©2011 Society of Economic Geologists, Inc.

Economic Geology, v. 106, pp. 1465–1478

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TRACE ELEMENT GEOCHEMISTRY OF ENARGITE IN THE MANKAYAN DISTRICT, PHILIPPINES

C. L. DEYELL†,1,*AND J. W. HEDENQUIST2
1 CODES, the Australian Research Council’s Centre of Excellence in Ore Deposits, University of Tasmania,
Private Bag 126, Hobart, Tasmania 7001, Australia
2 Department of Earth Sciences, University of Ottawa, Ottawa, Ontario K1N6N5, Canada

Abstract
We report the first laser ablation-inductively coupled plasma-mass spectroscopy (LA-ICP-MS) study of trace
element substitution in enargite. Results indicate significant variability in the composition of enargite samples
from a single ore system. Samples come from the Mankayan district, Philippines, which hosts the Lepanto
high-sulfidation Cu-Au deposit, now mined out, and the adjacent Far Southeast porphyry Cu-Au deposit; the
genetic relationship between these deposits has been documented in previous studies. LA-ICP-MS analyses
indicate significant incorporation of Sb and Fe in enargite (locally exceeding 1 wt %). Other elements such as
Bi, Sn, Se, Te, Ag, and Zn occur at concentrations exceeding 0.1 wt percent. The distribution of selected trace
elements in enargite correlates with previously published variations in fluid inclusion homogenization and
melting temperatures and gas compositions. The spatial distribution of data indicates enargite is enriched in
Au and Te close to the Far Southeast porphyry. Enargite is enriched in Silver, Fe, and Pb in the center of Lep-
anto, and Zn (± Cd) is enrich the ore distal to the Far Southeast porphyry. Locally elevated Sb contents occur
in samples from subsidiary branch vein structures and may indicate that mineralizing fluids along these struc-
tures were modified compared to those that formed the main orebody.

Introduction porphyry system (Mancano and Campbell, 1995), and a more

The Mankayan mineral district of northern Luzon, Philip-
pines, is one of the richest mining districts in the Philippine
archipelago. The region hosts several porphyry copper and
epithermal precious and base-metal deposits, including the
Lepanto high-sulfidation Cu-Au deposit and the adjacent Far
Southeast porphyry Cu-Au deposit (Fig. 1). Several previous
studies have documented the geologic (Garcia, 1991) and ge-
netic relationship between the epithermal and porphyry sys-
tems (Arribas et al., 1995; Mancano and Campbell, 1995;
Hedenquist et al., 1998; Imai, 2000; Chang et al., 2011), the
latter based on fluid inclusion, stable isotope, and geochrono-
logical data. These studies have shown that the two deposits
are genetically linked, and that the primary source of fluids
responsible for both alteration and mineralization in the Lep-
anto system originated at depth within the Far Southeast por-
phyry system.
Detailed studies of fluid inclusions in enargite have been
instrumental in determining the genetic relationship between
the Lepanto and Far Southeast orebodies (Mancano and
Campbell, 1995; Lindaas et al., 1998). Enargite and luzonite
occur as the most abundant sulfosalts in the Lepanto orebody,
and also occur as an overprint to the upper parts of the Far
Southeast porphyry system. Enargite is predominant in the
southeastern part of the Lepanto deposit, near the Far South-
east system, whereas luzonite is dominant to the west (Imai,
1999). Studies have shown that fluid inclusions in the enargite
record the overall progressive cooling and dilution of miner-
alizing fluids to the northwest, away from the Far Southeast
† Corresponding author: e-mail, c.wurst@comcast.net
*Present address: Spectral International Inc., Arvada, Colorado.
recent study of zoning in the earlier-formed alunite (Chang et
al., 2011) is consistent with this northwesterly cooling. This
district therefore provides an ideal site at which to examine
trace element substitution in enargite, particularly in relation
to zonation in or around ore deposits. Few other studies have
examined the trace element variability in enargite, or other
sulfosalts, in detail and these rely on electron microprobe
data (e.g., Ackerman and Petersen, 1987; Takagi and Brimhall,
1998; Camprubi et al., 2001). In some cases, the concentra-
tion of elements such as Ag, Sb, Sn, V, and Pb within enargite
have been shown to vary with distance from the center of the
deposits.
The development of laser ablation-inductively coupled
plasma-mass spectroscopy (LA-ICP-MS) offers a reliable
method for microanalyses of a diverse suite of elements at low
detection limits. Several studies have applied this technology to
the examination of trace elements in sulfides, and pyrite in par-
ticular (e.g., Norman et al., 2001; Morey et al., 2008; Cook et
al., 2009; Pass et al., 2009), but the trace element chemistry of
enargite, particularly across a deposit, has not yet been investi-
gated with LA-ICP-MS. The objectives of this study are, there-
fore, to determine the suitability of LA-ICP-MS techniques
for enargite trace element analysis, and to examine the range
concentrations for a selection of trace elements. This study
uses the same sample suite from the Mankayan district that
was studied by Mancano and Campbell (1995) and Lindaas et
al. (1998); our results define the zonation of trace elements in
enargite across the Lepanto orebody. In addition, our study is
the first to report trace element variability in enargite within
an orebody and correlate the results with data from fluid in-
clusion infrared microthermometry on the same samples.

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FIG. 1. Map of the Mankayan district showing major geologic units and structures (based on mapping and compilation by
LCMC Geological Staff; Garcia, 1991; Chang et al., 2011). Also shown are the maximum extents of major orebodies (Lep-
anto, Far Southeast, and Guinaoang), projected to surface. The locations of major veins from the Victoria and Teresa mines
are shown in bold black lines (projected to surface).

Geology and Ore Deposits in the Mankayan District
The Mankayan district is located within the Luzon Central
Cordillera. Significant porphyry and epithermal mineraliza-
tion occurs in both the Mankayan and Baguio districts of the
cordillera (Fig. 1; Arribas et al., 1995; Hedenquist et al., 1998;
Claveria et al., 1999; Sajona et al., 2002; Chang et al., 2011;
Cooke et al., 2011; Hollings et al., 2011; Waters et al., 2011).
Mineralization occurred in both districts during the last 3 m.y.
(Arribas et al., 1995; Waters et al., 2011; Cooke et al., 2011).
The geology of the Mankayan district consists of Creta-
ceous to early Tertiary basement, comprising the Lepanto
metavolcanic rocks (tectonized pillow basalts and basaltic to
andesitic lava flows) and the Apaoan volcaniclastic rocks (Rin-
genbach et al., 1990; Garcia, 1991). These units are overlain
unconformably by the Balili sequence (polymictic volcanic
conglomerates), that is, middle to late Miocene in age (Gar-
cia, 1991). A large Miocene tonalite intrusion forms the west-
ern margin of the mineral district (Gonzalez, 1956; Fig. 1).
Mineralization is temporally and spatially related to Pliocene-
Pleistocene quartz diorite intrusions and dacitic volcanic rocks
(Fig. 2). The Imbanguila hornblende dacite (2.2–1.8 Ma; Ar-
ribas et al., 1995) predates mineralization and is the principal
host for the Lepanto orebody. The unaltered Pleistocene Bato
hornblende-biotite dacite postdates mineralization.
The Far Southeast porphyry Cu-Au deposit is centered on
a shallow quartz diorite stock, dated at 1.45 Ma (Arribas et al.,
1995), that intruded the basement Balili volcaniclastic unit.
Mineralization is related to quartz stockwork veins with chal-
copyrite, pyrite, and minor bornite, Bi-Te–bearing tennantite,
and rare native gold (Garcia, 1991; Imai, 2000). Fluid inclu-
sion data indicate early quartz veins formed from hypersaline
(50–55 wt % NaCl equiv) fluids at temperatures ~450° to
550°C (Hedenquist et al. 1998; Imai, 2000), with the associ-
ated biotite dated at 1.41 Ma (n = 6; Arribas et al., 1995).
Quartz-alunite alteration occurs over the top of the porphyry
and extends northwest, where it hosts the Lepanto orebody.
Alunite within this alteration has been dated at 1.42 Ma (n =
5; Arribas et al., 1995), identical in age (within analytical
error) to the biotite alteration at depth.
At Lepanto, Cu-Au mineralization (Figs. 1, 2) is largely
controlled by the northwest-trending Lepanto fault. Mineral-
ization is also controlled by the unconformity between the
Imbanguila dacite and the underlying basement rocks (Gon-
zalez, 1956; Garcia, 1991). The ore interval is deepest at the
southeast end, as deep as 700 m elevation, but the level of
enargite ore is as shallow as 1,200 m to the northwest, follow-
ing the unconformity (Fig. 2). Near the southeastern end of
the deposit, the oblique intersection of the Lepanto fault with
east-west–trending branch faults, which splay from the main

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FIG. 2. Schematic northwest-southeast cross section through the Lepanto and Far Southeast (FSE) deposits (from Gar-
cia, 1991). The main geologic units and the extent of epithermal Cu-Au and porphyry Cu-Au mineralization are shown (from
Concepción and Cinco, 1989; Garcia, 1991). The white line indicates the location of the Lepanto fault.

Lepanto fault, results in a significantly wider ore zone (~400
m compared to ~100 m at its northwestern end; Hedenquist
et al., 1998; Claveria, 2001).
Alteration and mineralization at Lepanto are typical of
high-sulfidation epithermal deposits. The ore is hosted by
strongly leached and silicified zones (with textures of both
massive and vuggy quartz) that are surrounded by halos of
quartz-alunite (± pyrophyllite, kaolinite, dickite, and dias-
pore; Chang et al., 2011). Enargite and luzonite are the pri-
mary Cu sulfosalts, along with abundant pyrite, and lesser
chalcopyrite and tetrahedrite-tennantite, sphalerite, galena,
and tellurides (calaverite and petzite). Rare Bi selenides and
Sn-bearing phases (colusite) are also present (Claveria, 2001).
Gold mineralization is associated predominantly with tennan-
tite-tetrahedrite and chalcopyrite, and generally appears to be
paragenetically later than the enargite-luzonite (Gonzalez,
1956; Claveria, 2001).
A genetic relationship between the Far Southeast and Lep-
anto orebodies has been demonstrated previously by narrow
age constraints, as well as fluid inclusion and stable isotope
data (Arribas et al., 1995; Mancano and Campbell, 1995;
Hedenquist et al., 1998; Lindaas et al., 1998; Imai, 2000).
Mancano and Campbell (1995) examined the microther-
mometry of fluid inclusions hosted in enargite along a section
from the Far Southeast porphyry to the Lepanto orebody
(Table 1). They showed a distinct cooling trend away from the
porphyry center, with an accompanying decrease in salinities
(from averages of 3.3 to 1.6 wt % NaCl equiv, with a total
range from 4.5 to 0.2 wt %). Lindaas et al. (1998) examined
the composition of fluid inclusion gases (N2-CH4-Ar-H2S-
CO2-CH4) in enargite, again from Far Southeast through to
the Lepanto orebody, using the same sample suite as Man-
cano and Campbell (1995). They report higher N2/Ar and
H2S/Ar ratios in samples from the branch veins, combined
with slightly higher salinities and homogenization tempera-
tures (Th) of fluid inclusions from the same samples (Man-
cano and Campbell, 1995), and suggested upward flow of
fluid along the branch fault intersections in the Lepanto ore-
body (Lindaas et al., 1998), in addition to the general north-
westward flow of mineralizing fluids outward from the Far
Southeast orebody (Mancano and Campbell, 1995).
Methods of Analysis
The sample suite used in this study is the same as that ex-
amined by Mancano and Campbell (1995) and Lindaas et al.
(1998). Enargite crystals (Table 1) were taken from samples
collected along the main Lepanto high-sulfidation orebody,
from the top of the Far Southeast porphyry to the distal
margins of the high-sulfidation deposit 2 km to the north-
west, as well as samples from the hanging-wall and footwall
branch veins (Fig. 3). Samples consisted of individual enar-
gite grains, all less than 1 cm in length, with rare associated
pyrite. Only one sample (U-85-21) had any visible mineral
inclusions (tennantite).
A subset of the enargite samples (n = 12) was analyzed by
electron probe microanalysis (EPMA) at the University of

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TABLE 1. Enargite Samples from the Mankayan District, Philippines

Sample UTM UTM Elevation Location1 Mean Th2 Max Th2 Mean Tm2 Min Tm2
no. northing easting (m) (°C) (°C) (°C) (°C)

2-2-2 1864100 265475 950 FW 249 267 –1.6 –2

2-5-2 1864955 264395 1030 MOB –1.7 –1.7
2-6-4 1865811 263591 1030 NOA 166 196 –1 –1.2
2-8-4 1865160 264220 1070 MOB 207 207 –1.3 –1.3
2-9-2 1865195 264520 950 HW 225 238 –1 –2.7
2-12-1 1864250 265365 700 MOB 230 259 –1 –1.7
2-13-2 1863810 265240 900 FW 206 245 –1.2 –1.8
2-18-2 1865480 263845 1000 MOB 198 214 –1.4 –2.2
2-19-2 1864415 265115 700 MOB 201 223 –1 –1.7
2-19-3 1864290 265405 1100 FW 209 241 –1.5 –2.3
3-6-2 1864390 265225 950 MOB 248 254 –1.3 –1.5
3-6-3 1865175 264520 1000 HW 231 245 –1.3 –2
3-25-4 1864425 265230 850 MOB 220 252 –1.3 –1.9
4-2-1 1864460 264675 1030 FW 224 237 –1.7 –2
4-3-1 1865165 264325 1030 MOB 194 232 –1.2 –2.2
4-3-2 1864732 264673 1030 MOB 207 219 –1.8 –2.3
U-85-21 1864274 265846 592 FSE 285 294 –1.9 –2.6

Note: Also shown are corresponding fluid inclusion homogenization (Th) and ice melting temperatures (Tm) from Mancano and Campbell (1995)
1 FW = footwall, HW = hanging wall, MOB = main orebody (Lepanto), NOA = northern extension zone, FSE = Far Southeast orebody
2 Data from Mancano and Campbell (1995)

Tasmania to determine their major and selected trace ele-
ment compositions, with an average of five analyses per sam-
ple (using 50nA and 5-µm spot size). These samples were an-
alyzed for seven elements (S, Fe, Cu, As, Sb, Te, and Bi); 64
points were analyzed in total (Table 2). The entire sample
suite (n = 17) was analyzed by LA-ICP-MS techniques, also
at the University of Tasmania. Details of LA-ICP-MS
methodology, including descriptions of instrumentation, sam-
ple preparation, laser analysis, data reduction, and interpreta-
tion are documented by Large et al. (2009) and Danyu-
shevsky et al. (in press).
In this study, the enargite samples were analyzed by LA-
ICP-MS for a total of 17 elements: Ti, V, Fe, Zn, Se, Zr, Mo,
Ag, Cd, Sn, Sb, Te, Ba, W, Au, Pb, and Bi (Table 3). Spot size
varied between 60 and 100 µm, depending on the enargite
grain size. Multiple enargite grains were analyzed from each

FIG. 3. Map showing the location of all enargite samples analyzed in this study. Sample locations are superimposed on
shaded areas showing the maximum extents of the Lepanto (light gray) and Far Southeast orebodies (dark gray), projected
to surface (based on mapping and compilation by LCMC geologic staff).

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TABLE 2. Summary of Electron Microprobe (EPMA) Data for Selected Enargite Samples
(data for each sample represents the mean of multiple data points)

All samples

Mean 1σ 2-2-2 2-6-4 2-8-4 2-9-2 2-13-2 2-18-2 2-19-3 3-6-2 3-6-3 3-25-4 4-2-1 4-3-2

Wt % S 32.19 0.2 32.12 32.28 32.47 31.88 32.02 32.26 32.20 32.26 32.19 32.18 32.18 32.16
Fe 0.03 0.1 - - - - - - - 0.21 0.02 - - -
Cu 48.65 0.4 48.27 48.60 48.88 48.29 48.62 48.81 48.79 48.78 48.77 48.65 48.76 48.57
As 17.73 0.9 16.60 18.01 17.69 16.05 17.64 18.34 17.89 18.18 18.48 18.11 17.66 18.27
Sb 1.17 1.3 2.90 0.79 1.17 3.59 1.26 0.43 0.90 0.19 0.22 0.68 1.28 0.49
Te 0.03 0.0 0.03 - - - - - 0.05 0.06 0.03 0.03 - -
Bi 0.06 0.1 - 0.11 - 0.07 0.07 - - 0.13 - - - -
Total 99.9 100.0 99.8 100.3 99.9 99.7 99.9 99.9 99.8 99.8 99.7 100.0 99.5

No. moles Fe 0.0 - - - - - - - 0.0 0.0 - - -

based on 4 S Cu 3.1 3.0 3.0 3.0 3.1 3.1 3.1 3.1 3.1 3.1 3.1 3.1 3.0
As 0.9 0.9 1.0 0.9 0.9 0.9 1.0 1.0 1.0 1.0 1.0 0.9 1.0
Sb 0.0 0.1 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Te 0.0 0.0 - - - - - 0.0 0.0 0.0 0.0 - -
Bi 0.0 - 0.0 - 0.0 0.0 - - 0.0 - - - -

Note: - denotes below detection limit

sample, and the number of analyses per grain was dependent
on crystal size. Data reduction and quantification used stoi-
chiometric Cu as the internal standard, based on the near-sto-
ichiometric Cu/S ratios returned by EPMA analysis (Table 2).
Detection limits (averaged over all analyses) for the LA-ICP-
MS data are given in Table 4.
Analytical Results
EPMA results
EPMA analyses (Table 2) indicate near-stoichiometric
enargite compositions of Cu, As, and S for the majority of
samples analyzed. The Sb contents are variable, with values
up to 5.7 wt percent (sample 2-9-2). In general, EPMA values
of minor elements Bi, Te, and Fe are below detection (with
average detection limits of 16, 28, and 70 ppm, respectively).
The distribution of Sb to As ratios in the enargite (Fig. 4) is
variable. High Sb/As ratios occur in the branch vein struc-
tures, whereas this ratio is generally low in the main Lepanto
orebody.
LA-ICP-MS results
A summary of enargite LA-ICP-MS data for each sample is
given in Table 4. There is significant variability in most ele-
ments analyzed, and particularly in Fe, Te, V, and Mo (Table
4; Fig. 5). Nearly all elements are consistently above ICP-MS
detection limits (Table 3; Fig. 5), with the exception of Cd,
with mean values (2.3 ppm) close to detection.
A direct comparison between the LA-ICP-MS and EPMA
data cannot be made because the sample volume of the two
techniques is significantly different. Both Bi and Te are con-
sistently below detection for EPMA analyses, although locally
very high values are reported in LA-ICP-MS results. The
larger beam size, 60 to 100 µm for LA-ICP-MS analysis, com-
pared with the EPMA beam (5 µm), provides a better esti-
mate of the bulk composition of individual enargite grains and
can be used to sample across small zones of compositional
variability.
The compositional variability between multiple LA-ICP-
MS analyses of individual enargite crystals is due either to
mineral inclusions, fluid inclusions, and/or growth zones.
However, most samples exhibit relatively simple composi-
tional patterns determined from LA-ICP-MS (Fig. 6a, b).
Very few silicate inclusions are present, with the exception of
rare Zr-bearing phases. The most common inclusion types are
minor Au (± Ag, Te), as discussed below, as well as inclusions
containing variable combinations of Bi-Te-Sn-Fe (Fig. 6c).
Complex growth zoning was also noted locally. This com-
positional variability is due primarily to different combina-
tions of Fe-Bi-Te-Sb-Sn-Se, but overall there are very few
consistent elemental correlations in the enargite. As indicated
in Table 5, Sb correlates weakly with Sn, and to a lesser extent
with Te. Weak correlations also occur between Ag-Sb, Ag-Bi,
Te-Se, and Te-Sb (Table 5).
Discussion
Nature of Au in enargite
The nature of Au in the enargite is of particular interest at
Lepanto because Au was a significant contributor to the eco-
nomic viability of the mine. Both Cu and Au were mined
from the deposit during large-scale mining operations from
1936 to 1996, with an average grade over the life of produc-
tion of 3.4 g/t Au, 14 g/t Ag, and 2.9 wt percent Cu, the latter
largely from enargite (Chang et al., 2011). Previous studies
have shown that the Au occurred mostly as electrum or in as-
sociation with tellurides, selenides, and Bi- and Sn-bearing
phases (Tejada, 1989; Claveria and Hedenquist, 1994; Clave-
ria, 2001). In this study, Au is above detection in most enar-
gite samples, with maximum values up to 70 ppm (Fig. 5).
Three distinct forms of Au occurrence are recognized in the
Lepanto enargite. In most cases, the Au exhibits smooth LA-
ICP-MS traces in analytical traverses across enargite (Fig. 7b)
and therefore it is thought to be structurally bound within the
enargite crystal lattice (e.g., Danyushevsky et al., in press).
Rare inclusions of native gold with elevated concentrations of

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TABLE 3. Summary of LA-ICP-MS Data for Mankayan Enargite Samples

Sample no. 2-2-2 (n = 6) 2-5-2 (n = 3) 2-6-4 (n = 5) 2-8-4 (n = 5) 2-9-2 (n = 5) 2-12-1 (n = 4) 2-13-2 (n = 7) 2-18-2 (n = 4) 2-19-2 (n = 5)
Element Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ

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Ti (ppm) 10.4 0.8 7.5 0.2 11.3 2.4 9.4 0.5 9.0 0.6 7.7 0.7 9.7 0.6 10.0 0.8 38.2 68.8
V (ppm) 0.6 0.5 0.0 0.0 0.3 0.2 0.9 2.1 8.9 3.8 8.6 11.1 1.4 2.4 0.0 0.0 0.5 0.6
Fe (ppm) 20.4 10.5 21.3 10.5 29.5 41.6 83.2 128.1 22.6 39.8 83.8 75.6 88.7 49.6 2.9 0.4 38.4 39.6
Zn (ppm) 14.9 19.1 1.5 0.4 10.5 8.9 1.7 1.2 10.9 6.6 43.9 59.8 7.7 3.6 708.8 1414.9 3.6 2.9
Se (ppm) 344.9 335.0 188.0 99.7 12.3 10.2 530.3 506.5 57.4 21.1 24.7 6.9 66.1 18.3 66.6 19.4 33.3 9.5
Zr (ppm) 0.1 0.0 0.0 0.0 0.0 0.0 0.1 0.0 0.1 0.0 0.0 0.0 0.1 0.0 0.1 0.0 0.4 0.8
Mo (ppm) 6.3 9.8 n/a n/a 0.4 0.0 5.8 11.8 4.6 2.1 n/a n/a 0.5 0.4 0.7 0.5 n/a n/a
Ag (ppm) 0.6 0.1 527.0 729.0 22.1 19.0 3.1 0.6 5.4 1.5 39.6 12.5 38.2 57.9 2.0 0.4 64.5 28.9
Cd (ppm) 1.3 0.6 0.5 0.3 1.2 0.1 1.6 0.3 1.5 0.1 4.2 3.8 1.1 0.7 8.0 13.6 1.1 0.8
Sn (ppm) 1058.0 604.4 306.6 86.2 8.5 5.6 1154.5 984.6 127.8 77.4 13.9 13.7 28.3 17.6 611.1 452.2 28.6 28.8
Sb (%) 2.9 1.9 0.4 0.1 1.1 0.3 1.8 3.1 4.4 1.5 0.3 0.2 2.3 1.1 0.6 0.1 0.3 0.3
Te (ppm) 235.9 221.4 151.4 104.5 17.7 17.2 46.2 37.3 115.7 100.0 20.9 27.1 77.2 78.5 20.9 21.0 13.8 17.8
Ba (ppm) 0.4 0.3 0.1 0.0 0.1 0.1 0.3 0.3 0.4 0.2 0.1 0.0 0.3 0.1 0.1 0.1 15.7 34.0
W (ppm) 2.5 2.1 n/a n/a 0.5 0.4 0.9 1.9 0.4 0.4 n/a n/a 0.4 0.9 0.2 0.2 n/a n/a
Au (ppm) 0.5 0.4 1.1 1.1 0.1 0.1 0.1 0.1 1.1 1.4 0.8 0.9 0.7 0.6 0.1 0.1 0.2 0.2
Pb (ppm) 1.1 0.9 6.7 5.5 2.3 2.7 0.5 0.5 2.0 2.6 2.6 3.6 2.8 2.5 4.6 9.2 8.5 16.9
Bi (ppm) 164.2 100.8 30.8 34.8 1701.9 960.8 559.7 875.4 653.9 1316.7 140.5 167.3 934.9 647.7 128.9 85.3 432.2 550.5

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Sample no. 2-19-3 (n = 6) 3-6-2 (n = 7) 3-6-3 (n = 7) 3-25-4 (n = 6) 4-2-1 (n = 5) 4-3-1 (n = 3) 4-3-2 (n = 6) U-85-21 (n = 3)
Element Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ Mean 1σ

Ti (ppm) 13.8 0.5 11.5 2.2 10.4 0.8 8.9 0.4 10.2 0.5 8.0 0.5 10.7 0.9 6.6 0.1
V (ppm) 0.1 0.1 44.1 114.4 7.3 11.0 10.0 16.2 8.6 6.2 0.2 0.1 0.0 0.1 0.1 0.1
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Fe (ppm) 41.0 33.0 1128.1 2498.7 243.2 157.1 229.2 344.0 33.5 18.1 30.1 24.6 7441.2 18152.5 385.9 641.6
Zn (ppm) 15.6 6.5 32.4 28.2 15.1 16.5 2.9 1.5 6.9 3.8 4.9 2.9 34.8 52.3 73.2 65.6
Se (ppm) 178.4 61.5 368.7 384.5 415.7 200.6 200.6 200.1 207.6 90.9 205.3 142.6 387.6 460.0 176.9 70.8
Zr (ppm) 0.1 0.0 0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Mo (ppm) 41.3 58.3 0.2 0.3 0.2 0.1 0.2 0.2 0.6 0.2 n/a n/a 1.4 2.0 n/a n/a
Ag (ppm) 164.0 115.7 30.4 17.6 81.7 41.2 70.5 40.3 92.1 13.2 116.3 34.9 93.8 67.9 1.3 1.0
Cd (ppm) 3.3 2.2 5.8 3.1 1.8 0.9 0.3 0.1 0.3 0.2 0.4 0.1 2.4 2.9 4.2 0.5
Sn (ppm) 934.1 682.1 108.7 114.7 192.4 133.9 194.7 273.4 15.8 5.9 48.2 36.8 1134.1 425.4 645.2 88.6
Sb (%) 1.6 1.4 0.3 0.2 0.2 0.1 0.8 0.6 2.0 0.5 0.6 0.7 1.5 1.0 0.9 0.5
Te (ppm) 510.7 817.8 851.6 650.1 143.1 134.7 128.0 120.7 77.5 39.1 108.1 149.6 19.6 21.4 80.6 24.6
Ba (ppm) 0.1 0.0 0.0 0.0 0.1 0.1 0.1 0.0 0.2 0.0 0.2 0.2 0.2 0.1 0.3 0.2
W (ppm) 0.1 0.2 24.0 58.2 10.8 22.8 4.9 4.4 0.2 0.1 n/a n/a 0.0 0.0 n/a n/a
Au (ppm) 1.6 1.8 21.5 27.2 3.1 2.7 26.3 29.6 0.2 0.1 5.5 6.7 0.2 0.3 0.4 0.4
Pb (ppm) 21.4 35.5 2.0 1.5 2.8 2.5 0.9 1.0 1.1 1.3 9.3 6.0 14.0 32.5 0.5 0.4
Bi (ppm) 411.4 378.4 1716.0 2318.5 1132.4 352.3 997.0 900.4 190.8 72.7 824.2 694.3 36.4 46.1 5.8 7.4
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TABLE 4. LA-ICP-MS Detection Limits (values in ppm)

Element Ti V Fe Zn Se Zr Mo Ag Cd Sn Sb Te Ba W Au Pb Bi

Mean 0.38 0.03 4.14 0.33 1.3 0.02 0.32 0.03 1.03 0.09 0.17 0.2 0.08 0.03 0.04 0.03 0.02
1σ 0.2 0.0 2.0 0.1 0.1 0.0 0.3 0.0 1.0 0.1 0.2 0.1 0.0 0.0 0.0 0.0 0.0

Note: Data shown are average values for all analyses in this study

FIG. 4. Map showing 100*Sb/As ratios in enargite, based on mean wt percent EPMA results. Gray circles represent sam-
ples taken from hanging-wall and foot wall branch veins; white circles are from the main Lepanto orebody and northern ex-
tension zone. Sample locations are superimposed on shaded areas showing the maximum extents of the Lepanto (light gray)
and Far Southeast orebodies (dark gray), projected to surface.

FIG. 5. Range of enargite LA-ICP-MS trace element data for all analyses in this study (as ppm). The mean of all analyses
and mean detection limits (DL) for each element are also shown.

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100
Counts

10
0 20 40 60 80 100 120
Time(s)

100000

100
Counts

10
0 20 40 60 80 100 120

Time(s)

100000

100
Counts

10
0 20 40 60 80 100 120
Time(s)
FIG. 6. Photomicrographs and raw LA-ICP-MS element data (shown as element counts over time) for selected enargite
samples. (A) Sample 2-12-1. (B) Sample 2-19-2. (C) Sample U-85-21. Scale bar = 100 µm. Black circles on photographs in-
dicate the locations of associated LA-ICP-MS analyses.

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TABLE 5. Correlation Matrix Showing “r” Values of Elements Based on Average LA-ICP-MS Results

Ti V Fe Zn Se Zr Mo Ag Cd Sn Sb Te Ba W Au Pb Bi

Ti 1.0
V 0.1 1.0
Fe 0.0 0.1 1.0
Zn 0.1 0.0 0.1 1.0
Se 0.1 0.1 0.0 0.0 1.0
Zr 0.0 0.0 0.0 0.0 0.0 1.0
Mo 0.0 0.1 0.1 0.0 0.1 0.0 1.0
Ag 0.1 0.1 0.2 0.1 0.2 0.0 0.1 1.0
Cd 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0
Sn 0.1 0.1 0.0 0.2 0.3 0.0 0.0 0.3 0.1 1.0
Sb 0.1 0.1 0.0 0.1 0.4 0.0 0.0 0.4 0.0 0.6 1.0
Te 0.1 0.1 -0.1 0.1 0.4 0.0 0.0 0.3 0.0 0.4 0.4 1.0
Ba 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0
W 0.0 0.2 0.2 0.0 0.0 0.0 0.0 0.1 0.0 0.1 0.1 0.0 0.0 1.0
Au 0.0 0.1 0.2 0.1 0.0 0.0 0.0 0.2 0.0 0.1 0.0 0.0 0.0 0.2 1.0
Pb 0.1 0.1 0.2 0.2 0.0 0.0 0.0 0.2 0.0 0.1 0.1 0.0 0.0 0.1 0.2 1.0
Bi 0.1 0.2 0.3 0.1 0.1 0.0 0.1 0.4 0.0 0.2 0.3 0.1 0.1 0.3 0.3 0.3 1.0

Ag, Te, and Pb also occur in the enargite (Fig. 7a). The third
occurrence of Au is as complicated growth zones and/or
multi-element inclusions within the enargite (Fig. 7c). In
these analyses of growth zones and/or inclusions, there is a
strong association of Au with anomalies of Fe-Ag-Pb-Bi ± Sn,
Mo.
Comparison with fluid inclusion measurements
Direct comparison of the enargite LA-ICP-MS data (Table
4) and fluid inclusion homogenization and melting tempera-
ture measurements can be made for the same samples, using
the data from Mancano and Campbell (1995) (Table 1). In
most samples, there is poor correlation between the datasets
and few trends are present, due to the large range of LA-ICP-
MS results for individual elements within a single enargite
sample. However, selected elements show some trends with
respect to either homogenization temperature (Th) or fluid
salinity (Tm) (Fig. 8).
Correlations of Pb and Te (Fig. 8a, b) to fluid inclusion ho-
mogenization temperatures show opposite trends. Average
Pb concentrations are lowest (<1 ppm) in samples with the
highest recorded Th measurements, and gradually increase to
a maximum (>10 ppm) at Th values of ~210°C (Fig. 8a);
Chang et al. (2011) found a similar pattern in terms of Pb hav-
ing the highest concentration in alunite samples that are dis-
tal, which formed at the lowest temperature. In contrast, Te
values exhibit an overall positive trend with respect to Th (Fig.
8b). However, relatively lower Te concentrations occur at the
highest Th value, corresponding to enargite mineralization
that overprints the Far Southeast porphyry in a hydrothermal
breccia (sample U85-21).
Similar trends are observed between Bi and Se with respect
to fluid inclusion Tm measurements (Fig. 8c, d). A strong neg-
ative correlation occurs between Bi and increasing fluid salin-
ity (lower Tm values; Fig 8c), i.e., low Bi correlates with high
salinity, perhaps due to Bi remaining in high salinity solutions.
In contrast, Se concentrations exhibit a weak positive correla-
tion with respect to fluid salinity, with the lowest Se values
corresponding to the lowest salinity measurements.
Sb substitution in enargite
The nature and temperature dependence of Sb substitution
in enargite is well documented in studies of phase relation-
ships between enargite and the luzonite-famatinite solid-so-
lution series (e.g., Skinner, 1960; Maske and Skinner, 1971;
Pósfai and Buseck, 1998). Studies have shown that Sb can
substitute in the enargite crystal structure up to a maximum
of about 20 mol percent Cu3SbS4 (Springer, 1969). In the pre-
sent study, Sb contents of the enargite are low, averaging
about 4 mol percent Cu3SbS4, and only a few analyses had val-
ues above 10 mol percent Cu3SbS4 (Table 2). The highest
Sb/(Sb+As) ratios occur in the branch vein structures (Fig. 9),
but there is no consistent zonation in Sb values away from the
Far Southeast deposit or the Lepanto main orebody. A com-
parison of Sb/(Sb+As) ratios in samples from the deposit to
fluid inclusion homogenization temperatures (Fig. 9) indi-
cates that there is a broad trend of increasing Sb/(Sb+As) with
decrease in temperature in samples from the main Lepanto
orebody and northern extension zone. However, there is no
similar trend in samples from the branch veins, which have
variable Sb/(Sb+As) over a range of temperatures. These data
suggest that temperature is not the only factor that deter-
mines Sb concentrations in enargite at Lepanto. Given the re-
sults of the fluid inclusion gas study and the recognition of ad-
ditional fluid input along the branch structures (Lindaas et
al., 1998), we suggest that the variation in Sb/(Sb+As) content
of the enargite can be attributed to different fluid pathways
and different fluid compositions, as well as temperature. Min-
eralizing fluids within the branch veins had generally higher
Sb/(Sb+As) ratios compared to the predominantly northwest-
ward flowing fluids sourced from the Far Southeast porphyry
(e.g., Hedenquist et al., 1998).
Spatial distribution of trace elements in enargite
Trace element substitution in Cu sulfosalts has previously
been shown to vary with distance from some epithermal ore-
bodies, although specific element enrichments or depletions
appear to vary between deposits (e.g., Ackerman and Pe-
tersen, 1987; Takagi and Brimhall, 1998; Camprubi et al.,

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1000000

100000

10000
Counts

1000

100

10
0 20 40 60 80 100 120
Time(s)

10000000

1000000

100000
Counts

10000

1000

100

10
0 20 40 60 80 100 120
Time(s)
10000000

1000000

100000
Counts

10000

1000

100
FIG. 7. Raw LA-ICP-MS element data (se-
lected elements only) for selected Au-bearing
10 enargite samples showing variability of Au occur-
0 20 40 60 80 100 120 rences. (A) Sample 3-25-4; (B) Sample 3-6-3; and
Time(s) (C) Sample 4-3-2.

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100 10000
A B

1000
10
Pb (ppm)

Te (ppm)
100
1
10

0.1
1

0.01 0.1
150 180 210 240 270 300 150 180 210 240 270 300
mean Th (°C) mean Th (°C)

10000
C 10000
D

1000 1000
Bi (ppm)

Se (ppm)
100
100

10

10
1

1
0.1
-2 -1.75 -1.5 -1.25 -1 -0.75
-2 -1.75 -1.5 -1.25 -1 -0.75
mean Tm (°C)
mean Tm (°C)
FIG. 8. Comparison of selected LA-ICP-MS trace element contents of enargite (a: Pb, b: Te; c: Bi, d: Se) with fluid in-
clusion homogenization (Th) and average melting (Tm) temperatures. Fluid inclusion data from Mancano and Campbell
(1995).

100

MOB & NOA

FW & HW
Sb/Sb+As *100

10

FIG. 9. Scatter plot showing enargite EPMA 100*Sb/(Sb+As) (el-

ement levels as wt %) compared to mean fluid inclusion homoge-
nization temperatures (Th) from Mancano and Campbell (1995). Er-
0.1 rors shown are 1 standard deviation on EPMA measurements.
150 170 190 210 230 250 270 Abbreviations: FW = footwall, HW = hanging wall, MOB = main
mean Th (°C) Lepanto orebody, NOA = northern extension zone.

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 1476
2001). Similar results are recorded in the Mankayan district,
where several elements are preferentially enrich or deplete
the ore relative to their distance from the Far Southeast por-
phyry (Fig. 10). Enargite samples close to the Far Southeast
porphyry system are relatively enriched in elements such as
Au, Te, and, to a lesser extent, V (Fig. 10a, b). The main Lep-
anto orebody is preferentially enriched in Ag near the core of
the epithermal deposit (Fig. 9a), along with Fe and, to a lesser
extent, Pb (Fig. 10c). The only elements that enrich the
northwestern distal extent of the Lepanto deposit are Zn and,
to a lesser extent, Cd (Fig. 10e, f).
The distribution of elements between enargite samples in
the main Lepanto orebody is also different to that within the
branch vein structures. Elements such as Sn and Te show lit-
tle variability between the main orebody and branch vein
structures. Only enargite is enriched in Sb within the branch
vein structures, based on both EPMA (Table 2) and LA-ICP-
MS analyses (Table 4), whereas concentrations of Au and Zn
are highest in enargite from the main Lepanto orebody and
the overprint to the Far Southeast system (Fig.10a, e). These
data are consistent with the conclusions of Lindaas et al.
(1998), who suggested a distinct upflow of mineralizing flu-
ids along the branch vein structures. As noted above, this
branch vein fluid may have had a slightly different composi-
tion to the fluid originating from the Far Southeast porphyry
and that flowed along the Lepanto fault, with lower Au but
higher Sb contents. This may have been caused by a differ-
ent fluid ascent path, a greater degree of wall-rock interac-
tion, or both.
Our results indicate that the trace element content of
enargite is influenced by a range of factors and does not
solely reflect the composition of the mineralizing fluids, nor
the temperature.
Conclusions
We report the first LA-ICP-MS study of trace element sub-
stitution in enargite. The methodology described by Danyu-
shevsky et al. (in press) for analysis of pyrite and other sulfides
is also applicable to enargite. Results indicate significant vari-
ability in trace element compositions of enargite samples
from a single ore deposit. The LA-ICP-MS technique has sig-
nificant advantages over EPMA analysis, as ICP-MS detec-
tion limits are one to two orders of magnitude lower than
electron microprobe levels.
Results from this study of the Lepanto deposit indicate sig-
nificant incorporation of Sb in enargite, averaging 1.3 wt per-
cent; by contrast, the average of Fe is typically <0.1 wt per-
cent. Other elements such as Bi, Sn, Se, Te, Ag and Zn are
also present at values exceeding 0.01 wt percent. In general,
the most abundant trace elements recorded in the enargite
are those that also form discrete sulfosalt, selenide, and tel-
luride accessory phases in the deposit (e.g., Claveria and
Hedenquist, 1994; Arribas et al., 1995; Claveria, 2001).
FIG. 10. Plan maps showing trace element contents of enargite based on mean LA-ICP-MS results. The footprint of the
Lepanto and Far Southeast deposits are indicated. a) Au, b) Te, c) Ag, d) Pb, e) Zn, and f) Cd. Gray circles represent sam-
ples taken from hanging-wall and footwall branch veins; white circles are from the main Lepanto orebody (MOB) and north-
ern extension zone (NOA). Sample locations are superimposed on shaded areas showing the maximum extent of the Lep-
anto (light gray) and Far Southeast orebodies (dark gray), projected to surface.
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The distribution of some trace elements in the enargite
samples from Lepanto can be related to systematic variations
in fluid inclusion homogenization and melting temperatures
(Mancano and Campbell, 1995), as well as broad changes in
fluid inclusion gas chemistry (Lindaas et al., 1998). General
trends in the spatial distribution of some elements suggest en-
richment in Au and Te (in particular) close to the Far South-
east porphyry system, where the paleotemperatures were the
highest (Mancano and Campbell, 1995); however, there is sig-
nificant variability in some elements between individual
grains and/or samples. Enargite is enriched in elements such
as Ag and, to a lesser extent, Fe and Pb in the center of the
Lepanto orebody, whereas Zn (± Cd) enrich the enargite dis-
tal to the Far Southeast porphyry, where temperatures were
lower (Mancano and Campbell, 1995). Locally, elevated Sb
and Sb/(Sb+As) ratios in the enargite occur in samples from
the branch vein structures. These data, combined with varia-
tions in elements such as Au and Zn, are consistent with the
conclusion of Lindaas et al. (1998), that mineralizing fluids in-
troduced along the branch veins were distinctly different
compared to those that flowed from the Far Southeast por-
phyry northwest along the Lepanto fault to form the main
orebody, where 70 percent of the ore originated.
Our results have implications for exploration around enar-
gite-rich high sulfidation ore deposits. Lateral variations in
the trace element geochemistry of enargite, from distal Zn
enrichment to proximal Ag, Fe, and Pb enrichment, may help
to locate the center of hydrothermal activity, thereby provid-
ing explorers with the best chance of locating any cogenetic
porphyry-style mineralization.
Acknowledgments
This study was funded by a NSERC PDF fellowship to C.
Deyell, with analytical expenses funded through CODES,
Centre of Excellence in Ore Deposits, Hobart. We thank D.
Mancano for providing the polished samples from his original
study of fluid inclusions in enargite, D. Steele for assistance
with electron microprobe analyses, L. Danyushevsky for as-
sistance with interpretation of LA-ICP-MS data, and S.
Gilbert for technical assistance with the LA-ICP-MS instru-
ment. LCMC is acknowledged for approving the use of
updated geological maps and information. Comments and
contributions by D. Cooke and N. White are gratefully ac-
knowledged. Critical reviews by James Pope and David John
are appreciated.
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