Journal of Geochemical Exploration 105 (2010) 117–136

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Journal of Geochemical Exploration

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / j g e o ex p

Defining trace-element alteration halos to skarn deposits hosted in heterogeneous

carbonate rocks: Case study from the Cu–Zn Antamina skarn deposit, Peru
A. Escalante, G.M. Dipple ⁎, S.L.L. Barker, R. Tosdal
Mineral Deposit Research Unit, Department of Earth and Ocean Sciences, 6339 Stores Rd, University of British Columbia, Vancouver, BC, Canada V6T1Z4

a r t i c l e i n f o a b s t r a c t

Article history: The presence of geochemical anomalies, defining haloes around hydrothermal ore deposits, can be used to
Received 2 November 2009 vector towards mineralization, or identify ore bodies buried at depth. Several important types of ore
Accepted 22 April 2010 deposits, including skarn deposits, are often hosted within carbonate-rich sedimentary rocks. Identifying
Available online 3 June 2010
anomalous trace-element concentrations in carbonate rocks is complicated by variable lithology (i.e.
siliciclastic component) and volume loss during hydrothermal alteration. In this study of the world-class
Keywords:
Skarn
Antamina skarn deposit in Peru, we use the ratio of metals:immobile elements (e.g. La, Al2O3) to differentiate
Geochemical halo genuine and false geochemical anomalies in limestones and marbles surrounding the skarn deposit.
Carbonate Unaltered limestones are used to define threshold values for metal:immobile element ratios (through use of
Copper the median value ± 2 median absolute deviations). Genuine anomalies are identified when metal
concentrations exceed those predicted using median + 2 median absolute deviations. In addition,
comparison of “four acid” and lithium-borate fusion analytical techniques reveals that the lower cost four-
acid techniques give reliable results. Our approach can be used to identify geochemical anomalies and halos
related to hydrothermal alteration of carbonate-rich rocks, which have direct application to skarn deposits.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction can lead to passive enrichment of trace elements. Both of these

Geochemical anomalies, or “haloes” around hydrothermal ore
deposits, formed as a result of metasomatism of host rocks by
hydrothermal fluids, have been extensively used as an exploration
tool for the discovery of economic ore deposits (Boyle, 1967;
Korzhinskii, 1968; Rose et al., 1979). The detection of trace-element
anomalies is dependent on accurate characterization of the range of
values for the particular trace element(s) or metal(s) of interest (e.g.
Cu, As, and Au) in unaltered rocks, thus allowing trace-element haloes
(i.e. statistical outliers; Barnett and Lewis, 1994) to be distinguished
from background variations.
Skarn deposits form when magmas, intruded into carbonate-rich
host rocks, generate a hydrothermal system. Subsequent thermal
metamorphism and hydrothermal alteration convert carbonate-rich
host rocks into skarn, marble and diopside. In this study, we describe a
method for distinguishing trace-element metasomatism related to
hydrothermal mineralization in impure carbonate rocks. This tech-
nique has applications for both regional and local exploration of ore
deposits in carbonate rocks (e.g. skarns, Carlin-type gold deposits).
Impure carbonate rocks contain fine clastic material that may
generate a broad range of trace-element and metal concentrations. In
addition, volume loss (commonly caused by carbonate dissolution)
⁎ Corresponding author.
E-mail address: gdipple@eos.ubc.ca (G.M. Dipple).
phenomena generate “false positives” within geochemical datasets. In
order to successfully distinguish geochemical haloes from “false
positives” in impure carbonate rocks, the influence of variable clastic
components and volume loss must be taken into account. Clastic
material commonly contains elements that remain immobile during
metamorphism and hydrothermal alteration (MacLean and Barrett,
1993).
This study proposes a method to account for varying protolith, and
to determine the threshold values of metals in the marble, hornfels
and limestone rocks that commonly surround skarn deposits, through
the use of immobile elements. The characterization of thresholds
permits robust identification of geochemical alteration halos to the
fluid flow pathways in hydrothermal ore deposits. Lateral and vertical
zonation of trace-element halos may be important in the exploration
of skarn and other carbonate-hosted deposits, especially where visible
alteration features are subtle or indistinguishable.
Gresens (1967) designed a mathematical method to estimate the
changes in volume and concentrations during metasomatism. This
method was modified and simplified to a graphical scheme by Grant
(1986, 2005), in which the gain or loss of the elements is related
graphically to several selected immobile elements (the “isocon”).
Aluminum and some high field strength elements such as niobium,
zirconium, yttrium and titanium have been used as immobile
elements during intense hydrothermal alteration (Finlow-Bates and
Stumpfl, 1981; Campbell et al., 1984; Jenner, 1996). Some rare earth
elements (REE) such as La, Ce and Nd can also be used to infer the

0375-6742/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.gexplo.2010.04.011
118 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136

gains and losses of other trace elements because of their relative
immobility (MacLean and Barrett, 1993).
Determination of geochemical halos distal to a skarn deposit
requires the estimation of accurate background and threshold values,
which are complicated by the impure nature of the protolith
(limestone). The Antamina Cu–Zn skarn deposit provides an excellent
opportunity to define geochemical haloes around a skarn deposit, as it
has a wide marble and hornfels aureole around it, and country and
mineralized rocks are exposed over a large vertical extent. This study
characterizes the chemical composition of protolith and alteration at
Antamina, and the trace-element distribution in the host rocks around
Antamina to define the existence of outliers and the alteration halos at
different distances and levels outside this deposit.
2. Geologic framework
The Antamina copper–zinc skarn deposit is located in the eastern
flank of the western Peruvian Andes, at 9°32′S and 77°03′W, at

Fig. 1. Simplified geology map of the Antamina–Condorcocha skarn systems, showing the visible alteration zoning and the sampling areas and transects used in this study. Modified
from Compania Minera Antamina, 2002.
 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136
4300 m altitude (Fig. 1). This deposit consists of several high-grade
copper and zinc skarn ore bodies developed on a series of Miocene
quartz-monzonite porphyries and dikes of 10.57 to 10.83 Ma age
(zircon U–Pb; Escalante, 2008). These porphyritic stocks intruded into
the transition zone between the Upper Cretaceous Jumasha and
Celendin formations. The Jumasha formation consists of gray, thick
bedded, relatively pure limestone interbedded with thin layers of
marly limestone, nodular limestone and marls (Jaillard, 1986;
Angeles, 2002), which grades upwards into a sequence of thin bedded
marls, marly limestone and shales, classified by Benavides (1956) as
Celendin Formation. Not all these rocks occur at Antamina, however, a
transitional stratigraphic contact between these two formations has
been inferred by the prevalence of massive limestone horizons
converted to marble close to the skarn (Love et al., 2004).
The skarn system is recognized in a NE-SW elliptical area of
4.5 × 2 km that coincides with a subtle deflection zone of the NW-
trending, Incaic thrust and fold belt (Benavides, 1999; Love et al.,
2004). Thrust faults at Antamina apparently reactivated as exten-
sional structures in the Late Miocene at the time of intrusion and skarn
formation (Redwood, 1999). The large Cu–Zn Antamina skarn is
connected with the relatively barren Condorcocha skarn, 1.3 km to
the north, by a series of subparallel quartz feldspar porphyry (QFP)
dikes dated at 10.79 and 11.03 Ma (Fig. 1; Escalante, 2008). These
dikes are accompanied by narrow calcite + sulfide veins, which get
thicker in the upper levels of the mine, especially at Fortuna (650 m
north and 500 m above the Antamina skarn).
Five visible alteration zones are recognized around the central
quartz-monzonite porphyry: a pink to brown skarn altered intrusion
(endoskarn), a brown to green garnet skarn (exoskarn), a white and
gray marble zone, a tan hornfels and marble zone, and a external zone
of gray and light green hornfels. Fossiliferous gray limestone and
marly limestone with variable siliciclastic content predominates
outside the hornfels zone. The massive gray and white marble zone
may correspond to the relatively pure Jumasha formation, whereas
the interbedded sequence of thin bedded marble and hornfels grading
into limestone may correspond to the Celendin formation. Skarn
comprises a broad spectrum of mainly garnet-bearing rocks besides
minor amounts of diopside, calcite, quartz and vesuvianite. The white
and gray marble zone adjacent to the skarn consists mainly of coarse-
grained calcite with minor amounts of scapolite, Ca-plagioclase, K-
feldspar, phlogopite and pyrrhotite. Intermediate and distal to the
mineralized skarn at Antamina, the host rocks (tan, gray and light
green marble and hornfels) are characterized by their fine-grained
texture and the presence of phlogopitic biotite and K-feldspar
(especially the tan marble and hornfels), whereas the white, light
green and gray hornfels and marble sequence distal to the skarn
contain variable amounts of diopside, tremolite and epidote (Esca-
lante, 2008).
Sulfide mineralization is concentrated in massive sulfide bodies
and crosscutting veinlets especially within garnet-bearing rocks.
Sulfide minerals comprise pyrite, chalcopyrite, and sphalerite, with
lesser amounts of magnetite, pyrrhotite, bornite, molybdenite, and
copper-bismuth sulfosalts. Galena, bournonite, realgar and proustite
are present in trace amounts (Lehne, 1996, 1997). Pyrite is relatively
abundant in the skarn and in the thermal aureole. However,
disseminated pyrrhotite is common in the proximal white and gray
marble aureole, as well as within the 75 m outside the gray and light
green hornfels zone (Escalante, 2008).
Proximal alteration at Antamina is controlled by folded sedi-
mentary layers, thrust faults, dikes and rock schistosity. Distal
alteration at elevations above and to the north of the Antamina pit,
which is the focus of this study, is concentrated along QFP dikes that
connect the Antamina stock to the poorly mineralized Condorcocha
skarn. Meter-scale hornfels alteration aureoles enclose the dikes.
These dikes are accompanied by multiple generations of centimeter-
scale calcite ± base-metal sulfide veinlets (distal to the skarn) and
119
quartz + fluorite ± calcite ± sulfide veinlets (proximal to the skarn).
The major concentration of calcite + sulfide veins (sphalerite± galena)
occurs at Fortuna, which represent an Ag-base metal vein deposit
(Fig. 1). Calcite ± sulfide veins and veinlets occur parallel and
crosscutting the QFP dikes suggesting that these dikes acted as
conduits for escaping fluids. The stable isotopic composition of calcite
in marble, hornfels and limestone is also depleted in proximity to the
QFP dikes from sedimentary values of approximately 26‰ (VSMOW)
to values as low as 14‰ VSMOW (Escalante, et al., 2006). The lowest
d18O values in calcite are consistent with isotope exchange equilib-
rium with magmatic volatiles from the quartz-monzonite porphyries
(Escalante, 2008). Meinert et al. (2005)) have interpreted planar Fe–
Mn coatings on fracture surfaces in white marble at Antamina West as
escape conduits to mineralization (their Fig. 20D). However, because
we have not detected sulfide, trace element, or oxygen isotope
depletion halos around these features, we dispute their significance
to the overall hydrothermal system. It is interesting that there is in
general very limited oxygen isotope depletion in white marble at
Antamina West, suggesting that lateral escape of mineralizing fluid was
negligible (Escalante, 2008).
3. Sampling and methods
Ninety-eight samples chosen from a suite of over 600 hand-size rock
samples collected between 2002 and 2004 from drill core, the open pit,
and surrounding outcrops represent the various lithological units
recognized between the Antamina and Condorcocha skarn systems.
Most of the samples were taken from transects across QFP dikes that
likely acted as fluid escape conduits to the skarn deposit (Fig. 1). Transect
locations are shown in Fig. 1, and full UTM locality information for each
sample is provided in Appendices 1 and 2 in the supplemental material.
The vertical distance between each transect was approximately
30 m, and the sampling interval within each transect was 5 m on
average. Care was taken to exclude visible veins from the analyzed
sample, although it is probable that a few b1 mm-thick calcite veins
were unavoidably included. Four samples of unaltered limestone from
Jumasha and Celendin formations (two from each formation) were
taken at Yanacancha, 3 km south of the mine (Fig. 1) as a basis of
comparison of limestone around Antamina.
The selection of a specific analytical method for a geochemical study is
of crucial importance in mineral exploration and it depends on many
factors, such as element coverage, detection limits, reliability, cost, and
host rock mineralogy (Berkman, 1997). Samples were analyzed at ALS
Chemex Canada for major-element oxides, REE and trace elements on
whole rocks. Major-element oxides used in this study were determined
by X-ray fluorescence, whereas REE were analyzed by inductively
coupled plasma-mass spectrometry (ICP-MS). These analytical methods
include the fusion of samples with lithium metaborate that insure the
total dissolution of resistate minerals yielding reliable values of REE,
especially heavy REE that cannot easily be dissolved from very resistant
phases (Hall and Plant, 1992). Limits of detection for the major-element
oxides and REE are listed in Table 1. Trace elements were analyzed by ICP-
MS in samples previously dissolved with HF, HNO3, HClO4 and HCl (Four
acid, “near total” digestion procedure of ALS-Chemex). This method was
chosen because acid digestion of samples reduces solutes in the analyte
or solution matrix that lowers background or detection limits for the
trace elements than total fusion procedures (Kerrich and Wyman, 1996;
Lentz, 2009, pers. Comm.). Four acid digestion methods are preferred by
exploration companies, because it is not as expensive and time
consuming as total digestion methods. Limits of detection for trace
elements determined by the “four acid” method are listed in Table 2.
3.1. Quality assurance and quality control
Several different techniques were used in order to ensure the
reproducibility of data. As part of a larger study of the lithogeochemical
120 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136

Table 1
Averages and range of compositions of host rocks from Antamina (major elements and REE). Database obtained by XRF and ICP-MS analysis of samples previously fused with lithium
borate.

XRF Limit of detection Marble (n = 32) Limestone (n = 38) Hornfels (n = 27)

wt.%
(wt.%) Mean S.D. Range Mean S.D. Range Mean S.D. Range

SiO2 0.01 12.27 10.56 1.54–46.81 17.55 8.02 2.45–37.28 36.61 10.66 11.57–58.71
Al2O3 0.01 3.53 3.40 0.35–14.59 4.98 2.36 0.65–10.79 11.24 3.01 3.02–15.29
Fe2O3 0.01 1.31 1.01 0.25–3.66 2.01 0.76 0.44–3.47 3.21 0.85 1.17–4.98
CaO 0.01 46.03 9.45 12.17–54.1 39.29 7.09 21.82–52.71 25.25 9.18 6.79–47.21
MgO 0.01 1.69 0.86 0.85–3.72 2.20 0.65 0.91–3.93 2.83 0.49 1.73–4.16
Na2O 0.01 0.20 0.19 0.01–0.83 0.24 0.22 0.02–0.77 0.66 0.41 0.06–1.48
K2O 0.01 0.83 1.59 0.02–9.08 1.01 0.65 0.06–3.13 3.83 2.76 0.65–10.78
Cr2O3 0.01 0.01 0.01 b 0.01–0.04 0.01 0.00 b 0.01–0.03 0.01 0.01 b 0.01–0.02
TiO2 0.01 0.21 0.17 0.04–0.76 0.29 0.14 0.04–0.65 0.57 0.16 0.18–0.8
MnO 0.01 0.05 0.04 0.02–0.19 0.06 0.04 0.02–0.31 0.08 0.08 0.02–0.44
P2O5 0.01 0.08 0.05 0.02–0.21 0.10 0.04 0.03–0.19 0.15 0.03 0.1–0.24
SrO 0.01 0.09 0.05 0.04–0.26 0.08 0.02 0.03–0.11 0.06 0.02 0.03–0.09
BaO 0.01 0.01 0.01 b 0.01–0.04 0.01 0.01 b 0.01–0.03 0.03 0.02 0.01–0.09

ICP-MS ppm

Ce 0.5 30.7 31.7 4.7–131 38.1 22.6 5.6–122 76.8 25.6 26–121
Cs 0.1 2.49 2.60 0.4–10.9 4.70 3.84 0.2–19.6 3.46 2.77 0.4–10.25
Dy 0.1 1.56 1.58 0.3–6.59 2.15 1.15 0.3–5.6 4.53 1.26 1.4–6.8
Er 0.1 0.96 0.96 0.2–4.02 1.31 0.72 0.2–3.4 2.81 0.79 0.8–4.4
Eu 0.1 0.44 0.40 b 0.1–1.36 0.64 0.42 0.14–1.4 1.04 0.34 b0.1–1.8
Gd 0.1 2.04 2.07 0.3–8.58 2.63 1.39 0.4–7.4 5.42 1.45 1.8–7.83
Ho 0.1 0.32 0.33 b 0.1–1.28 0.42 0.22 b0.1–1 0.88 0.25 0.2–1.21
La 0.5 13.7 15.9 1.7–70 16.5 9.5 2.3–52.5 39.2 13.0 11.8–63.4
Lu 0.1 0.14 0.13 b 0.1–0.55 0.16 0.08 b0.1–0.4 0.38 0.13 b0.1–0.56
Nd 0.5 10.5 11.7 1.9–51.4 13.5 7.6 1.9–41.3 29.7 9.3 8.3–48.1
Pr 0.1 3.08 3.50 0.5–15.2 3.96 2.36 0.5–12.8 8.62 2.81 2.4–14.3
Rb 0.2 41.6 63.5 2.4–332 57.0 30.8 4.5–129.5 135.6 76.5 18.8–302
Sm 0.1 2.13 2.17 0.3–9.13 2.91 1.61 0.4–8.3 5.62 1.54 2–8.2
Sr 0.1 765 416 354–2130 640 152 367–999 629 154 274–880
Tb 0.1 0.27 0.30 b 0.1–1.25 0.34 0.19 b0.1–0.9 0.80 0.24 0.1–1.16
Tm 0.1 0.13 0.14 b 0.1–0.59 0.16 0.08 b0.1–0.4 0.39 0.13 b0.1–0.58
Yb 0.1 0.89 0.88 0.2–3.77 1.20 0.67 0.2–3.1 2.62 0.78 0.7–4.3
LaN/YbN 9.79 2.39 5.43–13.93 9.54 1.60 6.96–14.27 10.36 2.25 2.53–13.20
Ce/Ce* 1.23 0.19 0.96–1.62 1.19 0.17 0.79–1.61 1.04 0.10 0.95–1.37
Eu/Eu* 0.87 0.80 0.048–3.41 0.74 0.39 0.23–2.29 0.57 0.15 0.08–1.02

Ce/Ce* = CeN/((LaN)0.667 × (NdN)0.333); Eu/Eu* = EuN/(SmN × GdN)0.5; N = chondrite-normalized (data from McDonough, W.F. and Sun, S.S., 1995).

characteristics of intrusive and mineralized rocks in and around the
Antamina region. In order to assess the reproducibility of the
analytical method of ALS Chemex, ten samples were submitted as
blind duplicates to ALS Chemex. One sample for Au, Mn, and Zn,
two samples for Ag and Pb, and 4 samples for As, fall outside
the 20% (relative) range indicating poor precision or sample
heterogeneity. Overall duplicates for Au, Ag, As, Mn, Pb, and Zn
average within 15% (relative) of each other and show acceptable
reproducibility.
Four samples of Canmet standard MA-2C were submitted for
analyses along with the rock samples to help constrain the accuracy of
the analytical method. The values obtained for Ag, Cu, and Zn are
mostly within 20% of the accepted mean values for the standard, and
only one Ag value falls below 20%. The values obtained for Pb are
greater than 20% higher than the accepted mean for the standard, and
the values obtained for As and Sb are greater than 20% lower than the
accepted mean for the standard. The good precision for the duplicates
and standards suggests the relative values obtained from these
samples are real and meaningful, even if the precise values may be
significantly off for some elements.
In addition, a comparison of results from the fusion and four acid
techniques indicates a strong linear correlation for many elements
between the analytical methods, for example Al (r2 = 0.9993), Cu
(r2 = 0.973), Zn (r2 = 0.998). This means that the relative ratios of
trace elements between techniques would remain constant. As this
study utilizes elemental ratios in order to distinguish the presence or
absence of trace-element haloes, we consider that this comparison of
independent analytical techniques on samples yields the best
measure of quality of data analysis.
4. Geochemical characterization of the host rocks at Antamina
Average concentrations and ranges for major elements, REE and
trace elements in limestone, marble and hornfels are presented in
Table 1 (lithium-borate fusion) and Table 2 (“four acids”). Results of
the major and rare earth elements obtained by ICP-MS analysis of
samples prepared with lithium-borate fusion, including sample
location and description are listed in Appendix 1, whereas trace-
element data obtained by ICP-MS analysis of previously four acid
digested samples are listed in Appendix 2. All the appendices of this
study can be found in the repository data.
4.1. Major elements
4.1.1. Limestone
Major-element constituents of limestone are: CaO (22–53%), MgO
(0.9–3.9%), SiO2 (2.5–37%), Al2O3 (0.6 to 10.8%), Fe2O3 (0.4–3.5%) and
K2O (0.06–3.1%). P2O5 and Na2O are present at trace abundances,
while Cr2O3 and BaO concentrations are generally below detectable
limits (Table 1). The major-element composition of limestone around
Antamina is similar to samples of Celendín Formation limestone
collected at Yanacancha, which contains more SiO2, Al2O3, Fe2O3,
MgO, K2O, Na2O, TiO2 and La than unaltered Jumasha limestone.
Chemical composition of unaltered limestone samples taken distal to
 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136 121

Table 2
Averages and range of compositions of host rocks from Antamina (trace elements) Database obtained by ICP-MS analysis of samples previously dissolved by four acids.

Limit of Marble (n = 32) Limestone (n = 38) Hornfels (n = 28)

detection
Mean S.D. Range Mean S.D. Range Mean S.D. Range
a
Au 0.005 0.003 0.001 b 0.005–0.008 0.006 0.017 b 0.005–0.105 0.006 0.007 b0.005–0.021
Ag 0.01 0.68 1.98 0.05–11.3 0.19 0.32 b 0.01–1.91 0.61 1.05 0.04–4.05
Al % 1.00% 2.13 1.97 0.24–8.09 3.04 1.43 0.4–6.63 6.46 1.59 1.94–8.31
As 0.2 14.6 23.3 b 5–128 17.8 28.4 b5–143 47.1 54.5 5.1–243
Ba 10 65.9 72.1 10–330 85.0 49.3 10–210 305.0 192.8 40–850
Be 0.05 0.66 0.62 b0.05–2.38 0.91 0.49 0.17–2.11 2.20 0.80 0.61–3.89
Bi 0.01 2.41 5.71 0.04–30.5 0.11 0.11 0.01–0.67 1.02 1.76 0.11–7.38
Ca % 0.01 29.44 5.70 9.05–36 25.39 4.58 14.8–35.3 17.21 5.97 5.48–30.1
Cd 0.02 0.41 0.49 b0.02–1.6 0.48 0.41 0.02–1.89 0.55 1.25 b 0.02–6.47
Ce 0.01 25.58 27.06 4.45–123.5 34.60 21.14 4.86–112 73.77 23.56 25.1–110.5
Co 0.1 3.3 2.5 1.2–10 5.4 2.0 1.4–9.3 9.6 4.4 3.9–23.3
Cr 1 17 12 4–52 25 26 6–174 42 18 13–93
Cs 0.05 2.96 3.14 0.45–13.75 5.76 4.77 0.31–23.6 3.79 3.06 0.58–12.05
Cu 0.2 58.6 69.9 6.6–222 9.2 4.7 2.5–31.5 71.6 173.5 4.8–904
Fe % 0.01 0.90 0.73 0.17–2.68 1.37 0.53 0.33–2.45 2.23 0.58 0.79–3.41
Ga 0.05 5.22 4.91 0.69–21.4 7.25 3.39 1.01–15.9 16.49 6.77 4.43–44.8
Ge 0.05 0.12 0.04 0.05–0.21 0.16 0.06 0.05–0.31 0.16 0.05 0.11–0.32
Hf 0.1 0.4 0.4 0.1–1.6 0.8 0.3 0.2–1.5 1.1 0.3 0.4–1.6
Hg 0.01 0.01 0.00 b0.01–0.01 0.01 0.01 b 0.01–0.06 0.02 0.06 b 0.01–0.3
In 0.005 0.033 0.027 b 0.005–0.116 0.026 0.013 b 0.005–0.071 0.064 0.058 0.017–0.331
K% 0.01 0.71 1.00 0.03–5.56 1.01 0.61 0.09–3.12 3.10 1.72 0.65–6.88
La 0.5 12.9 13.2 2.3–56.3 17.6 10.4 2.8–55.9 38.2 14.2 13.1–80.9
Li 0.2 9.1 8.3 1.3–39.9 19.8 9.8 3.4–41.2 16.9 12.2 2–60.3
Mg % 0.01 1.05 0.55 0.48–2.41 1.38 0.41 0.56–2.46 1.69 0.28 1–2.34
Mn 5 289 263 99–1280 404 324 154–2240 601 563 224–2960
Mo 0.05 1.11 0.80 0.21–3.5 0.86 0.37 0.13–1.78 1.39 0.89 0.65–5.17
Na % 0.01 0.16 0.15 0.01–0.65 0.19 0.18 0.01–0.62 0.50 0.33 0.04–1.24
Nb 0.1 5.1 5.4 0.5–25.1 6.5 3.8 0.9–17.5 16.4 5.2 3.6–24.5
Ni 0.2 7.6 6.1 b 0.2–21.6 12.5 4.9 b 0.2–19.7 18.0 4.0 11.4–27.7
P 10 365 229 80–1010 467 174 120–860 735 168 500–1210
Pb 0.5 56.5 161.4 2.9–915 14.9 28.9 1.1–180.5 108.0 338.4 3.6–1800
Rb 0.1 38.4 58.6 1.8–325 52.8 27.6 4–119 131.0 66.8 26.2–319
Re 0.002 0.002 0.002 b 0.002–0.011 0.001 0.001 b 0.002–0.004 0.001 0.001 b0.002–0.004
S% 0.01 0.43 0.39 0.03–1.67 0.49 0.21 0.006–1.06 0.83 0.44 0.16–2.56
Sb 0.05 0.77 1.10 0.1–5.97 0.70 0.89 0.05–3.56 1.30 1.16 0.36–5.48
Se 1 1 1 b 1–3 1 1 b1–3 3 1 0.1–5
Sn 0.2 0.9 0.8 0.1–4 1.0 0.6 b 0.2–2.2 2.4 0.7 0.7–3.5
Sr 0.2 878 446 361–2330 741 165 437–1090 662 164 298–889
Ta 0.05 0.37 0.40 b0.05–1.81 0.47 0.30 0.05–1.32 1.18 0.38 0.24–1.78
Te 0.05 0.23 0.21 0.08–1.03 0.10 0.05 b 0.05–0.25 0.32 0.46 b 0.05–2.29
Th 0.2 4.0 4.4 0.3–20.4 5.2 3.3 0.6–14.7 12.9 4.4 2.8–21.4
Ti % 0.005 0.102 0.100 0.009–0.416 0.145 0.074 0.016–0.344 0.335 0.088 0.086–0.455
Tl 0.02 0.33 0.36 0.03–1.68 0.54 0.32 0.05–1.84 0.78 0.67 0.18–3.45
U 0.1 1.5 0.7 0.5–3.3 1.5 0.4 0.7–2.5 2.0 0.6 0.9–4.4
V 1 34 35 5–118 71 32 5–133 110 19 58–148
W 0.1 1.1 1.9 0.1–9 0.7 0.5 0.1–2.2 2.4 3.8 0.3–21.4
Y 0.1 8.2 6.8 1.8–28.9 12.0 5.3 2–26.1 23.0 5.8 8.7–32.9
Zn 2 126 166 5–610 78 74 15–436 151 311 14–1650
Zr 0.5 12.7 12.3 1.4–48.3 27.7 10.6 5–49.3 30.4 8.8 12.6–49

Trace-element data are in ppm, otherwise stated.

S.D. = standard deviation.
Data reported as not detected were assigned values to one-half the analytical detection limit (Sanford et al., 1993).
a
Au results are based on 27 samples of marble, 36 samples of limestone and 6 samples of hornfels.

the QFP dikes (N100 m) spans a range of values between Celendin and
Jumasha, which makes it difficult to identify the stratigraphic unit that
host the mineralization at Antamina. In general, SiO2 correlates with
Al2O3, Fe2O3, K2O and La (Fig. 2A to E), which together are taken to
reflect variations in the siliciclastic component of limestones. Low
SiO2/Al2O3 ratios for limestone (average 3.63) are consistent with a
detrital source of silica in limestone (Slack et al., 2004). The plot of
SiO2/Al2O3 versus TiO2 (Fig. 2F) for limestone shows that some
samples taken at distances less than 100 m from QFP dikes generally
contain more TiO2 than limestone distal to dikes.
4.1.2. Marble
Five different marble units are recognized in Antamina based on
color: gray, light gray, light green, tan and white. Gray and white
marble have higher CaO and lower Al2O3, SiO2, Fe2O3 and K2O content
than average limestone (Fig. 3A, B and C). Fine-grained marble found
outside the Antamina West zone (tan, light gray and light green)
generally contains more MgO than the gray and white, coarse-grained
marble units. The chemical composition of marble units close to the
skarn front, especially at Antamina West, is very similar to that of the
unaltered Jumasha limestone taken at Yanacancha. The green and tan
marble units are generally richer in most of the major elements (SiO2,
Al2O3, Fe2O3, MgO and La) than other marble units and unaltered
limestone (Fig. 3A, B). The K2O and Na2O contents of the green and tan
marbles are also high with the exception of one sample of tan marble
taken at Antamina West, which contains the lowest value of K2O and
Na2O. The green and tan marbles also contain the lowest values of
calcium. Fig. 3F shows a trend between tan marble with low SiO2/
122 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136

Fig. 2. Plots of representative major elements versus silica (A, B, C) and bivariate plots of relatively insoluble elements for limestone rocks from Antamina (D, E, F). Observe the
relative low silica and titanium content of samples taken at distances greater than 100 m from QFP dikes. Observe also the composition of limestone taken at Antamina is similar to
the Celendin Formation limestone taken at Yanacancha.

Al2O3 white, light gray, green and gray marble with progressively
higher SiO2/Al2O3 values and lower TiO2 content. Plots of La versus
SiO2 and La versus Al2O3 show that some samples of tan marble occur
outside the limestone field. The near constant SiO2: La and Al2O3: La
ratios between limestone and tan marble and the higher content of
SiO2, La and Al2O3 in tan marble (Fig. 3D and E) require either that
they were derived from a limestone protolith that is not prevalent
outside the area of alteration, or that the value represents chemical
alteration. One way to elevate concentrations at fixed ratios is passive
enrichment during mass loss. Therefore, covariations of SiO2, Al2O3
and La are attributed to hydrothermal alteration via carbonate
dissolution.
4.1.3. Hornfels
In general, hornfels silica content is greater than unaltered
limestone. Gray and light gray hornfels show a broad range of values
in SiO2 content, but it is generally similar to those found in limestone
proximal to the QFP dikes (Fig. 4A and B). Tan, white, light green and
green hornfels contain slightly higher Al2O3, SiO2 and K2O values (Fig.
4A and C) and lower CaO and SrO. Average SiO2, Al2O3 and K2O
contents of white hornfels are higher than other hornfels. In general,
there is not a significant variation in the Fe2O3, MgO, Na2O and MnO
content of all hornfels, which are similar to concentrations in
limestones and marbles. A plot of SiO2/Al2O3 versus TiO2 for hornfels
(Fig. 4F) shows that similar SiO2/Al2O3 ratios between unaltered
limestone and hornfels, but striking higher amounts of TiO2 in
hornfels especially in white, tan, green and light green hornfels. Plots
of La versus SiO2 and Al2O3 for hornfels suggest that elevated
siliciclastic content are the product of carbonate dissolution (Fig. 4D
and E).
4.2. Rare earth elements (REE)
Rare earth element (REE) abundances (see Appendix 1) were
normalized to chondrite (McDonough and Sun, 1995; see Appendix 3).
Chondrite-normalized values were plotted for each rock type, and
compared to limestones, in order to determine REE variations in the
different alteration zones around Antamina (Figs. 5 and 6).
4.2.1. Limestone
Variations in chondrite-normalized variations (1–100× chondrite)
for limestones from Antamina (n = 38) are interpreted to represent
 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136 123

Fig. 3. Plots of representative major elements versus silica (A, B, C) and bivariate plots of relatively insoluble elements for the different types of marble recognized at Antamina
(D, E, F). Fields of all limestone samples as well as limestone located at distances greater than 100 m from QFP are plotted for reference. Observe the almost linear correlation of
lanthanum with silica and aluminum (D, E) suggesting that tan marble is the product of strong dissolved limestone.

variable siliciclastic input (Fig. 5A). Samples from the Jumasha
formation taken at Yanacancha contain the lowest REE values,
whereas the rest of samples show a broad range of REE that overlaps
with the REE composition of the Celendin Formation. The broad range
of REE suggests significant variations in the amount of siliciclastic
material in limestone around Antamina.
4.2.2. Marble
REE contents of gray, light gray and green marble span almost the
same range defined by limestone (Fig. 5B, C and E) where light gray
marble shows a negative Eu anomaly.
4.2.3. Hornfels
REE contents of hornfels span the upper end of the range defined
by limestone, especially gray and light gray hornfels (Fig. 6A and B).
Light green, white, green and tan hornfels have very similar profiles
characterized by higher REE content than limestone (Fig. 6C, D, E and
F). REE concentrations are higher than those found in the REE profile
of the samples taken at Yanacancha and distal to the QFP dikes
(N100 m).
5. Interpretation of geochemical data
Bivariate plots of SiO2, Al2O3, TiO2, Zr, La, Ce and Nd were used to
identify the least-mobile elements and determine the removal or
addition of other components. Lanthanum and Al2O3 were considered
as parameters to calculate the variation in siliciclastic content of
samples because of their relative abundance and highly correlated
trends with other insoluble elements. Lanthanides are also good
tracers of the source of sediments because of their low mobility,
uniform distribution and they are relatively easy to measure (Zhang
et al, 2001). It is demonstrated in this study that threshold values
calculated by using the ratio of metal/La or metal/Al2O3 for each
sample permit the identification of genuine anomalous metal
concentrations, rather than the traditional statistical methods,
which analyze only metal values. Normalization of measured metal
values against an “immobile” element like La (MacLean and Barrett,
1993) helps to recognize the addition or subtraction of elements, and
the extent of alteration and is used in a similar fashion to assess
alteration in VHMS environments (Finlow-Bates and Stumpfl, 1981;
MacLean and Barrett, 1993; Gifkins et al., 2005). The inclusion of
124 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136

Fig. 4. Plots of representative major elements versus silica (A, B, C) and bivariate plots of relatively insoluble elements for the different types of hornfels recognized at Antamina
(D, E, F). Fields of all limestone samples as well as limestone located at distances greater than 100 m from QFP dikes are plotted for reference. The relative high amount of
insoluble elements in hornfels and the linear correlation of lanthanum with silica in limestone and hornfels suggest that hornfels especially white, light green, green and tan
hornfels are the products of limestone dissolution.

individual threshold values in the plots of measured metal values
versus distance from dikes permits the identification of anomalous
samples and geochemical halos to fluid flow conduits more
accurately.
Marble and hornfels span a greater range in major-element
content than limestone at Antamina. Strong correlation of SiO2 with
Al2O3, Fe2O3, K2O and La reflects variations in the siliciclastic
component of limestone. The low siliciclastic component of Jumasha
limestone from Yanacancha indicates the predominance of Celendin
formation around Antamina and Fortuna also recognized with
stratigraphic analysis (Love et al., 2004). Relative higher contents of
SiO2, Al2O3 and TiO2 in limestone proximal to the fluid conduits
(b100 m) suggest increased carbonate dissolution in these rocks.
However, major-element and REE content of host rocks, especially
marble and hornfels, do not always show a progressive enrichment
towards the dikes (Fig. 7).
The silica-poor, carbonate-rich extremes in marble composition
reflect isochemical derivation from Jumasha limestone, whereas the
large overlap of limestone with marble in major-element composition
reflects predominance of the Celendín formation at Antamina (Fig. 3).
Samples of Jumasha limestone from Yanacancha are similar in
composition to gray and white marble at Antamina West and are
broadly representative of protolith marble at that area. The carbonate-
rich composition and REE pattern of white marble resemble that of
Jumasha limestone (Figs. 3, 5A and D), whereas the broad range of REE
values of gray and light gray marble (Fig. 5B and C) suggests they
derive from both Jumasha and Celendín formations.
On the other hand, the siliciclastic content of tan and green
marble is at the high end of the range defined by limestone (Fig. 5E
and F). This may reflect carbonate dissolution during hydrothermal
circulation or derivation from limestone with above average
siliciclastic content. The trend between tan marble with low SiO2/
Al2O3 and relative high TiO2, and light gray, green and gray marble
with progressively higher SiO2/Al2O3 and low TiO2 suggests that
titanium enrichment of tan marble is due to carbonate dissolution
(Fig. 3F).
 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136 125

Fig. 5. CI chondrite-normalized REE diagrams for limestone and marble from Antamina. CI chondrite-normalizing values from McDonough and Sun (1995). (A) Limestone from
Antamina and Yanacancha. Graphs B, C, D, E and F show the REE content of gray, light gray, white, green and tan marble, respectively, in relation to the field of REE determined for
limestone samples. Gray pattern shows range of REE patterns for limestones.

Similar siliciclastic content of gray hornfels and limestone (Fig. 4)
suggests a thermal metamorphic origin for gray hornfels. Green, light
green, white and tan hornfel compositions suggest that they may
represent the products of alteration and hydrothermal circulation
because of their relatively high Al2O3 and SiO2 content (Fig. 4). Similar
REE patterns of hornfels and limestone (Fig. 6) suggest that hornfels
are the products of carbonate dissolution.
5.1. Trace-element composition of host rocks
In contrast to major and REE compositions, trace-element
abundances vary substantially within outcrop, with variations most
notable in samples collected proximal to major fluid conduits (i.e.
skarn front and QFP dikes — see Fig. 7). Samples proximal to these
fluid conduits commonly contain higher metal values than distal ones
(Rose et al., 1979). In general, trace-element concentrations in
limestone, hornfels and marble located distal to dike and major vein
systems have similar trace-element concentrations to the Yanacancha
limestones. The concentrations of trace-elements in samples collected
adjacent to the fluid conduits are irregular and are controlled by the
host rock and the amount of sulfides associated with the mineralizing
conduit.
Standard statistical distributions are commonly used to describe
low concentrations of trace elements (Monecke et al., 2005).
Frequency distribution of elements was used to observe the shape,
symmetry and modality of each element within the host rocks to
Antamina skarn deposit. Nine metals (Ag, As, Bi, Cu, Mo, Pb, Sb, Tl
and Zn) were selected because of their abundance and strong
association with each other. Frequency histograms were prepared
for these metals for each type of rock. These histograms show the
distribution of 38 samples of limestone, 25 of hornfels and 31 of
marble. Three samples of hornfels (2PAE233, 3PAA121, and
4PAA211) and 1 sample of marble (3PAA134) were excluded from
this analysis because of their extremely high values of Ag, As, Bi, Cu,
Pb and Zn. The histogram bin width was determined using Scott's
formula (Scott, 1979):
1=3
Bin width = 3:49*σ = N ð1Þ
126 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136

Fig. 6. CI chondrite-normalized REE diagrams of hornfels from Antamina. CI chondrite-normalizing values from McDonough and Sun (1995). Most of the hornfels occupy the upper
sector of the limestone field (C, D, E, F) with the exception of gray and light gray hornfels (A,B), which are similar to the composition of tan marble (Fig. 5F). Gray region shows range
of REE patterns for limestones.

where σ is the standard deviation of the distribution and N is the
number of samples. This formula provides the most efficient, unbiased
estimation of a probability density function (Scott, 1979).
Combined metal histograms for limestone, hornfels and marble
indicate two types of statistical distributions for the nine most
abundant metals in Antamina: normal (Mo and Tl) and exponential
(Ag, As, Bi, Cu, Pb, Sb, and Zn). These distributions are confirmed by
logarithm-transformed histograms that yield normal distributions for
Ag, Bi, Cu, Mo, Pb, Sb, Tl and Zn with slight positive and negative
skewness. Log-transformed histogram of As displays a bimodal
distribution. Representative histograms for Ag, As, Cu, Mo and Zn
are shown in Appendix 4. The existence of diverse statistical
distributions for the trace elements at Antamina suggests that the
proper selection of threshold values requires the statistical estimation
of the variability of the dataset.
5.2. Background and threshold determination
The selection of background geochemical values for areas affected
by hydrothermal metasomatism should consider the frequency
distribution of the element concentration, the spatial variability and
the original composition of the protolith. Traditionally, the geochem-
ical threshold or the upper limit of a range of background values is
defined as the high value resulting in the mean ± 2σ formula. The
identification of outliers requires the estimation of the threshold
values that define the extreme range of a statistical distribution
(Reimann et al., 2005). Background is defined as the normal
distribution of a series of samples (mean ± 2σ) assuming that the
samples belong to a normal or lognormal distribution (Matschullat
et al., 2000). However, geochemical datasets rarely follow a normal
distribution (Reimann and Filzmoser, 2000). In that case, the mean ±
2σ is not a robust estimator of background and threshold (Reimann
et al., 2005). In order to avoid assumptions of normal statistical
distributions, the median and the median absolute deviation (MAD)
may instead be used because these estimators are shown to provide
the lowest threshold values and would help to identify the highest
number of outliers (Reimann et al., 2005).
Bivariate graphs reveal strong correlations between selected
lanthanides and major elements (Fig. 7). Therefore, ratios of trace
elements (metals) to immobile elements allow recognition of variable
 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136
Fig. 7. Diagrams of SiO2, Al2O3 and La content versus distance to the fluid conduit for transects 5, 2, 16 and 17. Values of limestone at Fortuna show a progressive enrichment towards the dike. However, this feature is not observe in transects
proximal to the skarn at Antamina.

127
 128
A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136
Fig. 8. Bivariate plots of selected immobile elements for limestone, marble, hornfels and skarn from Antamina. (A, B, C) SiO2 versus La, Ce and Nd. (D, E, F) Al2O3 versus La, Ce and Nd. G, H, I: TiO2 versus La, Ce and Nd.
 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136 129

siliclastic content in limestones. In order to estimate thresholds, we

ppm

225

138
100

177
65
62

90

15
62
95

55
Zn
normalize the metal concentration of the host rocks to the
concentration of “immobile or least-mobile” elements. Ratios of

ppm
metal to immobile element concentrations have been used in

0.6
0.6
0.2
0.6
0.4
0.9
0.2
0.5
0.5
0.1
0.1
W
previous studies (Farmer, 1991; Klassen, 2001) to determine the
effects of weathering and anthropogenic enrichment. We have

ppm

0.31
0.31

0.38
0.47
0.48
0.23
0.37
0.55
0.06
0.05
0.3
Tl
selected La and Al2O3 as “immobile” elements to normalize the
ppm metal values at Antamina because of their relative abundance and
1.1 strong positive linear correlation with other low-solubility elements
0.9
0.4
1.1
0.7

0.4

0.2
0.2
Sn

1
1
(Fig. 8), and use La as an example to determine threshold metal:
immobile element ratios. The vast majority of samples presented in
ppm

0.37
0.29
0.63
0.35
0.22
1.63
0.14
0.19
0.25
0.05
0.23
this study were collected from limestones and marbles distal to the
Sb

skarn. Therefore, these samples most likely never reached tempera-

ppm

tures were significant Al or La mobility would be likely (Leitch and

15.3
8.7
7.6
4.8

8.4
9.9
3.9
8.9
7.2
1.5
1.1
Pb

Lentz, 1994). Moreover, the relatively constant ratios of La to Si and La

to Al require either that these elements were altered in the same ratio
ppm

0.53
0.82
0.63

0.52
1.59
0.36
0.66
0.47
0.31
0.13
Mo

0.7

at which they were originally present, or where functionally immobile

during alteration.
Histograms of normalized metal values for hornfels, marble and
ppm

297
363
496
313
303
335
192
249
278
154
172
Mn

limestone also show variable distributions with the predominance of

exponential distributions (Appendix 5). Histograms of the logarithm
ME-MS61

of these normalized values provide normal distributions for the

0.0025
0.0025
0.025
0.028
0.017
0.026
0.019
0.026
0.011
0.021
0.025

majority of trace elements examined, however some bimodal

ppm
In

distributions are also observed in the histograms of Ag in limestone

and, As, Mo and Zn in marble (Appendix 5). Therefore, the use of the
Hg-CV41

mean ± 2σ even of the metal/immobile elements to estimate the

0.005

0.005
0.005
0.005

0.005
0.005
ppm

0.03

0.01

0.02
0.03
0.01

geochemical threshold would lead to erroneous estimation of

Hg

anomalous geochemical halos to fluid conduits. We consider that

the geochemical background (or threshold) of a suite of impure
ppm

2.5
10.4

10.7
6.1
6.8

6.3

3.3

2.6
Cu

10

10
7

carbonate rocks should be estimated by using the median ± 2MAD

formula of the normalized values of metals to an immobile element.
ppm

The problem of the spatial variability of samples (Li et al., 2003)

0.49
0.38
1.89
0.56
1.08
0.59
0.14
0.54
0.67
1.25
0.02
Cd

can be ignored in this case because of the relative small number of

samples and the small area they represent. Eleven samples of
ppm

0.09
0.08
0.09

0.07
0.08
0.04
0.08
0.08
0.01
0.02
0.1

limestone were used to calculate the background and threshold

Bi

values (Table 3). These samples included four samples of unaltered

limestone from Yanacancha (3 km south of the mine) and seven
ppm

70
80
20
90
40
80
40
40
50
30
10
Ba

samples of limestone taken at distances greater than 100 m from the

QFP dikes, which are considered the most likely fluid escape conduits
ppm

2.5

2.5

2.5

2.5

2.5

to the Antamina ore deposit because of visible signs of fluid flow and
40

15
8

5
5
As

alteration such as calcite + sulfide veins.

ME-MS61

0.005

0.005
ppm

0.05
0.22
0.11
0.07
0.22
0.04
0.03
0.06

0.05

5.2.1. Mathematical procedure

Ag

The procedure to calculate the geochemical background and

threshold of one metal (i.e. Cu) used in this study start with the
from dike (m)

estimation of the median of the metal/La ratios (MedianCu/La) and the

Distance

median absolute deviation of the metal/La ratios (MADCu/La) of the 11

100
103
108
132
132
144
162
N 100
N 100
N 100
N 100

unaltered limestone samples taken at Antamina. The values obtained

were 0.6446 and 0.1246 for the Median Cu/La and MAD Cu/La ,
respectively.
Fortuna East
Fortuna East

Fortuna East

Fortuna East

Samples in bold numbers are half the detection limit.

Yanacancha
Yanacancha
Yanacancha
Yanacancha
Samples used to estimate geochemical background.

Fortuna

Fortuna

Fortuna
Locality
Northing

8946509
8946064
8946098
8946528
8946080
8946044
8946100
8941908
8941606
8941344
8941034

Table 4
Upper background values of metal/La ratios calculated 1 using the median + 2MAD
formula on 11 unaltered samples from Antamina.

Metal Geochemical Metal Geochemical Metal Geochemical

273885
273637
273126
273911
273092
273595
273044
276497
275598
275208
275510
Easting

background background background

Ag 0.01701 Hg 0.0023 Sn 0.0864

As 0.7829 In 0.0021 Tl 0.0375
Ba 6.7045 Mn 38.97 V 6.646
4PAA124
3PAA250
4PAA164
4PAA223
4PAA165
4PAA224
4PAA166
4PAA233
4PAA238
4PAA235
4PAA236
Sample

Bi 0.0085 Mo 0.0738 W 0.0465

Table 3

Cd 0.0609 Pb 0.706 Zn 14.453

no.

Cu 0.8939 Sb 0.0330
130 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136

The upper background limit (U.B.) was then obtained by adding
MedianCu/La plus 2 × MADCu/La values (0.8939). This value is consid-
ered as the upper background limit of the Cu/La ratio for all the
samples at Antamina. The upper background results (U.B.) for the 17
elements examined are shown in Table 4.
Positive and negative threshold values of one element for each
sample are defined by multiplying its lanthanum content by the
Median + 2MAD or Median − 2MAD results, respectively. Plotting
these values in a metal versus lanthanum graph appear as two lines
that we define as the upper and lower limits of threshold,
respectively. We use the upper limit of threshold in this study
because positive anomalies suggest a source for metal enrichment
other than surrounding country rocks (Shi Changyi and Wang
Caifang, 1995). These graphs can also be used to identify true and
false positive and negative anomalies in relation to an empirical
threshold line determined graphically, or using the traditional
statistical methods (as it is shown in Fig. 9 for Cu).
Results of the product of upper background value multiplied by the
La content of each sample identify an individual threshold value for all
the samples. Threshold determination for each sample addresses the
problem of spatial variation of samples. The plot of threshold values
and the measured metal values versus the distance to a fluid conduit is
used to constrain the presence of geochemical halos in all the
sampling transects at Antamina (Fig. 10). The database and systematic
procedure to calculate the high and low threshold of Cu using the
median + 2MAD formula for marble samples taken at Antamina are
given in Appendix 6. Appendix 6 also contains the data used to plot
the mean Cu/La, and the median Cu/La for each sample as well as the
threshold values determined by the mean Cu + 2σ and the visual cut-
off.
Bivariate plots of metals and lanthanum along with the values of
the upper and lower threshold values are used to determine the
outliers in set of samples related to a specific type of rock. Threshold
values follow a linear distribution (Fig. 9) and all the values above
the upper threshold line represent positive outliers probably
derived from the alteration of the rock. This plot is also used to
identify true and false anomalies relative to a pre-determined visual
cut-off, which are determined in bivariate graphs of metal content
versus distance to the fluid conduit (Fig. 10C). Visual cut-offs
determined at Antamina for the 18 elements used in exploration of

Fig. 9. Copper content versus lanthanum graphs for (A) limestone, (B) marble and (C) hornfels from Antamina. Observe the distribution of samples in relation to the upper and lower
threshold lines, to the mean and median of Cu/La, and relative to the visual cut-off obtained by construction of the graph of metal content versus distance to a dike. Threshold values
of these graphs have been estimated by using the median ± 2MAD of the Cu/La ratios.
 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136 131

Table 6
Alteration halos to the skarn front at Antamina West determined by analytical and
empirical methods.

Element Lithium-borate Four acid Median + Mean + Visual

fusion digestion 2MAD 2SDEV cut-off

Ag 147 147 147 98 147

As 68 68 0 0 0
Ba 0 0 0 0 0
Bi 145 145 98 98 98
Cd 29 29 0 0 0
Cu 247 247 71 71 71
In 29 29 29 27 29
Mn 29 29 0 0 0
Mo 157 157 98 0 98
Pb 147 147 0 0 0
Sb 147 147 0 0 0
Sn 18 22 0 0 0
Sr 247 247 0 0 0
Tl 0 0 0 0 0
V 0 0 0 0 0
W 125 125 27 27 27
Zn 118 118 98 70 98

immobile elements reveal samples affected by carbonate dissolution.

Fig. 10. Plots of Cu abundance in marble versus distance to the skarn front at Antamina
West. Graphs A and B show the distribution of individual threshold values calculated by
using the median + 2MAD of Cu/La values multiplied by the La content of each sample.
Lanthanum values used in figure A come from lithium metaborate fusion + ICP-MS
analysis (ME-MS81), whereas La values used in figure B come from four acid digestion
+ ICP-MS analysis (ME-MS61). Figure C shows the geochemical halo obtained by
comparison of the measured data with a visual cut-off line and with a threshold line
estimated by the mean + 2SDEV (σ) of unnormalized data.
base-metal deposits are shown in Table 5. Samples below the upper
threshold and visual cut-off lines will identify totally unaltered
samples (Fig. 9).
6. Geochemical halos to fluid conduits
6.1. Criteria of identification
Major and REE compositions of samples indicate a varied suite of
carbonate host rocks around Antamina. Plots of metals versus
Measured and threshold values for each sample are plotted against
distance to a closer mineralizing fluid conduit (i.e. skarn front, sulfide
vein or igneous intrusion body; Fig. 10). Geochemical anomalies or
alteration halos are defined as a cluster of one or more samples
proximal to a fluid conduit with measured values higher than their
respective threshold values. Samples with metal concentrations that
do not exceed threshold values may be included within a geochemical
halo if they occur within a broader cluster of elevated values. Trace-
element halos defined at Antamina using metal:immobile element
ratios vary in extent from a few centimeters to hundreds of meters.
The presence of sporadic anomalous samples far away from a main
fluid conduit may indicate the proximity of another fluid conduit or
may represent false anomalies (reflecting high siliciclastic content of
the protolith or contaminated samples). Metal versus La or Al2O3 plots
may be used to test for false anomalies (Fig. 9).
Three plots of metal content versus distance to the fluid conduit
were created for each transect (Escalante, 2008). The first considers
threshold values calculated using lanthanum values obtained by
lithium-borate fusion extraction, the second graph shows threshold
values calculated using lanthanum values obtained by four acid
digestion methods, and the third graph shows all the measured values
in the sampling transect along with the threshold lines determined
visually and using the mean + 2σ formula. An example of these plots
showing the graphical procedure to define the geochemical anoma-
lous halo for copper at the Antamina West transect is shown in Fig. 10.
The complete list of alteration halos for the 17 metals examined at
Antamina West is shown in Table 6. This table also includes alteration
halos estimated by the use of the median + 2MAD and mean + 2σ of
measured samples without normalization.

6.2. Definition of alteration halos

Table 5 The graphs of alteration halos determined for Cu at the Antamina

Visual cut-off values of trace elements in Antamina host rocks. West transect by different methods (Fig. 10) indicate a high
Element ppm Element ppm Element ppm correlation between data obtained using both lithium-borate fusion
and four acid digestion chemical procedures. Therefore, any of these
Au 0.01 Cu 10 Sb 1
Ag 0.1 Hg 0.01 Sn 2
analytical methods can be reliably used to define the geochemical
As 10 In 0.03 Tl 1 threshold in a suite of carbonate rocks. Geochemical alteration halos
Ba 100 Mn 800 V 150 determined and examined in this study are based on threshold values
Bi 0.1 Mo 1 W 1 of metal/La ratios, where lanthanum values were obtained by lithium
Cd 1 Pb 25 Zn 100
metaborate fusion procedures.
 132
A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136
Fig. 11. Anomalous halos of Cu, As, Pb and Tl to the paleo fluid escape conduits of the Antamina skarn deposit. Observe the wide halos at depth and almost no halos at shallow levels for Cu.
 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136 133

Fig. 12. Trace-element halo with depth proximal and distal to the Cu–Zn Antamina skarn deposit. Observe the progressive thinner halos of Cu, Sb and Pb as we move away from the
skarn front (4250 m). Also, notice moderate to low temperature indicator elements (Tl) define halos at shallow levels but not close to the skarn.

Diagrams of metal abundance versus distance to the skarn front or conduits at Antamina are shown as examples in Fig. 11. These graphs
the QFP dikes were constructed for Ag, As, Ba, Bi, Cd, Cu, Hg, In, Mn, indicate the presence of four groups of elements, based on the lateral
Mo, Pb, Sb, Sn, Tl, W and Zn, and plotted in relation to their distance to and vertical extension of the halos they determine (Fig. 12). Copper,
the Antamina skarn deposit. Halos of As, Cu, Pb and Tl to the fluid Bi, Mo and Zn form the first group with strong halos at deeper levels
134 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136
Fig. 13. Synthesis of geochemical halos proximal and distal to the Cu–Zn Antamina skarn deposit.
(N100 m) that diminish in extension at intermediate levels disap-
pearing at shallower levels. Cadmium and Sn form the second group of
elements with small halos only at deeper levels. Prevalent deep to
shallow halos characterize the third group of elements, which consists
of Ag, As, Pb, Sb, In, Mn and W. These elements form halos that range
between 30 and 150 m at depth, and average 35 m in width at shallow
levels. Thallium and barium form the fourth group of elements with
moderate (60 m) to thin halos (5 m) from shallow to intermediate
levels. No halos are recognized for Hg and V.
A synthesis of the geochemical halos distal to the Antamina skarn
deposit is shown in Fig. 13. Large geochemical halos (∼150 m)
characterize the zone of coarse-grained white and gray marble
adjacent to the skarn (Antamina West), which include the presence
of anomalous values of Cu, Ag, Bi, Mo, Zn, Pb, Sb, Cd, Sn and W. Halos
up to 85 m of Cu, Pb and In are distinguished in the aureole of fine-
grained marble and hornfels zone (Quarry Bench). Geochemical halos
vary in extension from less than 1 m up to 66 m within the sequence
of thin-layered limestone that surrounds Antamina. At intermediate
levels (4450 m to 4550 m) these halos are formed by Pb, Sb, Cu, Mo,
As, Tl and Ba, whereas at shallow levels (4700 m) they consist of As, Tl,
Pb, Sb, In, Mn, Ag, W and Ba. Halos in limestone correlate with the
presence of sulfide veins along dikes, suggesting a leakage from these
mineralized structures.
In summary, high temperature indicator elements (Cu, Bi and Mo)
form large geochemical halos close to the skarn deposit, whereas
moderate to low temperature indicator elements, such as Tl define
halos at higher and more distal levels.
7. Discussion
Major and trace element as well as REE values of most of the
country rocks to the Antamina skarn deposit indicate an important
siliciclastic component of these rocks. Linear correlation observed in
the bivariate diagrams of major elements versus silica (Figs. 2–4) and
versus immobile elements for limestone, marble and hornfels (Fig. 8)
indicates a progressive siliciclastic enrichment of limestone closer to
the QFP dikes, as well as tan, green, light green, white marble and
hornfels. The progressive reduction in the CaO and LOI content of
these rocks suggests strong carbonate dissolution by acidic fluids and
permeability enhancement due to volume change (Lentz, 2005). The
trend between tan marble with low SiO2/Al2O3, white, light gray,
green and gray marble with progressively higher SiO2/Al2O3 (Fig. 3F)
supports this hypothesis.
The high volume of mineralized skarn (endo- and exoskarn) at
Antamina suggests the production of high amounts of carbonic acid
and CO2 that apparently got trapped in the skarn area by the coarse-
grained marble envelope. Fluid escape through more permeable
fractures and certain sedimentary layers explains the heterogeneous
distribution of marble and hornfels around Antamina. The presence of
quartz and calcite + sulfide veins adjacent to the QFP dikes from the
deep to shallow levels at Antamina indicates they were the preferred
pathways of the spent mineralizing fluids. However, low SiO2/Al2O3
ratios of limestone indicate no addition of silica in these rocks even in
samples proximal to the dikes, confirming a passive trace-element
enrichment of the rocks close to the dikes mainly due to processes of
carbonate dissolution.
Constraints on the recognition of geochemical halos in heteroge-
neous carbonate rocks distal to a skarn deposit are based on three
observations. Firstly, the identification of the large-scale fluid escape
pathways to these deposits. Secondly, the recognition of the trace-
element enrichment processes on the country rocks and, thirdly, the
systematic selection of anomalous values relative to a geochemical
threshold determined for each sample. The identification of the
longest fluid escape conduits is important to track the lateral and
vertical zonation of the spent mineralizing fluids. Mineralogy, trace-
element composition and stable isotope analysis on veins associated
with large structures (dikes, faults) can be used to determine the link
between proximal and distal expressions of an intrusive-centered ore
deposit such as Antamina. Trace-element halos to the QFP dikes
extend farther than the thermal aureole of the Antamina skarn.
However, these halos can be linked to the Antamina deposit, because
they reflect the interaction of progressively lower temperature fluids
with carbonate rocks (as suggested by the metal zonation).
It is demonstrated in this study that the relative enrichment of
major and trace elements in marble and hornfels around the skarn,
and limestone adjacent to the QFP dikes is due to processes of
carbonate dissolution. Therefore, metal concentrations normalized
against a least-mobile element (e.g. La) avoid the influence of the
inherited siliciclastic material and allow the recognition of true
anomalous values.
Determination of anomalous values demands the appropriate
estimation of background and threshold values besides the proper
selection of representative samples. Drawbacks in the selection of the
 A. Escalante et al. / Journal of Geochemical Exploration 105 (2010) 117–136
best method to determine threshold values in carbonate rock
environments may be solved by the proper geochemical character-
ization of the rocks, and then by the analysis of the statistical
distribution of samples to select the appropriate threshold formula. In
this study we have selected the use of the median ± 2 median
absolute deviation of samples (MAD; Reimann et al., 2005),
considering that most of the metals do not follow a normal
distribution and the fact that the use of the mean ± 2σ may be
misleading. Plots of metal versus lanthanum (along with the
threshold value for each sample) are key to identify the existence of
false positive and negative anomalous values, and provide a robust
estimator of the anomalous geochemical halos to fluid conduits
outside a mineral deposit.
Determination of halos using the threshold value for each sample
can be a straightforward process when measured values close to fluid
conduits are several orders of magnitude higher than threshold
values. Measured values slightly higher than or similar to threshold
values close to the fluid conduits can yield some uncertainty to this
procedure. Therefore these values should not be considered as
anomalous, and no halos should be reported to these transects.
7.1. Implications for Mineral Exploration
The results of our lithogeochemical study of the Antamina skarn
deposit and surroundings have potential applications in the general
exploration for intrusion-centered polymetallic deposits. Identifica-
tions of mineralizing fluid conduits and trace-element anomalous
halos to mineral deposits are key factors to enable recognition of the
extent of rock–fluid interaction in areas with subtle or no visible
alteration. Large-scale zonation of trace elements from the skarn to
limestone defines a wide halo at depth and moderate to thin halos in
limestone around fluid conduits. These halos are continuous and can
be recognized up to 1000 m away from the skarn deposit (along fluid
conduits). As shown in this study, these halos define patterns of
alteration that also indicates the spatial variability of the elements
according to the typical patterns of zonation and paragenetic
sequences established by Emmons (1936) for many hydrothermal
deposits. This zoning can be used to vector towards concealed Cu–Zn
skarn deposits such as Antamina in areas with poor exposure of
mineralized showings.
Acknowledgements
This study is part of the PhD dissertation of the senior author
developed at the Mineral Deposit Research Unit at the University of
British Columbia. Anglo American Exploration Peru, BHP Billiton,
Compania Minera Antamina, Compania de Minas Buenaventura,
Noranda, Phelps Dodge, Teck Cominco and the Natural Science and
Engineering Research Council of Canada (NSERC) provided financial
support. Eric Lipten, Manuel Pacheco, Michael Sanchez and John
Espinoza supported fieldwork. This is MDRU publication 260.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.gexplo.2010.04.011.
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