 1993; Moolick and Durek 1966).
The main host rocks are Laramide quartz–granodiorite to
monzonite stocks that intruded Paleozoic and Cretaceous
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shales and limestones that have been altered to calc-silicate,
hornfels, and skarn. Cretaceous gabbro dikes are common
(Moolick and Durek 1966; Reber 1916). Low-grade chalco-
pyrite and pyrite±sphalerite hypogene stockwork veins are
pervasively altered to sericite (Enders et al. 2006). Multiple
leaching and enrichment events led to the formation of a Cu-
poor, limonitic leached cap that overlies an enrichment zone
of chalcocite and covellite with chrysocolla and malachite
(Enders et al. 2006). The Morenci porphyry Cu and skarn
deposit is divided into five orebodies: Morenci, Garfield, Sun
Ridge, Producer, and Shannon.
Magnetite
Six of 19 samples from the Morenci orebodies were selected
for LA-ICP-MS analyses (ESM 1). Magnetite is widespread
in all rocks but is particularly abundant in the associated Cu–
Fe–Zn skarn associated with the Shannon orebody. The
Cretaceous gabbro hosts disseminated igneous magnetite
(Fig. 2f) and hydrothermal magnetite in quartz±pyrite veins
in samples from the Morenci and Garfield orebody.
Disseminated igneous and hydrothermal magnetite is also
abundant in the Precambrian granite from the Sun Ridge
orebody. Igneous magnetite is mostly associated with horn-
blende and biotite, but it also occurs as isolated disseminated
grains. Magnetite and magnetite–pyrite veins with later
sericitic alteration selvages are common. At Producer, hydro-
thermal magnetite occurs in diorite in magnetite veins that are
crosscut by later magnetite–pyrite veins, and as millimeter- to
centimeter-scale massive magnetite aggregates.
Safford district
The Safford district consists of four porphyry Cu deposits
(Dos Pobres, Lone Star, San Juan, and Sanchez) and is located
approximately 13 km north of Safford (Fig. 1d). The four
porphyry Cu deposits formed during the Laramide orogeny
(Harris and Richard 1998). The main host rocks in all four
deposits are Cretaceous andesitic metavolcanic rocks that are
up to 1,700 m thick, and consist of massive flow breccias,
lahars, mudflows, and hypabyssal andesitic intrusions
(Langton and Williams 1982; Robinson and Cook 1966).
These were intruded by a variety of Laramide tonalite to
quartz-monzonite stocks and dikes that resulted in widespread
propylitic alteration (Cook and Robinson 1962; Gerwe et al.
2007; Robinson and Cook 1966). The 31- to 24-Ma-old Gila
volcanic rocks that consist of intermediate flow breccias, lithic
tuffs, pyroclastic units, and scoriaceous basalts (25 to 22 Ma)
preserve the oxides in the leach cap. The Lone Star stock is the
oldest (68 Ma) and least differentiated porphyrytic body; it is
chiefly a hornblende-biotite granodiorite. Potassium–argon
dates from Dos Pobres, Sanchez, and San Juan range from
58 to 55 Ma, and the intrusions range in composition from
500
quartz-monzonite to granodiorite (Cook and Robinson 1962;
Gerwe et al. 2007; Robinson and Cook 1966). Potassic and
sericitic alteration are the dominant alteration types. Early-
stage calcic-sodic alteration and chloritic alteration are wide-
spread and contain albite, chlorite, epidote, and magnetite.
Magnetite
Thirteen samples from Safford were selected for LA-ICP-MS
analysis (ESM 1). Igneous and hydrothermal magnetite is
abundant in andesitic and granodioritic host rocks. Vein types
at Safford include early simple magnetite veins and complex
quartz±calcite–magnetite–pyrite–chalcopyrite–epidote veins,
some of which contain biotite selvages. Early magnetite veins
occur in andesite with calcic–sodic alteration, whereas the
more complex magnetite veins occur in potassically altered
andesite. Oxidation and exsolution are common features in
magnetite from the Safford district. Ilmenite exsolution lamel-
lae, martitization, as well as complete alteration of magnetite
by oxidation and sulfidation to pyrite and chalcopyrite are
common (Fig. 3a, b). Magnetite with extensive martitization
was not analyzed for trace element composition.
Results
Summary statistics for magnetite from the individual deposits
and host rocks are listed in Table 2. A number of elements—
Na, Si, S, Ca, Cr, Cu, Ge, As, Se, Sr, Y, Mo, Ag, In, Sb, Ba,
Ce, Au, Tl, Pb, and Th—occur at concentrations less than their
respective LOR (Table 1). The LOR for elements such as Si,
Ca and Cr are relatively high (hundreds to thousands of parts
per million) even at larger analytical spot sizes. However, in
cases where elements such as Ca, P, REE, Si, Cu, and S are
present at concentrations above the LOR, they can be helpful
in identifying possible contamination by inclusions (Nadoll
and Koenig 2011; Nadoll 2013). Apatite, silicates, and
Fig. 3 Igneous magnetite (mt) in andesite from Safford displaying (a) extensive exsolution, martitization (hematite (hm) after magnetite), and (b)
sulfidation to pyrite (py) and chalcopyrite (cpy)
Miner Deposita (2015) 50:493–515
sulfides are the most common inclusions from the examined
porphyry and skarn deposits.
Normalization to Inner Zone Batholith magnetite
We normalized our magnetite data to the median concentra-
tion of 15 LA-ICP-MS analyses on magnetite from the
unmineralized magnetite-series granodiorite of the Inner
Zone Batholith in southwest Japan (Ishihara 1977; Spong
1998). Comparing the Inner Zone Batholith magnetite with
igneous and hydrothermal magnetite from the five porphyry
and skarn deposits provides insights into how magnetite from
an unmineralized intrusive body compares to magnetite from
porphyry and skarn deposits (Fig. 6).
Statistical analysis
To quantify the compositional variability of magnetite, we
calculated discrimination measures with a variable principal
normalization (IBM 1989, 2011). The discrimination mea-
sures value for each element (Mg, Al, Ti, V, Cr, Mn, Co, Ni,
Zn, and Ga) indicates its significance for the geochemistry of
magnetite, with larger values indicating a greater degree of
discrimination. A distinct separation is apparent where ele-
ments show high values for one dimension and low values for
the other. Elements that plot close to the origin do not dis-
criminate well in the first and second computed dimensions
that account for the majority of variance in the dataset
(Fig. 4a, b). The concentration of an element does not relate
to its significance if there is a narrow range in concentrations
for that particular element. For example, Al has comparatively
higher absolute concentrations than elements such as Zn but in
many instances shows no significant variation among magne-
tite from different deposits, and therefore scores a low dis-
crimination measure. The key elements that account predom-
inantly for compositional variations are Mg and Mn for hy-
drothermal magnetite from skarn, and Mg, Ti, V, Mn, Co, and
Miner Deposita (2015) 50:493–515
Zn for hydrothermal porphyry magnetite (Fig. 4a, c, d).
Titanium, Mn, Al, Zn, and V are the key elements for igneous
magnetite (Fig. 4b). The computed dimensions are ordered
according to their average discrimination measure (largest to
smallest). In the case of igneous and hydrothermal magnetite
the two first dimensions account for 94 and 85 % of compo-
sitional variance. Aluminum, Cr, Ni, and Ga are the least
significant elements for hydrothermal magnetite from the
porphyry deposits (Fig. 4c). Magnesium is particularly impor-
tant for the composition of hydrothermal magnetite from
magnesian skarn because it plots close to dimension axis 1
whereas most of the other spinel elements plot relatively close
together with equal proportional variance for both dimensions
(Fig. 4e). Calcic skarn shows a more pronounced spread of
Mg, Zn, Mn, and Co, which indicates that magnetite from
calcic skarn can be further discriminated based on varying
concentrations of these elements (Fig. 4f). Gallium, Ti, and V
are less significant for compositional variations in magnetite
from calcic skarn.
Comparison of igneous and hydrothermal (porphyry
and skarn) magnetite
Igneous magnetite has, on average, higher Al, Ti, V, and Ga
concentrations than hydrothermal porphyry and skarn magne-
tite (Fig. 5). Titanium concentrations higher than 3,560 ppm
can only be found in igneous magnetite (Fig. 6a). The highest
Ti concentrations, up to median concentrations of 0.6 wt%, are
present in igneous magnetite from gabbro and monzonite.
High Ti concentrations in magnetite from gabbro may reflect
the magma composition. Magnetite from mafic igneous rocks
such as gabbro commonly contains higher Ti concentrations
than their intermediate to felsic equivalents (Frost and
Lindsley 1991; Grigsby 1990). Titanium concentrations in
igneous magnetite from andesite vary greatly from values
<LOR to several weight percent, whereas igneous magnetite
from granite, granodiorite, and granodiorite breccia has sig-
nificantly lower Ti concentrations and largely overlaps with
hydrothermal porphyry magnetite (Table 2, Figs. 5 and 6a, b).
Igneous magnetite from porphyry Cu deposits has significant-
ly higher Ti concentrations than igneous magnetite from the
unmineralized Inner Zone Batholith (Fig. 6b). In contrast,
median V and Mn concentrations are lower in igneous mag-
netite from the porphyry deposits than in magnetite from the
Inner Zone Batholith. However, the highest median V and Mn
concentrations occur in igneous magnetite from gabbro at
Morenci.
Vanadium and Ga display a similar trend for the different
types of magnetite. The lowest median concentrations are in
hydrothermal skarn magnetite whereas the highest median
concentrations are in igneous magnetite from the porphyry
deposits and the Inner Zone Batholith. The range of Co
concentrations is virtually identical in hydrothermal and
501
igneous magnetite from the porphyry deposits, whereas hy-
drothermal magnetite from calcic skarn and igneous magnetite
from the Inner Zone Batholith have slightly higher median
concentrations. Cobalt seems to be significantly depleted in
magnetite from magnesian skarn, with median concentrations
that are an order of magnitude lower than in any of the other
settings (Fig. 5). Median concentrations for a number of
elements (i.e., V, Mn, Co, and Ga) are higher in igneous
magnetite from the barren Inner Zone Batholith granodiorite
than in any of the magnetites from the porphyry and skarn
deposits. Titanium concentrations on the other hand are
among the lowest in magnetite from the Inner Zone Batholith.
Major and trace element variations within individual deposits
Multi-element “spidergrams” and scatterplots are used to il-
lustrate the chemical fingerprints of different magnetite popu-
lations that are described in detail in the following section.
Elemental concentrations stated in this section are median
values (Table 2).
Chino
Depending on the type of hydrothermal magnetite (porphyry
vs. skarn) and the host rock composition of igneous magnetite,
there are a number of compositional patterns that can be used
to fingerprint magnetite from Chino. Igneous magnetite from
a monzonite dike has one of the most distinctive chemical
signatures (Fig. 7a). It has the highest Al and Zn contents
(6,550 and 1,880 ppm, respectively) and high Ti concentration
(21,400 ppm); (Table 2). The highest V concentrations are in
igneous magnetite from the granodiorite breccias
(2,470 ppm). Igneous magnetite from granodiorite has signif-
icantly less Mn, Co, Ni, Zn, and Ga than other igneous
magnetite from Chino and shows only subtle chemical varia-
tions in comparison with hydrothermal magnetite hosted by
the granodiorite stock (Fig. 7a). Gallium and Zn are higher,
and Mg concentrations lower in hydrothermal magnetite com-
pared to the igneous occurrences. Concentrations of Al, Ti, V,
and Mn overlap (Table 2). In vein-hosted hydrothermal mag-
netite from quartzite, only V and Mn concentrations exceed
the LOR and V concentrations are several 100 ppm lower than
in any other hydrothermal porphyry and igneous magnetite.
In calcic and magnesian skarn samples, hydrothermal mag-
netite has distinct compositional variations compared to igne-
ous and hydrothermal porphyry magnetite (Fig. 7b). Titanium
and V are generally at a low level or below the LOR in
magnetite from calcic and magnesian skarn. In magnesian
skarns magnetite has high Mg and Mn concentrations.
Variations in Mg concentrations may reflect different alter-
ation zones (Table 3). Magnetite from the chalcocite enrich-
ment zone has a median Mg content of 5,610 ppm whereas
magnetite from outside that zone has significantly higher
Table 2 Minimum, maximum, and median trace element concentrations (LA-ICP-MS data) in magnetite from the examined porphyry Cu (Mo) and skarn deposits in parts per million
502

Min Min Max Max MedMed Min

Min Max
Max Med
Med Min
Min Max
Max Med
Med Min
Min Max
Max Med
Med Min
Min Max
Max Med
Med Min
Min Max
Max MedMed

Deposit type host rock IZB (barren) igneous Chino hydrothermal Chino hydrothermal Chino hydrothermal Chino hydrothermal Chino hydrothermal calcic
granodiorite granodiorite magnesian skarn magnesian skarna quartzite skarn
N 15 7 9 8 6 34
Mg 362 <166 1,170 <166 21,900 26,700 24,100 5,140 7,450 5,610 <166 520 <166 <48 3,060 551
Al 110 1,190 2,400 1,840 1,100 2,240 1,810 <561 <561 <561 <561 <561 <561 <561 10,000 2,030
Ti 174 1,230 2,320 1,630 <15 86 <15 <160 <160 <160 <160 <160 <160 <75 1,680 139
V 2,450 982 2,920 1,660 <14 40 15 <70 281 <70 454 747 663 <35 2,510 <170
Cr <120 <36 <36 <36 <36 <36 <36 <920 <920 <920 <920 <920 <920 <120 <120 <120
Mn 2,080 387 672 553 1,390 1,610 1,510 972 1,370 1,230 355 684 509 351 2,600 944
Co 82 17 54 <20 <2 4 <2 <20 <20 <20 <20 <20 <20 <8 94 <20
Ni 60 66 153 <133 <12 <12 <12 <133 <133 <133 <133 163 <133 <47 61 <47
Zn 384 88 530 <190 175 311 220 <190 <190 <190 <190 <190 <190 <60 972 <190
Ga 16 57 138 74 26 30 28 <15 43 <15 <15 17 <15 <6 134 32
Deposit type host Rock Cobre hydrothermal Cobre hydrothermal calcic Copper Flat hydrothermal Morencihydrothermal Producer hydrothermal Shannon hydrothermal
hornfels skarn calcic skarn gabbro diorite calcic skarn
N 8 14 5 8 8 7
Mg <48 231 <48 <166 952 <166 <452 2,410 1,030 168 3,010 2,470 <166 1,200 <166 4,550 16,700 6,350
Al 384 886 549 <561 2,430 988 <929 2,950 1,100 776 3,650 2,480 <1,240 4, 480 1,770 <1,240 3,850 <1,240
Ti 188 1,840 944 <75 999 <75 <160 512 209 343 1,180 1,030 686 36,600 1,040 <330 601 <330
V 291 727 310 <35 150 <35 <170 289 171 1,700 3,140 2,180 1,830 3,880 2,690 <170 230 183
Cr <120 494 <120 <120 <120 <120 <120 <120 <120 <120 <120 <120 <920 <920 <920 <2,460 <2,460 <2,460
Mn 616 1,060 825 824 2,590 1,800 584 1,660 1,120 270 381 303 116 2,150 202 5,210 7,290 6,340
Co <8 17 <8 <20 104 61 <50 153 78 62 62 62 <50 103 72 <50 <50 <50
Ni <47 50 <47 <47 <47 <47 <47 <47 <47 138 389 264 <133 <133 <133 <330 399 <330
Zn <60 61 <60 <190 338 <190 <370 6,980 1,130 <190 <190 <190 <370 841 605 <370 1,280 451
Ga 13 38 31 <15 40 20 17 73 23 24 55 39 <32 43 <32 <32 104 <32
Deposit type host rock Sun Ridge hydrothermal Dos Pobres hydrothermal Dos Pobres hydrothermal Lone Star hydrothermal San Juan hydrothermal Chinoigneous granodiorite
granite andesite granodiorite andesite andesite
N 15 17 7 22 18 16
Mg <166 677 <166 <166 783 <166 <48 152 <48 <48 463 75 139 1,040 279 104 527 155
Al <561 3,270 <561 <561 4,590 <561 506 1,140 635 <561 4,890 1,160 701 5,760 3,000 <1,240 2,650 1,720
Ti <160 <160 <160 <160 804 <160 228 1,120 610 <160 1,980 455 603 12,600 1,720 <330 12,600 1,350
V <70 680 <70 1,690 2,510 1,870 2,070 2,470 2,150 443 1,840 996 223 1,710 274 437 3,780 1,190
Cr <920 <920 <920 <920 1,660 <920 <36 <36 <36 <120 <120 <120 <36 <36 <36 <120 423 <120
Mn 142 838 399 234 694 370 299 559 390 77 221 182 201 2,630 1,210 267 645 444
Miner Deposita (2015) 50:493–515
Table 2 (continued)

Min Min Max Max MedMed Min

Min Max
Max Med
Med Min
Min Max
Max Med
Med Min
Min Max
Max Med
Med Min
Min Max
Max Med
Med Min
Min Max
Max Med
Med

Co <20 58 <20 21 75 48 27 51 35 <8 36 <8 18 50 42 <20 50 <20

Ni <133 229 <133 <133 <133 <133 <47 49 <47 <47 309 <47 16 48 <47 <47 69 <47
Zn <190 390 <190 <190 260 <190 68 318 110 <60 230 <60 84 536 224 <190 652 <190
Ga 46 151 74 <15 60 16 <15 33 23 <15 61 32 25 71 55 <32 98 39
Deposit type host rock Chino igneous granodiorite breccia Chino igneous monzonite Cobre igneous granite Garfield igneous gabbro Morenci igneous gabbro Sun Ridge igneous granite
N 8 8 8 4 4 4
Miner Deposita (2015) 50:493–515

Mg <166 282 <166 <353 3,940 993 <103 225 143 372 1,130 429 302 665 559 <166 517 <166
Al <561 2,820 1,000 4,210 9,720 6,550 913 2,240 1,260 904 2,740 994 840 1,610 1,160 <561 2,070 <561
Ti 315 6,860 1,020 13,400 24,400 21,400 970 2,990 1,830 340 61,500 31,200 48,900 67,100 57,700 197 228 206
V 2,260 3,160 2,470 1,340 2,160 1,670 1,940 3,880 2,070 2,040 3,260 2,730 2,290 6,660 3,610 <70 <70 <70
Cr <120 527 <120 <920 594 <920 <120 194 <120 <120 <120 <120 <120 <120 <120 <920 <920 <920
Mn 426 3,260 1,320 1,670 5,370 2,070 190 684 336 214 7,290 2,610 5,860 7,090 6,750 745 1,450 962
Co <20 128 38 <20 62 38 8 59 17 26 64 48 50 84 58 52 70 60
Ni <133 160 <133 <47 <47 <47 <47 51 <47 231 448 324 378 378 <133 <133 <133 <133
Zn <190 1,850 499 1,370 2,430 1,880 <133 653 199 <190 762 650 93 538 315 <190 <190 <190
Ga 15 59 50 59 84 69 <15 71 45 <15 25 <15 20 35 28 64 100 79
Deposit type host rock Dos Pobres igneous granodiorite Lone Star igneous andesite San Juan igneous granodiorite
N 7 22 16
Mg <166 226 183 <166 2,160 616 <166 1,160 449
Al <561 567 <561 <561 9,520 2,070 2,580 4,490 3,300
Ti <160 327 210 <330 36,700 1,590 697 4,290 1,140
V 1,830 2,340 2,210 367 3,950 1,770 1,160 1,850 1,640
Cr <920 1,420 <920 <920 3,290 <920 <36 300 <120
Mn 219 1,490 371 115 5,590 210 241 730 433
Co 36 81 53 13 131 <20 5 55 <8
Ni <133 163 <133 <12 <12 <12 <47 157 62
Zn 67 815 <190 <190 693 <190 48 116 74
Ga <15 68 20 <15 56 38 33 108 87

The corresponding graph for this table is shown in Fig. 7. The Inner Zone Batholith magnetite is used to compare the igneous and hydrothermal magnetite from the different deposits with magnetite from an
un-mineralized granitoid (see text for discussion). Although Cr is a common spinel element, median Cr concentrations for all samples lie below the LOR and it is therefore not included in this table
N Number of analyses the median value is based on
a
Indicates chalcocite enrichment zone
503
504
Fig. 4 Discrimination diagrams for Mg, Al, Ti, V, Cr, Mn, Co, Ni, Zn,
and Ga for (a) hydrothermal magnetite (porphyry+skarn), b igneous
magnetite, c hydrothermal porphyry magnetite, d hydrothermal magnetite
median Mg concentrations of 2.4 wt%. Aluminum, Ga, Zn,
and Sn concentrations in magnetite from the chalcocite en-
richment zone are below LOR, whereas magnetite from out-
side that zone contains comparatively high concentrations of
Al (1,810 ppm), Ga (28 ppm), Zn (220 ppm), and Sn (85 ppm)
(Table 3, Fig. 7b). This is the only hydrothermal magnetite in
our dataset with Sn concentrations that exceed the LOR. The
lower element concentrations in magnetite from the chalcocite
enrichment zone are likely to reflect depletion due to second-
ary processes that formed the sulfidic enrichment zone.
A comparison of different hydrothermal magnetite compo-
sitions from Chino is shown in Fig. 8. Early magnetite veins in
Miner Deposita (2015) 50:493–515
(magnesian+calcic skarn), e hydrothermal magnetite from magnesian
skarn and f magnetite from calcic skarn
quartzite have lower Ti and V concentrations (less than 100
and 1,000 ppm, respectively). Hydrothermal magnetite from
calcic and magnesian skarns have an order of magnitude
higher Mg concentrations, whereas Ti concentrations are sig-
nificantly lower (by several 100 ppm) in magnetite from
magnesian skarn.
Hanover-Fierro and Copper Flat
Compositional variations in hydrothermal igneous magnetite
from Hanover-Fierro are displayed in Fig. 7c. Titanium
(1,830 ppm), V (2,070 ppm), and Ga (45 ppm) concentrations
Miner Deposita (2015) 50:493–515
Fig. 5 Box and whisker plots for igneous, hydrothermal (porphyry, calcic and magnesian skarn), Inner Zone Batholith magnetite
are significantly higher in igneous magnetite from granite than
in hydrothermal magnetite from skarn (<75, <35, 20 ppm,
respectively) and hornfels (944, 310, 31 ppm, respectively).
By contrast, median Mn concentrations are higher in hydro-
thermal magnetite (825 ppm in hornfels and 1,800 ppm in
skarn) than in igneous magnetite (336 ppm in granite).
Compared to igneous magnetite from the unmineralized
Inner Zone Batholith, Hanover-Fierro igneous magnetite has
lower concentrations of Mg, Mn, Co, Ni, and Zn. Vanadium
Fig. 6 Ti-V plot for igneous and hydrothermal magnetite from all exam-
ined deposits. In spite of an overlap between igneous and hydrothermal
magnetite, Ti concentrations above approximately 5,000 ppm indicate
igneous magnetite, whereas low Ti-V concentrations indicate hydrother-
mal magnetite. b Ti–V plot for igneous magnetite from different host
505
concentrations are similar, and Ti and Ga concentrations are
higher than in magnetite from the Inner Zone Batholith.
The different hydrothermal magnetite occurrences from
Hanover-Fierro and Copper Flat can be discriminated by their
trace element signatures shown in Fig. 7c. In particular, Mg,
Ti, Co, and Zn concentrations vary significantly between
hydrothermal magnetite from these deposits. Hydrothermal
magnetite from Copper Flat is enriched in Mg and Zn com-
pared to the Inner Zone Batholith magnetite. The observed
rocks. The Ti/V ratios of igneous magnetite hosted in gabbro, monzonite,
and granite are the most distinct from each other. The dashed square
indicates the Ti/V concentrations of igneous magnetite from the Inner
Zone Batholith in Japan (Spong 1998)
506 Miner Deposita (2015) 50:493–515

Fig. 7 Concentrations (left) and normalized (right) multi-element median LA-ICP-MS values for selected elements. All values are normal-
“spidergrams” for hydrothermal (orange shades) and igneous (blue ized to Inner Zone Batholith magnetite (Table 2; Ishihara 1977; Spong
shades) magnetite from (a) Chino (porphyry), b Chino (skarn), c 1998; Nadoll et al. 2012)
Hanover-Fierro-Copper Flat, d Morenci, and e Safford. Plotted are
Miner Deposita (2015) 50:493–515 507

Table 3 Compositional variations among magnetite hosted in magnesian and calcic skarn from Chino

Deposit Magnetite Skarn type N Mg Al Ti V Cr Mn Co Ni Zn Ga

type

Chino Hydrothermal Calcic 34 78 1,470 139 <LOR <LOR 944 <LOR <LOR <LOR 10
Hydrothermal Magnesian (chalcocite enrichment zone) 8 5,610 <LOR <LOR <LOR <LOR 1,230 <LOR <LOR <LOR <LOR
Hydrothermal Magnesian (outside enrichment zone) 9 24,100 1,810 <LOR 15 <LOR 1,510 <LOR <LOR 220 28

Shown are the median minor and trace element concentrations in parts per million
N Number of analyses the median values are based on

minor and trace element concentrations in hydrothermal mag-
netite from Hanover-Fierro are generally below the levels
recorded in the Inner Zone Batholith magnetite (Fig. 7c).
Morenci (Morenci, Garfield, Sun Ridge, Producer, Shannon)
The different orebodies at Morenci show distinct chemical
signatures in hydrothermal and igneous magnetite (Table 2;
Fig. 7d). In particular, igneous titaniferous magnetite hosted in
gabbro has comparatively high Ti (57,700 and 31,200 ppm,
respectively), V (3,610 and 2,730 ppm, respectively), and Mn
(6,750 and 2,610 ppm, respectively). Nickel concentrations in
igneous magnetite in gabbro from Garfield are also character-
istically high (324 ppm). The Ti concentrations recorded in
magnetite from gabbro exceed those found in igneous mag-
netite from the Inner Zone Batholith two orders of magnitude.
Concentrations of other elements lie at or below the levels
detected in igneous magnetite from the Inner Zone Batholith.
Hydrothermal magnetite in calcic skarn from Morenci has the
highest Mg and Mn concentrations of 6,350 and 6,340 ppm,
respectively. Aluminum, Ti, and Ga are less than the respec-
tive LOR and V concentrations are very low (183 ppm).
Concentrations of the suite of magnetite elements in igneous
and hydrothermal magnetite in granite from Sun Ridge are
comparatively low, commonly less than the respective median
concentrations in Inner Zone Batholith magnetites (Fig. 7d).
However, characteristic compositional variations include
higher Al, T, Mn, and Co contents in igneous magnetite
compared to the hydrothermal occurrences in early magnetite
veins and quartz–chalcopyrite–sericite–pyrite–magnetite
veins from the same host rock.
Safford district
Compositional variations in magnetite from the Safford dis-
trict are mostly less pronounced than those from other de-
posits. However, magnetite from the Dos Pobres, Lone Star,
and San Juan deposits still displays distinct trace element
signatures (Fig. 7e).
At Dos Probres, hydrothermal magnetite from magnetite–
quartz–chalcopyrite–epidote veins in andesite and granodio-
rite can be discriminated based on Al, Ti, and Zn concentra-
tions that are up to an order of magnitude lower in andesite-
hosted hydrothermal magnetite than in the corresponding

Fig. 8 a Ti–V plot and b Mg–Mn plot of LA-ICP-MS data for vein concentrations below 70 ppm and Mn concentrations between 500 and
magnetite and massive hydrothermal occurrences from Chino. Massive 1,500 ppm. Magnetite hosted in the Oswaldo calcic skarn has the lowest
hydrothermal magnetite from calcic skarn forms a cluster at Mg V concentrations compared to the other hydrothermal magnetites
508
hydrothermal magnetite from granodioritic host rocks
(Table 2, Fig. 7e).
Compositional variations between hydrothermal and igne-
ous magnetite from Lone Star are less pronounced than in
other deposits. However, Mg, Ti, and V concentrations are
higher in igneous magnetite (616, 1,590, 1,770 ppm, respec-
tively) than in hydrothermal magnetite (75, 455, 996 ppm,
respectively) (Table 2, Fig. 7e). LA-ICP-MS data for Lone
Star allow the direct comparison of hydrothermal magnetite
from different vein-types hosted in andesite (Fig. 9). Titanium
concentrations vary characteristically between early magnetite
veins that have Ti concentrations of around 1,000–2,000 ppm
whereas magnetite from magnetite–pyrite and magnetite–
quartz–chalcopyrite veins has lower Ti concentrations (300–
800 ppm). Early magnetite veins have V concentrations of
880 ppm, magnetite–pyrite veins have V concentrations of
495 ppm, and magnetite from magnetite–quartz–chalcopyrite
veins has the highest V content with median concentrations of
1,590 ppm (Fig. 9).
Magnetite from early magnetite veins in the San Juan
deposit has higher V concentrations compared to magnetite
from later quartz–chalcopyrite–pyrite–magnetite veins.
Magnetite from the later stage, more complex veins contains
more Ti, Mn, and Zn (2,570, 1,700, and 330 ppm; Figs. 7e and
9).
Discussion
Apart from the pioneering work of Borisenko and Lapin (1971,
1972) and Shcheka et al. (1988), few studies have examined
Fig. 9 Ti/V plot for vein magnetite in different host rocks at Safford.
Hydrothermal magnetite at Lone Star and San Juan shows differences in
Ti and V contents. The V and Ti concentrations in magnetite from similar
vein types but hosted in compositionally variable host rocks at the Dos
Pobres deposit are nearly identical
Miner Deposita (2015) 50:493–515
hydrothermal magnetite using statistical data exploration (i.e.,
principal component analysis, factor analysis, discrimination
measures) to discriminate sample groups (Nadoll et al. 2012).
Statistical data exploration tools such as discrimination mea-
sures allow assessing large data sets and help to determine
which elements are important for compositional variations in
magnetite of hydrothermal and igneous origin.
Our data show that a number of elements, including Na, Si,
S, Ca, Cr, Cu, Ge, As, Se, Sr, Y, Mo, Ag, In, Sb, Ba, Ce, Au,
Tl, Pb, and Th, are not commonly incorporated in magnetite at
concentrations greater than their respective LOR. Measured
and calculated phenocryst-matrix partition coefficients for
these elements in Fe-oxides indicate that they are highly
incompatible and therefore highly unlikely to be incorporated
into magnetite (Klemme et al. 2006; Nielsen et al. 1994).
Molybdenum and W can partition into Fe-oxide phases such
as magnetite, and published partition coefficients for Mo
(D∼20) are comparable to those for other transition metals
such as Co and Mn (Candela 1997; Mahood and Hildreth
1983). However, Mo was not detected in any magnetites from
our study area.
Our findings illustrate that Mg, Al, Ti, V, Co, Mn, Ni, Zn,
and Ga are the most variable elements for the minor and trace
element geochemistry of magnetite from porphyry Cu and
skarn deposits, and this broadly agrees with findings by other
workers (Dupuis and Beaudoin 2011; Rusk et al. 2009).
Chromium is another important element that is commonly
incorporated into magnetite, especially in magnetite from
ultramafic and mafic host rocks (Dare et al. 2012; Dupuis
and Beaudoin 2011; Frost and Lindsley 1991). Chromium
concentrations in our samples do not exceed the LOR for the
vast majority of samples. However, the LOR for Cr can be as
high as 2,460 ppm for the smallest analytical spot size of 10 μm
(Table 1) and therefore it is likely that low concentrations could
not be detected. Gallium concentrations in magnetite are typi-
cally low (<1–10 ppm range), which reflects its relatively low
partition coefficient (Ewart and Griffin 1994; Green 1994), but
nonetheless, Ga concentrations are commonly higher in
igneous magnetite than in hydrothermal occurrences.
Discrimination diagrams for magnetite
Dupuis and Beaudoin (2011) proposed that Ca, Al, Ti, V, Cr,
Mn, Cu, and Zn concentrations in magnetite may discriminate
various mineral deposit types. For example, they suggest that
a Ni+Cr vs. Si+Mg diagram can separate Ni–Cu–PGE and Cr
deposits, and that Ni/(Cr+Mn) vs. Ti+V or Ca+Al+Mn vs.
Ti+V diagrams can indicate IOCG, Kiruna, porphyry Cu,
banded iron formation, skarn, Fe-Ti, and V deposits.
Kamvong et al. (2007) presented preliminary data which
suggest that Sn/Ga vs. Al/Co diagrams can be used to dis-
criminate among different magmatic-hydrothermal ore depos-
it styles.
Miner Deposita (2015) 50:493–515
Our research supports the observation that element ratios
are useful for discriminating magnetite from different geologic
settings. For example, Ti+V versus Al+Mn broadly distin-
guish skarn versus porphyry deposits, with low Ti+Vand high
Al + Mn concentrations indicative of skarn magnetite
(Fig. 10), whereas high Ti + V and low Al + Mn reflect
porphyry deposits. However, a large area of overlap exists.
Although this is largely consistent with trends observed by
Dupuis and Beaudoin (2011) on their Ca+Al+Mn vs. Ti+V
diagram, the boundaries that discriminate skarn magnetite
from porphyry magnetite are slightly different from their
groupings. This suggests that boundaries are likely transitional
rather than sharp. The lack of Ca in our data may contribute to
small discrepancies. However, Ca concentrations are usually
orders of magnitude lower than Al and Mn concentrations and
can often be attributed to mineral inclusions in magnetite
(Nadoll et al. 2014), especially with LA-ICP-MS analyses.
EPMA is less affected by mineral inclusions (Dupuis and
Beaudoin 2011).
A number of authors have used multi-element
“spidergrams” to document compositional variations in mag-
netite of hydrothermal and igneous origin (e.g., Dare et al.
2012; Huang et al. 2013; Nadoll et al. 2012). However, there
are currently no standards as to how to plot these diagrams.
Dare et al. (2012) suggest plotting elements in order of their
compatibility, and divide lithophile from chalcophile
elements. Huang et al. (2013) follow their recommendation.
For magnetite formed under igneous conditions, where com-
patibility and partitioning behavior are relatively well
Fig. 10 Ti+V/Al+Mn diagram for hydrothermal magnetite from the
examined deposits. Dupuis and Beaudoin (2011) used a similar diagram
to discriminate Kiruna, iron oxide–copper–gold, porphyry Cu, skarn,
Fe–Ti–V, and banded iron formation deposits
509
constrained, this is a reasonable approach. However,
magnetite-melt partition coefficients range over orders of
magnitude and overlap significantly (EarthRef.org 2009).
We plot elements in order of increasing atomic numbers
because data for magnetite–fluid partition coefficients are
not available.
Mineral inclusions in magnetite
Magnetite commonly contains mineral inclusions, and these
can be readily sampled during geochemical analyses, so it is
important to distinguish elements that occur in solid solution
in magnetite, and those that can be attributed to mineral
inclusions, such as silicates and sulfides. Inclusions in min-
erals are common and widespread (Tracy 1982), and
LaTourrette et al. (1991) suggested that the geochemistry of
host minerals may inadvertently reflect the presence of inclu-
sions. Therefore, it is important to distinguish among elements
that are in solid solution, versus elements that are hosted by
micro- and nano-scale inclusions in magnetite (Nadoll and
Koenig 2011). For example, Hendry et al. (1982) reported up
to 1.5 wt% Cu in hydrothermal magnetite associated with
porphyry Cu deposits, but Ilton and Eugster (1989) suggested
that these exceptionally enriched Cu contents likely reflect
contamination or Cu-rich microscopic to submicroscopic in-
clusions. High concentrations (<1,000 ppm) of P and REE in
hydrothermal magnetite from Cu–Au skarn deposits have
been reported by Ray and Webster (2007). Other workers
have described magnetite as a significant host for Ba and Sr
(Kamvong et al. 2007), and as a minor host for Zr and REEs
(Ionov and Harmer 2002; Reguir et al. 2008). Silicon has also
been reported in magnetite (Newberry et al. 1982). Dupuis
and Beaudoin (2011) report Si in magnetite measured by
EPMA. However, Si can also often be attributed to silicate
inclusions, especially with LA-ICP-MS measurements
(Nadoll et al. 2014). Time-resolved signals from our LA-
ICP-MS analyses suggest that elements such as Cu, P, Ba,
Sr, REE, and Si in hydrothermal magnetite associated with
porphyry Cu and skarn deposits most likely reflect micro- or
nano-scale inclusions such as sulfides, apatite, carbonates, or
silicates (Fig. 11). Magnetite free of inclusions yields signals
that are stable, with no indication of significant heterogeneity
(Fig. 11a), whereas suspected sulfide inclusions yield syn-
chronous sporadic increases in Cu, Co, Sn, and S (Fig. 11b).
The occurrence of such inclusions, if overlooked, can lead to
misinterpretations of magnetite minor and trace element data.
Analytical techniques, such as LA-ICP-MS, that analyze larg-
er volumes of sample material are more prone to be affected
by mineral inclusions than analytical techniques with a small
spot size such as EPMA (Dupuis and Beaudoin 2011; Nadoll
and Koenig 2011; Nadoll et al. 2014).
Despite the adverse effect of inclusions, their occurrence,
abundance, and composition can provide useful petrogenetic
510
Fig. 11 Time resolved signals for LA-ICP-MS analyses of two samples,
showing signal intensity in counts per second (CPS) over time, with the
depth of penetration of the mineral increasing with time. After 30 s, the
laser starts to ablate the magnetite and minor and trace element data are
continuously collected for 60 s. a Stable signal and no indication for
significant heterogeneity, zoning or concentrations of elements that can be
attributed to inclusions. b A sulfide inclusion is indicated by the occur-
rence and synchronous increases of Cu, Co, and S concentrations. The
information (Audetat and Pettke 2006; Tracy 1982), and can
be an additional asset in discriminating magnetite from differ-
ent geologic settings. For example, the occurrence of chalco-
pyrite inclusions in magnetite can indicate Cu deposits. Our
petrographic observations and screening of the LA-ICP-MS
data show that sulfide inclusions are common features in
hydrothermal magnetite from porphyry and skarn deposits.
Igneous processes
The geochemistry of igneous magnetite has been studied
thoroughly and compositional variations in magnetite from
plutonic and volcanic rocks are well documented (e.g.,
Buddington and Lindsley 1964; Dare et al. 2012; Frost and
Lindsley 1991; Ghiorso and Sack 1991b; Ryabchikov and
Kogarko 2006). Compositional variations occur in response
to specific T–fO2–fS2 conditions, melt composition, and
cooling trends. Sub-solidus re-equilibration during cooling
of plutonic igneous rocks leads to major compositional differ-
ences between Fe-Ti oxides in plutonic rocks compared to
those in volcanic rocks (Frost and Lindsley 1991; Wones
1989). Magnetite from mafic igneous rocks often have higher
Ti concentrations and are more likely to display ilmenite
exsolution than Ti-poor magnetite crystallizing from felsic to
intermediate magmas (Dare et al. 2012; Grigsby 1990;
Lindsley 1991).
Our data show that Ti and V concentrations in igneous
magnetite from granodiorite, granite, gabbro, and andesite
vary significantly. These rock types represent a wide range
of whole rock compositions and cooling histories, so the
compositional variation in magnetite strongly suggests that
these magmatic factors and processes control Ti and V
concentrations in igneous magnetite.
Miner Deposita (2015) 50:493–515
position of the onset of the steep Cu increase in the signal coincides with a
depth of several microns below the polished surface, and explains how
such inclusions are not observed during petrographic examination. The
patterns of elements such as Sn are difficult to interpret because it could
be incorporated in the magnetite or the sulfide inclusion. However, it is
more likely that Sn is associated with the sulfide inclusion because Sn is
very rarely occurring at detectable concentrations in magnetite and Sn-
zonation has not been observed in any of the magnetites
Hydrothermal processes
The partitioning behavior of elements between fluid and mag-
netite under hydrothermal conditions are yet to be experimen-
tally constrained. However, considering the available petro-
genetic information and the composition of hydrothermal
magnetites from the investigated porphyry and skarn deposits,
one can discuss the degree of control that governing factors
such as temperature, fluid composition, fO2, and fS2 are likely
to exert on the composition of hydrothermal magnetite.
Similar to magma composition, the composition of hy-
drothermal fluids can be inferred to be a major controlling
factor for the composition of hydrothermal magnetite.
Indeed, McQueen and Cross (1998) present data that sug-
gest that the fluid composition is reflected in the composi-
tion of the corresponding hydrothermal magnetite.
Quantitative data for spinel element concentrations in hy-
drothermal fluids related to porphyry and skarn deposits
have become increasingly available in recent years (e.g.,
Audetat et al. 2008; Baker et al. 2004; Meinert et al. 2005;
Rusk et al. 2009). Our data show that in magnetite from
skarns, Mg and Mn are commonly present at higher
concentrations than in hydrothermal and igneous magnetite
from the porphyry deposits. High concentrations of Mg, Mn,
and Zn in hydrothermal magnetite from skarn compared to
associated igneous magnetite have also been reported by
McQueen and Cross (1998), and this presumably reflects the
relatively enriched concentrations of these elements in the
hydrothermal fluids associated with the formation of these
skarn deposits (Baker et al. 2004). Enriched Mg concentra-
tions in magnetite hosted in magnesian skarn may also reflect
host rock buffering of the hydrothermal fluid composition.
The enrichment of Mn in magnetite from skarn might simi-
larly reflect extensive fluid/host rock interaction (Einaudi et al.
Miner Deposita (2015) 50:493–515
1981; Meinert 1987). Variations in Al, Ti, and Zn concentra-
tions between hydrothermal magnetite from magnetite–
quartz–chalcopyrite–epidote veins in andesite and granodio-
rite at Dos Pobres may present a similar reflection of litholog-
ical control (Table 2, Fig. 7e). Assuming that initial fluid
compositions were comparable, this suggests that fluid–host
rock interaction had a strong control on the precipitating
magnetite composition.
A number of authors report that Cr, Cu, As, Mo, Ag, Au,
Pb, and a range of other elements including the REEs are
present in hydrothermal magnetite (Carew et al. 2006; Lee
et al. 2005; Lindsley 1991; Simon et al. 2008; Singoyi et al.
2006) and excluding Cr, also commonly occur in hydrother-
mal fluids related to porphyry and skarn deposits (Heinrich
2005; Rusk et al. 2004). However, these elements are all
below their LOR in our samples (Table 2). The LOR for Cu,
As, Mo, Ag, Au and Pb is generally well below 100 ppm for
spot sizes of 15 μm and larger. Only Cr has a LOR of up to
2,460 ppm for the smallest analytical spot size of 10 μm. It is
likely that low Cr concentrations could not be detected due to
the relatively high LOR.
The temperature of vein formation in porphyry deposits
ranges between 300 and 800 °C (Beane and Titley 1981;
Muntean and Einaudi 2001; Rusk et al. 2008; Seedorff et al.
2005; Sillitoe 2010). Many skarn deposits are formed by low
salinity fluids associated with late-stage retrograde alteration
at temperatures below those attributed to porphyry deposits,
i.e., 300–500 °C (Ahmad and Rose 1980; Audetat and Pettke
2006; Beane and Titley 1981; Einaudi et al. 1981; Manske and
Paul 2002; Meinert et al. 2005; Sillitoe 2010). Elements such
as Al and Ti are relatively immobile and their incorporation in
magnetite is largely temperature controlled (Nielsen et al.
1994; Toplis and Carroll 1995), with higher concentrations
expected under high-temperature igneous conditions. The
higher concentrations of Al and Ti in igneous magnetite
compared to hydrothermal magnetite from our study supports
this conclusion. Hydrothermal magnetite from calcic and
magnesian skarn in the Arizona and New Mexico deposits
contains Ti concentrations that are two to three orders of
magnitude less than most igneous magnetites. This trend has
also been observed by other authors (Dupuis and Beaudoin
2011; Ray and Webster 2007). Similarly, magnetite formed
under low pressure–temperature burial metamorphic condi-
tions and hydrothermal magnetite from moderate to low-
temperature epithermal veins have comparatively low Al
and Ti concentrations (Nadoll et al. 2012). The lower
solubility of Al at lower formation temperatures has also
been described for other spinel minerals by Sack and
Ghiorso (1991). The formation of Ti-rich magnetite under
high-temperature conditions has implications for elements
such as Au, Ag, and Cu that are more readily incorporated
into ulvöspinel than magnetite due to its higher Ti contents
(Simon et al. 2008).
511
Magnetite has been suggested as a host for Au in some
igneous rocks and hydrothermal ore deposits (Gammons and
Williams-Jones 1997; Larocque et al. 2002; Togashi and
Terashima 1997). The lack of measurable Au in our magnetite
samples could be attributed to the relatively high LOR
(Table 1) for Au when using small analytical spot sizes.
Alternatively, and perhaps more likely, Au partitions into
sulfide minerals and melts due to its strongly chalcophile
behavior (Jenner et al. 2010; Kesler et al. 2002; Sillitoe
2010; Tosdal et al. 2009), and therefore Au concentrations in
coexisting magnetite may be relatively depleted.
Under favorable fO2/fS2 conditions, sulfide minerals also
have considerably higher mineral-fluid/melt partition coeffi-
cients for other chalcophile elements such as Cu, As, Ag, Sb,
and Pb, compared to magnetite or other Fe-oxides (Cygan and
Candela 1995; Gaetani and Grove 1997; Lemarchand et al.
1987; Simon et al. 2008; Stimac and Hickmott 1994).
Molybdenum is not strongly chalcophile but can partition into
sulfide minerals.
Lastly, oxygen fugacity exerts a strong control on multiva-
lent elements such as Cr and V, whereas monovalent cations
such as Ga are less affected by changes in the availability of
oxygen in the system (Klemme et al. 2006; Nielsen et al.
1994; Righter et al. 2006b; Ryabchikov and Kogarko 2006).
Although this has been demonstrated for igneous conditions,
the effect that oxygen fugacity has on the composition of
hydrothermal magnetite is far less constrained. First principles
suggest a similar degree of control, depending on the prevail-
ing oxygen fugacity of the fluid.
Conclusions
We illustrate chemical variations of hydrothermal and igneous
magnetite from porphyry and skarn deposits and discuss how
physical and chemical factors associated with the formation of
magmatic-hydrothermal ore deposits translate into composi-
tional signatures that can discriminate magnetites of different
origin. Temperature, host rock/fluid composition, fO2, fS2, and
fluid–rock interaction are the major factors responsible for
compositional variations in igneous and hydrothermal mag-
netite. The best overall discriminators for the composition of
magnetite from the examined porphyry and skarn deposits and
their igneous host rocks are Mg, Al, Ti, V, Mn, Co, Zn, and
Ga. These elements are commonly incorporated in magnetite
at levels above their respective LOR and show characteristic
variations among the different deposits. Igneous magnetite
has, on average, higher Al, Ti, V, and Ga concentrations than
hydrothermal magnetite (including porphyry and skarn mag-
netite) reflecting higher formation temperatures and a differ-
ence between melt and hydrothermal fluid compositions. low
Ti and V concentrations, commonly in combination with
comparatively high Mg and Mn concentrations, induced by
512
extensive fluid/rock interaction, are characteristic features of
magnetite from skarn deposits. High Mg concentrations
(<1,000 ppm) are characteristic for magnetite from magnesian
skarn. In porphyry deposits, hydrothermal magnetite from
different vein types can be distinguished by their Ti, V, Mn,
and Zn contents. The suite of elements, i.e., Cr, Cu, As, Mo,
Ag, Au, and Pb, that have been reported in magnetite and,
apart from Cr, commonly occur in hydrothermal fluids related
to porphyry and skarn deposits, could not be detected at levels
greater than their respective LORs in the examined samples.
The chemical signature of igneous magnetite from the barren
Inner Zone Batholith suggests that in comparison, V, Mn, Co,
and Ga concentrations are depleted in magnetite from the
porphyry and skarn deposits.
Acknowledgements We thank Sarah Dare, Roberto Xavier, Georges
Beaudoin, Karen Kelley and one anonymous reviewer, who raised im-
portant questions and provided constructive comments that helped to
strengthen this paper.
Conflict of interest Research supported by the U.S. Geological Survey
(USGS), Department of the Interior, under USGS award number
3607415/06HQGR0173, and by Freeport McMoRan Copper & Gold
Inc. Any use of trade, product, or firm names is for descriptive purposes
only and does not imply endorsement by the U.S. Government.
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