©2020 Society of Economic Geologists, Inc.

Economic Geology, v. 115, no. 1, pp. 177–188

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CLASSIFYING SKARNS AND QUANTIFYING METASOMATISM AT THE ANTAMINA DEPOSIT, PERU:

INSIGHTS FROM WHOLE-ROCK GEOCHEMISTRY

Stephanie A. Mrozek,1,† Zhaoshan Chang,1,2 Carl Spandler,1 Steve Windle,3,4 Cesar Raraz,3 and Alberto Paz3
1Economic Geology Research Center (EGRU), James Cook University, Townsville, Queensland 4811, Australia
2Department of Geology and Geological Engineering, Colorado School of Mines, Golden, Colorado 80401, USA
3Compañía Minera Antamina, Av. El Derby #055, Surco, Lima 15000, Peru
4Monazita SAC, Enrique Palacios 210, Dpto 803, Miraflores, Lima 15074, Peru

Abstract
At the Antamina deposit, Peru, accurate classification of exoskarns and endoskarns can be problematic when
textures are mottled. In this study, we use whole-rock geochemical compositions (62 elements) of 221 samples
to differentiate texturally similar endoskarns and exoskarns by comparing their compositions to least altered
precursors (wall rocks and intrusive rocks). We present a simple method for discriminating these skarn types
using immobile element bivariate plots. The most effective discriminators partition endoskarn and exoskarn
into distinct domains defined by the composition of each precursor; these include Al2O3 versus heavy rare earth
elements and some high field strength elements. Using these geochemical parameters, undifferentiated skarn
samples can be more reliably classified as endoskarn or exoskarn. The effectiveness of these element pairs is
attributed to their significantly different initial concentrations in wall rocks versus igneous precursors and their
immobility during skarn formation. While immobile elements can differentiate the skarns, mobile element
gains and losses (quantified using isocon analysis) provide insight on the bulk mineralogical and mass changes
that take place during skarn formation.

Introduction to unaltered precursors from Antamina with the aim of devel-

Skarn formation is a metasomatic process that can affect both
wall rocks and igneous rocks, forming exoskarns and endos-
karns, respectively (Einaudi et al., 1981; Meinert et al., 2005).
Accurate classification of endoskarn and exoskarn has impor-
tant implications for exploration and mining. Systematic map-
ping of the rock types and mineralogical zoning patterns in a
skarn system can improve the accuracy of a deposit model and
reveal vectors to ore (Newberry et al., 1991; Meinert, 1997;
Meinert et al., 2005; Chang and Meinert, 2008b). Addition-
ally, the endoskarn-exoskarn contact can mark a change in ore
grade, metal distribution, and rock hardness. Therefore, dis-
tinguishing these skarn types can inform mining and milling
processes to improve metal recovery.
Field-based classification of skarns relies heavily on inher-
ited precursor textures; as such, skarns with relict textures
are the easiest to classify as either endoskarn or exoskarn.
Banded textures in exoskarn provide a clear link to a layered
metasedimentary precursor, while weakly altered endoskarns
commonly display patches of residual igneous rock (e.g., at
the Empire Zn-Cu skarn, Idaho; Chang and Meinert, 2008a).
Compared to endoskarns, exoskarns are less likely to retain
primary textures, because carbonate-rich wall rocks are more
reactive than igneous rocks in the presence of acidic magmatic-
hydrothermal fluids. At Antamina, mottle-textured skarns are
common, and although the precursor connection is not clearly
linked, they are typically classified as endoskarn because of a
subtle resemblance to porphyritic igneous rocks. In this study,
we compare the bulk-rock geochemical signatures of skarns
†Corresponding author: e-mail, stephanie.mrozek@my.jcu.edu.au
ISSN 0361-0128; doi:10.5382/econgeo.4698; 12 p.
Digital appendices are available in the online Supplements section. 177
oping a method to distinguish endoskarns from exoskarns.
We demonstrate that the geochemical classification of skarns
is more reliable than textural classification because mottle-­
textured skarns can be either endoskarn or exoskarn. Further-
more, we quantify the compositional changes that take place
during skarn formation in order to gain insight on the influ-
ence of immobile elements on our classification method.
At Antamina, Peru (Fig. 1), some endoskarns occur dis-
tinctly as veins and patchy replacements in intrusive rocks
(Fig. 2A-D), and some exoskarns (i.e., near the marble front)
clearly inherit banded textures from layering in the wall rocks
(Fig. 2M-P). In between, there are extensive zones of massive
skarns, locally with mottled textures (Fig. 2F-L). With this
geologic architecture, Antamina is an ideal location to exam-
ine whether bulk-rock geochemistry alone can be used to dif-
ferentiate texturally similar endoskarns and exoskarns. The
same data set is used to evaluate potential elemental gains and
losses during skarn formation.
Geologic Setting
Antamina is located approximately 270 km north of Lima,
Peru, at 9°46'S, 77°06'W in the central Peruvian Andes. It
is the largest skarn deposit in the world, with a resource of
~2,968 million tonnes (Mt) averaging 0.89% Cu, 0.77% Zn,
11 g/t Ag, and 0.02% Mo (Glencore, 2015). The deposit is
centred on a Miocene (10.95 ± 0.20–10.24 ± 0.23 Ma; zircon
U-Pb; Mrozek, 2018) multiphase porphyry system, herein
referred to as the Antamina Porphyry Complex (Fig. 1). The
complex comprises several intrusions, including early- and
intermineralization porphyries. All of the intrusive phases
Submitted: September 16, 2017 / Accepted: August 27, 2019

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 178 SCIENTIFIC COMMUNICATIONS

77°04’30”W 77°04’00”W 77°03’30”W 77°03’00”W

9°31’00”S
A

Peru

Antamina

9°31’30”S
9°32’00”S
limit of contact
metamorphism
t
ma rbl e fr on

9°32’30”S
77°2’W
B
ble Location of
ar Figure 1A

9°32’S
m

9°33’00”S
9°34’S

1 km 4 km 77°0’W

Host Rocks and Alteration Structures Samples

Antamina Porphyry Celendín Formation Anticline This study
Miocene

Cretaceous

Complex
Undifferentiated Jumasha Formation Syncline Paz et al. (2015)
endoskarn and exoskarn Santa, Carhuaz, Chimu Fms.
(undifferentiated, Inset B) Thrust fault
Fig. 1. Location and geology of the Antamina deposit, Peru. A. Location of samples from the Antamina mine area. Inset in
upper right corner shows location of study area in Peru. B. Near-mine sample locations and geology farther afield. Geology is
modified after Redwood (2004) and Escalante et al. (2010).

contain porphyry-style quartz stockworks and secondary
biotite alteration (Mrozek, 2018). Endoskarn alteration is
observed along the margins of at least two early porphyry
phases (Redwood, 2004; Chang et al., 2015; Mrozek, 2018).
Exoskarns surround the endoskarns, and all of the skarns are
mineralized, with the general trend of proximal Cu-Mo to
distal Zn-Pb (Lipten and Smith, 2005). The principal ore
minerals include chalcopyrite, sphalerite, and molybdenite,
with localized bornite and galena (Love et al., 2000). Some
intermineralization porphyries cut across endoskarn and
exoskarn, indicating a complex intrusive history (Mrozek et
al., 2015, 2017).

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 SCIENTIFIC COMMUNICATIONS 179

A A170-254.8 B A139-37.6 C A2589-818.3 D A206-143.5

E A1854-708.5 F A2589-805.4 G A2589-184.5 H A2084-1364.5

I A2589-426.3 J A136-169.0 K A2589-617.3 L A2589-559.0

M A2491-1804.0 N A2084-1455.1 O A2810-74.0 P A2589-1391.5

3 cm

Fig. 2. Representative endoskarns and exoskarns. A, B. Patchy endoskarn showing remnant porphyry texture and mineralogy,
including early secondary biotite alteration. C-E. Moderate pervasive endoskarn alteration; weak porphyry texture still appar-
ent. F, G. Strong endoskarn alteration resulting in a mottled texture. H-L. Strong exoskarn alteration. The mottled texture
of these exoskarns is difficult to distinguish from mottled endoskarn. M-P. Moderate-intensity exoskarn alteration showing
banded textures inherited from the wall rock; easily distinguished from weak-moderate endoskarns. Scale bar applies to all
images.

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 180 SCIENTIFIC COMMUNICATIONS

Characteristics of the metasedimentary precursors
District-scale host rocks consist of a complexly deformed
marine-deltaic package of intercalated limestones, marls,
and calcareous shale/siltstone of the Cretaceous Jumasha and
Celendín Formations (Fig. 3). These rocks have a variable
siliciclastic component, with a more diverse detrital miner-
alogy noted in the Celendín Formation compared to the
Jumasha Formation (App. Table A1; Escalante, 2008). The
mid-Cretaceous Jumasha Formation (Fig. 3A, D, E) is a topo-
graphically prominent, medium- to thick-bedded bioclastic

Jumasha Formation

Celendín Formation

B C

Fig. 3. Field characteristics of the Celendín and Jumasha Formations, within 3 km of the Antamina deposit. A. The break
in slope marks the approximate contact location between the prominent Jumasha and recessive Celendín Formations. B.
Contact metamorphosed Celendín Formation, displaying interbedded marly (dark-gray) and calcareous (light-brown) layers.
C. Thin-layered, dark-gray, marly Celendín limestone. D. Massive, light-gray Jumasha limestone with thin bioclastic layers.
E. Thick-bedded, cliff-forming Jumasha limestone.

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limestone with lesser amounts of marl, dolomite, and chert
nodules (Benavides-Cáceres, 1956; Wilson, 1963; Escalante
et al., 2010). Fresh and weathered surfaces are light gray,
likely reflecting lower organic carbon contents (compared to
the dark-gray Celendín Formation). Unit thickness ranges
from 200 to 800 m, although local structural thickening is
observed around Antamina. The Upper Cretaceous Celendín
Formation (Fig. 3A-C) is a fine-grained, moderately recessive
unit dominated by thin intercalations of carbonate and calcar-
eous shale/siltstone (Benavides-Cáceres, 1956; Wilson, 1963;
Escalante et al., 2010). Thickness varies by location, from
225 m at the type locality to 115 m in other parts of the region
(Wilson, 1963). Fresh rock surfaces are medium to dark gray,
reflecting an overall high organic carbon content. Weathered
surfaces display a creamy beige patina.
Within a few hundred meters of the Antamina Porphyry
Complex, the Celendín and Jumasha Formations have been
contact metamorphosed to marble and hornfels (Fig. 1); these
are the inferred precursors to exoskarn at Antamina. Struc-
tural thickening, metamorphic recrystallization, and skarn
development make it difficult to trace the stratigraphic con-
tact between the two formations; however, previous research-
ers generally agree that the deposit is hosted in the transition
zone between the Celendín and Jumasha Formations (Love
et al., 2004; Lipten and Smith, 2005; Escalante et al., 2010).
The marble and hornfels contain a significant component of
detrital minerals (i.e., quartz, feldspar, rutile, titanite, and
apatite), which are inherited from the sedimentary precursors
(App. Table A1; Escalante, 2008). Some typical skarn miner-
als (i.e., diopsidic pyroxene ≤53%; epidote ≤18%), as well
as traces of sphalerite and chalcopyrite, occur in fluid escape
structures outside of the main skarn orebody (App. Table A1;
Escalante, 2008); these minerals are hydrothermal in origin
and extend the geochemical footprint of the skarn beyond the
marble front.
Characteristics of the igneous precursors
The Antamina porphyries display a narrow range of composi-
tions from quartz monzonite to quartz monzodiorite, as well
as typical arc magma geochemical signatures (Mrozek, 2018).
A A1854-338.2
Fig. 4. Typical porphyries from Antamina. A-C. Representative samples displaying the characteristic quartz monzonite min-
eralogy and porphyry texture. Rocks such as these are the precursors to endoskarn at Antamina.
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SCIENTIFIC COMMUNICATIONS 181
Major minerals include quartz (≤10%), K-feldspar (≤15%),
plagioclase (≤55%), and biotite (≤15%) with lesser amphi-
bole (≤3%); these occur both as phenocrysts and in ground-
mass (Fig. 4). Accessory minerals include magnetite, apatite,
titanite, and zircon. The porphyries are variably altered to
secondary biotite (i.e., potassic alteration) ± endoskarn.
Stockwork quartz ± sulfide vein densities vary from rare to
abundant.
Characteristics of the skarns
Andraditic garnet (up to Ad98; Mrozek, 2018) is the domi-
nant skarn mineral, indicating oxidized conditions of forma-
tion, although clinopyroxene-rich layers and lenses are locally
common in exoskarn. Endoskarn alteration occurs along the
margins of early porphyry phases in contact with exoskarn.
Near the endoskarn-exoskarn contact the skarns display mas-
sive or mottled textures, typically rendering the two types
indistinguishable. With increasing distance from this contact,
the skarns bear an increasing textural resemblance to their
precursors. From the endoskarn-exoskarn contact toward the
porphyry center, endoskarn intensity decreases into second-
ary biotite alteration with a distinct porphyry texture (Fig. 2A,
B). Toward the marble front, exoskarns reveal banded tex-
tures inherited from metasedimentary precursors (Fig. 2G-I).
Overall, the skarns display a well-developed garnet color
zonation outward from the porphyry center to the marble
front, which generally transitions from proximal pink-red gar-
net to distal brown-green garnet (Lipten and Smith, 2005). All
of the skarns display variable intensities of retrograde altera-
tion manifested as epidote ± chlorite ± amphibole ± calcite ±
quartz. Copper-Zn-Pb mineralization is associated with retro-
grade alteration (Love et al., 2000; Mrozek, 2018).
Methods
Samples
A total of 221 rock samples were collected and analyzed for
this study (Fig. 1; App. Table A2). Massive and mottled skarn
samples (n = 63), intrusion samples (n = 43), marble (n =
7), and limestone (n = 2) were selected from drill core and
AB A1391-548.3
A1854-338.2 C A2589-203.0
 182 SCIENTIFIC COMMUNICATIONS
pit highwalls. Care was taken to ensure that each intrusion,
marble, and limestone sample was representative of the unit
or interval and free of veins, xenoliths, contacts, and other
heterogeneities. Sample sizes ranged from 5 to 15 cm of NQ
drill core or fist-sized hand samples from field outcrops and
open-pit highwalls. Least altered (i.e., loss on ignition [LOI]
≤1.8 wt %, total S ≤0.8 wt %; App. Table A2), early porphyry
intrusion samples were collected exclusively from drill core
and mine workings; these samples are the precursors to endos-
karn. An additional 106 samples of limestone ± marl were col-
lected by Antamina exploration geologists from within a 6-km
radius of the mine, mostly outside of the contact metamorphic
halo, using the same selection criteria defined for the samples
described above (Paz et al., 2015; Fig. 1). Metasedimentary
samples (i.e., variably metamorphosed limestone ± marl)
were classified in the field as either Jumasha or Celendín For-
mation based on stratigraphic criteria used in regional explo-
ration; these samples represent the closest approximation to a
least altered precursor to exoskarn.
Whole-rock analysis
All samples collected for this study were analyzed at ALS
Chemex in Lima, Peru, using a combination of techniques
including X-ray fluorescence (XRF), inductively coupled
plasma-atomic emission spectroscopy (ICP-AES), induc-
tively coupled plasma-mass spectrometry (ICP-MS), atomic
absorption (AA), and LECO analysis for 62 elements (includ-
ing major and trace elements plus total S and total C) and LOI
(App. Tables A2, A3). All analyses were conducted in ISO
standard (9001 and 17025) certified laboratories. Controls on
accuracy and precision of the data were monitored via analy-
sis of certified reference materials, internal standards, sample
preparation and analytical blanks, and duplicate samples in
regular intervals during sample analysis batches.
Nine samples of limestone (n = 2) and marble (n = 7) were
analyzed for total organic carbon at the James Cook University
Advanced Analytical Centre in Cairns, Australia. The analytical
procedure is described in Wurster et al. (2012). The organic C
content ranges from 0.09 to 3.63 wt % (App. Table A4).
Data preparation and plotting
The data set was screened for missing entries and values out-
side of the limit of detection (LOD) of each analyte. Four Cu
assays exceeded the upper LOD (10,000 ppm); these were
replaced with a value of 10,000.1 ppm. Values below the lower
LOD for any element were replaced by a value equal to 50%
of the LOD. Silver, Cd, Ta, and Li were not considered fur-
ther, as >30% of analyses for these elements were below the
LOD (see Martín-Fernández et al., 2012). Barium, Sr, and
Cr were analyzed twice, as major element oxides (i.e., BaO,
SrO, Cr2O3, in wt %) and as trace elements (i.e., Ba, Sr, Cr, in
ppm); only the trace element values were used in this study.
All plots were constructed using the reduced data set and
ioGAS™ software.
Framework for relating skarns to precursors
Among the 62 individual elements examined, only Al2O3,
SiO2, CaO, Ga, total C, and LOI can differentiate wall rocks
from igneous precursors (App. Fig. A1). Because of its rela-
tive immobility under hydrothermal conditions (i.e., Floyd
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and Winchester, 1978) and its capacity to differentiate the wall
rocks from igneous rocks at Antamina, Al2O3 was selected as
the control variable in relating the skarns to their precursors.
Bivariate plots, comparing Al2O3 versus all other elements,
were constructed to evaluate geochemical relationships
between the skarns and their precursors. The plots were visu-
ally assessed for skarn cluster separation and compositional
correlation (i.e., clustering and overlap) with each precursor.
The discriminatory quality (i.e., weak, moderate, or strong) of
each element combination was visually assessed based on the
degree of skarn overlap with each precursor cluster and the
overall partitioning of data clusters. The strongest element
combinations allow for unequivocal classification of endos-
karn and exoskarn. The reclassified skarns and precursors are
the input data for isocon analysis.
Isocon analysis
Mass changes and element mobility during skarn formation
were quantified using isocon analysis (Grant, 1986). Our anal-
ysis was conducted using the complete geochemical data set
for precursors and reclassified skarns, as described above. The
isocon method uses a modified version of Gresens’s (1967)
equation for calculating mass balance. Using the Gresens
method, the chemical components of a least altered rock
(precursor) are plotted against those same components of an
altered equivalent (in this case, the corresponding skarns) in
X-Y space. A common conversion factor is used to scale the
data (App. Tables A5, A6). Elements deemed to be immo-
bile define a best-fit linear array anchored through the origin;
this line is called the isocon. In this study, elements display-
ing gains or losses within ±10% of the mean analytical value
are considered immobile (App. Tables A5, A6). The isocon
slope (m) quantifies the total mass change in the system; m
< 1 corresponds to mass loss, m = 1 means no mass change,
and m > 1 corresponds to mass gain. In this study we used
the average value for each element, by rock type, to minimize
the effects of compositional heterogeneity as in Oliver et al.
(2004). Detailed explanations of the mass balance calculation
procedure are presented in Grant (1986), Leitch and Lentz
(1994), and Trepanier et al. (2016).
Results
Geochemical composition of the host rocks
The compositions of the metasedimentary host rocks range
from essentially pure limestone in some samples of the Juma-
sha Formation (~13 wt % C, ~55 wt % CaO; Fig. 5) to marl
or calcareous mudstone in the Celendín Formation (up to
46.2 wt % SiO2, 51.8 wt % CaO, and 12.6 wt % Al2O3; Fig.
5). In general, the Celendín Formation contains more SiO2
and Al2O3 and less CaO than the Jumasha Formation, which
is consistent with the field descriptions of these rock types.
Some samples from the Jumasha Formation contain up to
~3.4 wt % MgO, indicating that they are dolomitic (Fig. 5).
The decrease in total C content in the wall rocks correlates
with a decrease in CaO content and an increase in SiO2 and
Al2O3 (Fig. 5). Because the organic carbon content is low, the
total C is dominated by carbon from carbonates (App. Table
A4). Therefore, the observed trend indicates that the increase
in silicate minerals is compensated by a decrease in carbonate
 SCIENTIFIC COMMUNICATIONS 183

Celendín Fm.
Jumasha Fm.
Intrusion
Total C (wt. %)

CaO (wt. %)
A B

C D
Al2O3 (wt. %)

TiO2 (wt. %)
E F
MgO (wt. %)

La (ppm)

G H
Lu (ppm)

Y (ppm)

I J
LOI (wt. %)
Ga (ppm)

SiO2 (wt. %) SiO2 (wt. %)

Fig. 5. Composition of intrusive and metasedimentary precursors. Selected elements versus SiO2 are presented; see Appen-
dix Figure A2 for additional element plots and Appendix Table A2 for the complete data set.

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 184 SCIENTIFIC COMMUNICATIONS
minerals (Figs. 4B, 5A). This is consistent with the petro-
graphic findings of Escalante (2008) in that the wall rocks
contain varying proportions of calcite and quartz + alumi-
nosilicate minerals (App. Table A1). Given the negative cor-
relation between total C and SiO2 (Fig. 5A) and the positive
correlation between Al2O3 and SiO2, we use Al2O3 and SiO2 as
proxies for the clastic content of the wall rocks.
Total Fe expressed as Fe2O3, K2O, Na2O, and most litho-
phile trace elements (e.g., rare earth elements [REEs],
Y, TiO2) have positive linear correlations with SiO2 in both
Jumasha and Celendín samples (Fig. 5; App. Fig. A2), indi-
cating that these elements are also related to detrital miner-
als in the metasedimentary host rocks. The MnO content is
low (≤0.16 wt %), with slightly higher concentrations in rocks
containing >10 wt % SiO2 (App. Fig. A2). Barium concentra-
tions range from 17.1 to 429 ppm and display a weak positive
trend that is correlative with increasing siliciclastic contents
in the wall rocks (App. Fig. A2). The Sr content ranges from
~250 to 2,100 ppm, with some carbonate-rich rocks contain-
ing the highest Sr concentrations (App. Fig. A2).
Compared to the wall rocks, the intrusive rocks contain
significantly higher SiO2 (64.6–74.3 vs. 0.70–48.6 wt %), and
significantly lower total C (0.01–0.35 vs. 3.15–13.1 wt %) and
CaO (0.70–5.31 vs. 15.7–55.4 wt %; Fig. 5). In general, the
intrusive rocks contain more K2O, Na2O, and Ba than the wall
rocks (Fig. 5; App. Fig. A2). The intrusive rocks have similar
TiO2 and Zr concentrations and lower Ni, heavy rare earth
elements (HREEs), Y, and V contents compared with the
SiO2-rich sedimentary rocks (>30 wt %, Celendín Formation;
Fig. 5; App. Fig. A2). The intrusive rocks and wall rocks have
similar ranges of Fe2O3 and MnO content (App. Fig. A2),
although some intrusive rock samples extend toward higher
MnO concentrations (up to 0.19 wt % MnO).
Geochemical discrimination of the skarns
Element pairs involving Al2O3 versus HREEs and some high
field strength elements (HFSEs; i.e., TiO2, Sc, Y, and Nb)
clearly discriminate the skarns into two domains: one clus-
tering with the metasedimentary wall rocks (i.e., exoskarns)
and the other with the igneous rocks (i.e., endoskarns; Fig.
6). The strongest discriminators include Al2O3 versus HREEs
(i.e., Dy, Lu), Y, and TiO2 (Fig. 6). Moderate discriminators
include Al2O3 versus Sc, Nb, La, and Th (Fig. 6). All other
element combinations yield weak to moderate relationships
and are not considered to be useful discriminators of skarn
type at Antamina.
Mass changes and element mobility during skarn formation
Some elements identified in Figure 6 display a case for mod-
erate to strong immobility (i.e., Al2O3, Y, HREEs, Sc, Nb, and
Th); these elements define the isocons and are used to quantify
mass changes and element mobility during skarn formation
(Fig. 7; App. Tables A5, A6). Endoskarn formation (Fig. 7A;
App. Table A5) involves very little mass change as indicated by
the isocon slope of 1.04 (4% mass loss). In contrast, exoskarn
formation results in an overall mass loss of approximately 28%
(Fig. 7B; App. Table A6). In both endoskarn and exoskarn, sig-
nificant increases are observed in metals (Cu, Mo, Zn, Pb, U)
and some major skarn mineral components (i.e., Fe2O3, MnO,
and MgO). Alkalis (K2O, Na2O) decrease by more than 50%
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in both endoskarn and exoskarn. LOI increases by more than
50% in endoskarn but decreases by more than 50% in exos-
karn. SiO2 decreases in endoskarn (–33.9%) and increases in
exoskarn (168%; Fig. 7; App. Tables A5, A6). CaO increases in
endoskarn (767%) and decreases in exoskarn (–52.4%; Fig. 7;
App. Tables A5, A6). The light rare earth elements (LREEs)
display evidence for mobility in both skarn types (Fig. 7; App.
Tables A5, A6).
Discussion
Element mobility during skarn formation
The significantly different initial concentrations of immobile
elements in the igneous and metasedimentary precursors
contribute to the effectiveness of skarn discrimination using
our method. The immobile element geochemical fingerprint
of the precursor is preserved through contact metamorphism
and hydrothermal alteration and subsequently inherited by
the skarns.
HFSEs and Al are among the most immobile elements
identified in this study and under a variety of geologic con-
ditions (Floyd and Winchester, 1978; Finlow-Bates and
Stumpfl, 1981; Whitney and Olmsted, 1998; Jiang et al., 2005;
Lentz, 2005; Ranjbar et al., 2016). Because of their low solu-
bility, Al contents of the skarns are derived mainly from the
precursor rocks. Although the solubility and mobility of these
elements can be enhanced in strongly acidic fluids, their solu-
bilities drop dramatically with increasing pH. For example, at
250°C total dissolved Al in fluids in equilibrium with alunite +
kaolinite + quartz is ~2,000 ppm at pH = 2 but drops to only
~1 ppm when the pH increases to 4 (Stoffregen, 1987). In
carbonate-rich environments (where most skarns form), fluid
acidity ranges from weak to neutral due to buffering by excess
carbonate; such fluids cannot mobilize HFSEs or Al2O3.
In both the igneous and metasedimentary precursor rocks,
immobile elements are hosted in feldspars and relatively alter-
ation resistant accessory minerals, such as magnetite, zircon,
apatite, rutile, and titanite (Deer et al., 1992; Escalante, 2008;
Hammerli et al., 2016; Mao et al., 2016; Mrozek, 2018; App.
Table A1). During skarn formation, the bulk mineralogy of the
host rocks changes significantly; however, the low solubility of
these immobile elements allows them to be reincorporated in
skarn minerals as they form (Huggins et al., 1977; Nicolescu
et al., 1998, Gaspar et al., 2008). Consequently, immobile ele-
ment signatures of the Antamina skarns are preserved through
contact metamorphism and skarn formation; evidence for this
isochemical behavior is presented in Figure 7.
In both endoskarn and exoskarn, increases in Fe2O3, MnO,
and MgO are related to the formation of garnet and clinopy-
roxene during prograde skarn alteration; these components
are likely to be derived from magmatic-hydrothermal fluids.
SiO2 (168%) is added to exoskarn during prograde skarn for-
mation, but its source may be partly from SiO2 stripping from
the intrusions during endoskarn formation (as indicated by a
34% loss of SiO2; Fig. 7A; App. Tables A5, A6). Base metals
(Cu, Mo, Zn, Pb) and U increase significantly in both endos-
karn and exoskarn due to retrograde alteration (Fig. 7; App.
Tables A5, A6). Volatile (LOI) increases (323%) in endoskarn
may be related to the formation of hydrous or CO2-bearing
retrograde minerals (chlorite, amphibole, calcite), while LOI
 SCIENTIFIC COMMUNICATIONS 185

A B

TiO2 (wt.%)

Y (ppm)
Skarns (undifferentiated)
Celendín Fm.
Jumasha Fm.
Intrusion

C D

Dy (ppm)
Lu (ppm)

E F
Sc (ppm)

Nb (ppm)

G H
Th (ppm)
La (ppm)

I J
Nd (ppm)
Zr (ppm)

Al2O3 (wt. %) Al2O3 (wt. %)

Fig. 6. A-J. Skarn discrimination plots based on precursor clustering and overlap for selected combinations of Al2O3 versus
REEs and HFSEs. The strongest discriminators are Al2O3 versus HREEs (Dy, Lu), Y, TiO2, and Sc, which display complete
overlap with precursor clusters and no overlap between skarn clusters. Combinations of Al2O3 versus Nb and Th are moder-
ate discriminators based on less tightly constrained sample clusters for the skarns compared to the precursors. While Al2O3
versus La, Nd, and Zr display strong precursor clusters, the skarn sample clusters are too dispersed for reliable discrimination.

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 186 SCIENTIFIC COMMUNICATIONS

4% MASS LOSS 28% MASS LOSS

10.0 10.0
A B GE

AIN
LOI CaO AN
9.0 9.0 CH

SG
Ce

Metasedimentary wall rocks (n = 108)

SS

AIN
S
MA

MA

SG
8.0 NO

%
8.0 GE

S
50
AN

MA
LOSSES LOSSES
CH La

%
S

50
7.0 Si O₂ S N 7.0
MA CO Na ₂O
SO
Intrusions (n = 43)

NO I
6.0
Na ₂O 6.0 Ti O₂
MgO
K₂O
5.0 LOS
S 5.0
ASS Eu S
50%M LOS
4.0 4.0 ON A SS
OC Hf 50 %M
K₂O IS
3.0 3.0 Zr
GAINS
Fe₂O₃ P₂O₅
2.0 2.0 Si O₂
LOI MgO
Zn GAINS
1.0 Zn Sn Cu 1.0
CaO Mo MnO Fe₂O₃
MnO Sn Cu Mo
0.0 0.0
0.0 2.0 4.0 6.0 8.0 10.0 0.0 2.0 4.0 6.0 8.0 10.0
Endoskarn (n = 20) Exoskarn (n = 43)
Fig. 7. Isocon plots showing mass changes during skarn formation. Skarns are plotted along the x-axis, and least altered equiv-
alents (precursors) are plotted along the y-axis. The slope (m) of the isocon indicates the total mass change for the system; m
> 1 indicates an overall mass increase, and m < 1 indicates an overall mass decrease. The red line, m = 1, is a reference line
indicating constant mass (no change). The total mass change is indicated in the upper right corner of each plot, expressed as a
percentage. Elements plotting along the isocon (black circles along the dashed black line) are immobile; see Appendix Tables
A5 and A6 for the complete list of immobile elements. Elements plotting below the isocon have been gained during skarn for-
mation, while elements above the isocon have been lost during skarn formation. A. Element mobility and mass changes dur-
ing endoskarn formation (App. Table A5). B. Element mobility and mass changes during exoskarn formation (App. Table A6).

decreases in exoskarn (–97%) are largely related to CO2 lib- geochemical evidence indicates that exoskarns may also dis-
eration from marble during prograde skarn formation. play mottled textures. Impure carbonate rocks, like those at
The only elements lost in significant quantities (>38%) from Antamina, which contain siliciclastic layers or patches, may
both skarn types are the alkali elements (K2O, Na2O, Ba, and produce a mottled texture through a process of repetitive dis-
Rb; Fig. 7; App. Tables A5, A6). In both cases, the most com- solution, fragmentation, and replacement. When the rate of
mon and abundant skarn minerals do not incorporate these carbonate dissolution exceeds the rate of calc-silicate min-
elements into their crystal lattice. Some of this element loss eral precipitation, void space is created; this causes the more
may be related to alkali gain in the intrusive samples during resistant siliciclastic layers to become unsupported and col-
retrograde alteration (i.e., sericite), but significant amounts of lapse into fragments. Metasomatic replacement of these frag-
these elements were likely transported to distal parts of the mented rocks may produce exoskarns with mottled textures.
system via hydrothermal fluid escape structures (i.e., Meinert For example, the samples shown in Figure 2H-L display
et al., 2005). At Antamina we can only speculate that these mottled textures, but their whole-rock geochemistry indicates
alkalis were transported to overlying rock packages that have that they are exoskarns (Fig. 8). In contrast, the samples in
now been lost to erosion. Nevertheless, if alkali element loss Figure 2D-G are endoskarns based on their geochemical sig-
is a common feature of skarn formation, then upward flow and nature (Fig. 8).
reaction of these fluids with wall rocks may provide some of
the alkalis for the alteration assemblages that are characteris- Applicability in other skarns
tic of porphyry-epithermal environments. Elements in these This approach to skarn classification is particularly well suited
alteration assemblages are primarily considered to be magma for deposit-scale studies where the geologic framework has
sourced; however, some contribution from skarn alteration of been established and a range of rock types (from least altered
wall rock is consistent with Pb isotope evidence supporting to strongly altered) are available for analysis. Applying our
a wall-rock component to porphyry alteration fluids (Cooke procedures to other skarn localities, we suggest that wall
et al., 2014). If significant quantities of alkali elements are rocks, igneous rocks, and skarns should be characterized using
sourced from wall-rock alteration, recognition of this process the same analytical method. The precursor compositions are
would relax the requirements for very large magma volumes necessary to provide a geochemical baseline for comparison
as the primary source of alkali elements in porphyry alteration with skarns of unknown affinity. The success of this method
envelopes (Cathles and Shannon, 2007). in other localities will depend on the specific compositions
of wall rocks and igneous precursors. On the condition that
Formation of mottled texture in exoskarn precursor compositions are distinctly different in their HFSE
At Antamina, mottled skarn textures were interpreted to be and Al2O3 compositions, it may be possible to distinguish
inherited from a porphyritic igneous precursor; however, endoskarn and exoskarn just as we have done in this study.

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30 Reclassified Skarns
Endoskarn
Exoskarn
25
Sample image
in Figure 2
20 Precursors
Celendín Fm.
Y (ppm)
Jumasha Fm.
15 Intrusion
10
A136-169.0
5 A206-143.5
A2084-1364.5
0.0 2.5
Fig. 8. Skarns reclassified using the Al2O3 versus Y discrimination plot. Selected mottle-textured skarns (blue symbols) are
presented in Figure 2, as indicated.
This method may not work in localities with only one type of
precursor (i.e., only igneous rocks or only metasedimentary
rocks; see Chang et al., 2018) or where precursor composi-
tions are similar.
Conclusion
Using Antamina as a case study, we demonstrate a method
for comparing the whole-rock composition of skarns and their
precursors as a tool for discriminating endoskarns from exos-
karns, especially where skarns are massive or where primary
textures have been completely destroyed by hydrothermal
alteration. The most effective discriminators at Antamina
are element pairs of Al2O3 versus HREEs and Y, followed by
Al2O3 versus Sc, Zr, Nb, Th, TiO2, and LREEs. Skarn forma-
tion involves significant gains and losses of most elements,
therefore only immobile elements are useful for fingerprint-
ing and discriminating skarn type. The effectiveness of these
immobile elements is enhanced when there are significant
differences in geochemical signature between wall rocks and
igneous rocks. Mobile element behavior can explain the bulk
mineralogical changes that occur during skarn formation.
In particular, the mobility of alkali elements may contribute
alkali elements to porphyry and epithermal-style alteration
assemblages observed in higher levels of the system and in
zones peripheral to the main skarn orebody. Mottled texture
is not a reliable feature to distinguish massive endoskarns and
exoskarns, as it can be a texture common to both skarn types.
Acknowledgments
This study was funded by Compañía Minera Antamina (ana-
lytical funds and in-kind support) and a Society of Economic
Geologists Graduate Student Research Grant awarded to
Stephanie Mrozek. Christian Mendoza, David Paredes, Fred-
erick Sanchez, and the Antamina exploration crew provided
limestone samples and access to the whole-rock data set.
James Grant helpfully answered questions related to isocon
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by University of Waterloo user
SCIENTIFIC COMMUNICATIONS 187
A2589-426.3
A2589-617.3
A2589-559.0 A1854-708.5
A2589-805.4
A2589-184.5
5.0 7.5 10.0 12.5 15.0 17.5 20.0
Al2O3 (wt. %)
calculations. Andrew Norton provided invaluable technical
support. Rob Holm and Carlos Jimenez provided constructive
reviews on the manuscript. This manuscript benefited signifi-
cantly from the comments of Lucie Mathieu, associate editor
Andrew Tomkins, and Editor Larry Meinert.
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Stephanie Mrozek is an adjunct research asso-
ciate at James Cook University (Townsville, Aus-
tralia) and a resource geologist at Northern Star
Resources (Pogo Mine, Alaska). She received
her Ph.D. degree in 2018 at James Cook Univer-
sity, where her studies focused on the world-class
Antamina Cu-Zn skarn-porphyry deposit in Peru.
Her research combined field investigations with geochemistry, geochronol-
ogy, petrography, and fluid inclusion analysis to elucidate spatiotemporal
relationships between porphyry emplacement, host-rock composition, hydro-
thermal alteration, and mineralization. Stephanie has 14 years of experience
in mining and exploration, with a decade of that time devoted to working on
skarns.