holley2017
holley2017
holley2017
Abstract
The world-class Veladero high-sulfidation epithermal Au-Ag deposit is located in the Andean cordillera of
Argentina near the northern end of the El Indio-Pascua metallogenic belt. The deposit comprises two nearly
coalescing subhorizontal orebodies that are centered on an extensive zone of intense hydrothermal alteration.
Intensely altered volcanic rocks are composed of fine-grained groundmass quartz that formed as a result of
extreme acid leaching. These quartz grains contain ubiquitous rutile inclusions as well as healed microfractures
of vapor-filled inclusions that record magmatic vapor streaming through the Miocene volcanic host succession.
Condensation of the magmatic vapor into ambient groundwater generated the highly acidic waters responsible
for the alteration. Alunite is present in the fine-grained groundmass quartz and fills vugs in the altered rocks.
Stable isotope data indicate that the alunite formed through the disproportionation of SO2 in the condensed
magmatic vapor.
The fine-grained groundmass quartz is crosscut by later fracture-controlled euhedral quartz that is textur-
ally associated with ore minerals. The euhedral quartz crystals show oscillatory growth zoning and contain rare
primary fluid inclusions suggesting that quartz formation occurred at ~200°C from a moderately saline (<5 wt
% NaCl equiv) liquid-phase hydrothermal fluid. High-fineness native Au grains are hosted in euhedral quartz-
lined void spaces and along fractures. In addition to native Au, vugs and fractures in the silicified volcanic rocks
host Fe oxide/hydroxide and jarosite that are interpreted to represent the oxidation products of hypogene
sulfide minerals that formed during and after the late stages of quartz formation. Results of previous jarosite
dating suggest that pervasive oxidation of the orebody commenced during the waning stages of the hydrother-
mal activity or immediately thereafter. Oxidation of the orebody continued in the supergene environment for at
least 3 m.y. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) showed that jarosite,
which formed as a result of the oxidation of the orebody, is the principal host for Ag in Veladero ore, explaining
the low (ca. 10%) Ag recovery from the oxide ore.
The Veladero high-sulfidation epithermal deposit is interpreted to have formed in the shallow part of a
magmatic-hydrothermal system. Early alteration related to magmatic vapor discharge was followed by later
mineralization from liquid-phase hydrothermal fluids under reduced and slightly acidic to near-neutral condi-
tions. This change from early vapor-dominated to later liquid-dominated magmatic-hydrothermal fluid flow was
key in formation of the deposit.
Introduction (Charchaflié et al., 2007; Holley et al., 2016). The ore is con-
The Veladero Au deposit in the Cordillera Frontal of the tained in two orebodies, Filo Federico and Amable, which
central Andes in Argentina represents one of the largest low- are centered on nearly coalescing zones of intense alteration.
grade, high-tonnage high-sulfidation epithermal deposits An innermost zone of vuggy quartz alteration grades outward
in the world. Between 2005 and 2016, the deposit has pro- into a zone of vuggy quartz-alunite alteration. Volcanic rocks
duced 7.5 million ounces (Moz) of Au. Veladero has proven affected by vuggy quartz and quartz-alunite alteration are sili-
Au reserves of 602,000 oz at an average grade of 0.78 g/t and ceous and contain variable amounts of vugs resulting from the
probable reserves of 6.15 Moz at an average grade of 0.84 g/t. dissolution of former phenocrysts and volcanic particles that
An additional measured resource of 118,000 oz Au has been may have been originally glassy. The vugs may or may not have
identified at an average grade of 0.48 g/t, as well as indicated a mineral lining. In the periphery of the orebodies, alteration
mineral resources of 3.19 Moz Au at 0.48 g/t (Barrick Gold grades from advanced argillic through argillic into propylitic
Corporation, 2016). zones. The alteration halo surrounding Veladero covers an
The Veladero deposit is hosted in Miocene volcanic rocks area exceeding 9 km2 (Laidlaw, 2005). In addition to the main
that show the effects of interaction with extremely acidic fluids orebodies, two smaller satellite zones of intense hydrother-
mal alteration occur at Fabiana and Argenta. The Veladero
† Corresponding author: e-mail, [email protected]
ore deposit is pervasively oxidized, and Au occurs as dissemi-
*Present address: Goldcorp Inc., 3400–666 Burrard St., Vancouver, British nated high-fineness native Au grains. Iron oxide/hydroxide and
Columbia, Canada V6C 2X8. jarosite are present throughout the ore zones (Laidlaw, 2005).
doi: 10.5382/econgeo.2017.4528 Submitted: September 22, 2016
0361-0128/17/1747-25 1747 Accepted: June 6, 2017
The present contribution reports on the first detailed petro- border along the crest of the Cordillera Frontal of the Cen-
graphic and mineralogical study on intensely altered volcanic tral Andes (Fig. 1). The El Indio-Pascua metallogenic belt is
rocks from the Veladero deposit. As paragenetic relationships bounded by two NNE-striking high-angle reverse faults. The
in the fine-grained vuggy material are difficult to recognize Baños del Toro fault defines the western limit of the belt, and
macroscopically, a combination of microanalytical techniques the Colanguïl reverse fault defines its eastern margin (Fig. 1;
was used, including optical microscopy, optical cathodolu- Maksaev et al., 1984).
minescence microscopy, fluid inclusion petrography, scan- Basement rocks of the El Indio-Pascua metallogenic belt
ning electron microscopy, and electron microprobe analysis. include Paleozoic gneisses, Mesozoic granitoids of the Elqui-
The textural observations were integrated with stable isotope Limari batholith, and Permian to Jurassic volcanic, plutonic,
investigations on the alteration minerals. These data provide and sedimentary units of the Pastos Blancos Group in Chile
new critical insights into the evolution of magmatic-hydro- (Martin et al., 1999; Bissig et al., 2001) and the age-equivalent
thermal systems forming high-sulfidation epithermal precious Choiyoi Group in Argentina (Kay et al., 1989; Charchaflié
metal deposits, and they have implications for exploration and et al., 2007). The Choiyoi Group in Argentina is further subdi-
the processing of oxide ores common in this deposit type. vided into volcaniclastic and volcanogenic sedimentary rocks
and minor lava flows of the Permian Guanaco-Sonso Forma-
Regional Geology tion and bimodal lava flows and volcaniclastic rocks of the
Veladero is situated near the northern limit of the El Indio- Middle Triassic to Lower Jurassic Los Tilos Formation. These
Pascua metallogenic belt, which straddles the Argentina-Chile rocks are unconformably overlain by volcaniclastic deposits of
Pascua-
Lama
SOUTH Filo Federico
Fabiana AMERICA
Veladero N
o
24 S
6,750,000
Fabiana
Argenta
6,740,000
Amable
Río Apolinario Veladero
Sur
i
ARGENTINA
6,746,000
Sancarrón
CHILE
6,720,000
Libra
B
Argenta
Río del Medio
El Indio
0 3 km
Cerro Quaternary deposits
Doña Ana Tambo
6,700,000
ARGENTINA
Alturas Bocatoma intrusive unit Barite sample
Jarosite sample
Paleozoic to Jurassic
0 10 km
basement Fluid inclusion sample
Fig. 1. Location of the Veladero high-sulfidation epithermal deposit in Argentina. (A) Geology and deposits of the El Indio-
Pascua metallogenic belt (regional geology from Winocur et al., 2015). (B) Geological map of the Veladero area (modified
from Charchaflié, 2003, with unpublished data from Barrick Gold Corporation). The map also shows the location of samples
collected for fluid inclusion and stable isotope analyses.
the Upper Jurassic Cuartitos Formation (Martin et al., 1999). down to an elevation of 3,900 m (Charchaflié et al., 2007; Hol-
The basement rocks of the El Indio-Pascua belt were imbri- ley et al., 2016).
cated by thrust faults and gently folded (Charchaflié et al., At Amable, the main host rocks to ore are stratified tuffs of
2007). the Miocene Cerro de las Tórtolas Formation. The tuffs form
The high-sulfidation epithermal deposits in the El Indio- normally graded beds that range from 0.5 to 5 m in thick-
Pascua metallogenic belt, including Veladero, are predomi- ness. The bedding generally dips eastward from 5° to 30°. The
nately hosted in a thick (up to 1,500 m) package of Tertiary tuffs are composed of 95 to 99% ash with 1 to 5% lapilli. The
volcanic rocks unconformably overlying the basement. The Filo Federico ore zone is largely hosted by dacitic crystal tuffs
lithologic characteristics and age relationships of the Ter- of the Miocene Vacas Heladas Formation. These tuffs form
tiary volcanic rocks and associated intrusions have been dis- massive gray units that lack observable stratification. The tuffs
cussed in detail by Bissig et al. (2001), Litvak et al. (2007), are mostly composed of ash with rare phenocrysts and lapilli-
and Winocur et al. (2015). The oldest Tertiary rocks in the sized lithic fragments.
region are assigned to the Eocene to Oligocene (35.9 ± 1.2 The host rocks of the Amable and Filo Federico ore zones
to 30.0 ± 1.9 Ma; Bissig et al., 2001) Bocatoma intrusive unit, have been intensely altered and now show vuggy textures
which consists of dioritic to granodioritic stocks that are each formed by the dissolution of former phenocrysts and origi-
~1.5 km in diameter. The Oligocene Tilito, Río La Sal, and nally glassy volcanic particles. Vugs constitute approximately
Valle del Cura formations (25.1 ± 0.4 to 23.1 ± 0.4 Ma; Bis- 10% of the rock by volume. Hydrothermal brecciation is
sig et al., 2001; Charchaflié et al., 2007; Winocur et al., 2015) widespread throughout both orebodies. Brecciation occurs in
overlie much of the basement in the El Indio-Pascua metal- 0.5- to 500-m-wide zones having anastomosing, irregular, or
logenic belt and are largely composed of basaltic to rhyolitic pipe-like geometries (Charchaflié et al., 2007; Holley et al.,
flows, ignimbrites, as well as volcaniclastic and sedimentary 2016).
rocks (Martin et al., 1999; Bissig et al., 2001). On the Chilean Two additional satellite zones of intense hydrothermal
side of the border, ignimbrite deposits and lavas dominate, alteration have been recognized in the Veladero area (Figs.
whereas volcaniclastic and sedimentary rocks are prevalent in 1B, 2A). The Argenta ore zone is located approximately 6 km
Argentina (Reutter, 1974; Litvak et al., 2007; Winocur et al., south of Amable. Argenta is hosted by silicified dacite brec-
2015). Following compressional deformation at ~23 Ma, cias and tuffs of the Vacas Heladas Formation, which uncon-
andesitic flows and volcaniclastic rocks of the Miocene Esca- formably overlie felsic lavas and volcaniclastic rocks of the
broso Formation (21.9 ± 0.9 to 17.6 ± 0.5 Ma; Bissig et al., Permian to Triassic Guanaco-Sonso Formation and welded
2001) were deposited above an angular unconformity with ignimbrites of the Oligocene Tilito Formation. Open-pit min-
the Oligocene volcanic and sedimentary rocks. Deposition of ing at Argenta commenced in 2010. The weakly mineralized
the Escabroso Formation was accompanied by emplacement Fabiana prospect is located 5 km east of Amable. This zone
of volumetrically minor subvolcanic intrusions (Bissig et al., of mineralization and associated alteration is hosted primarily
2001). by dacitic ignimbrites assigned to the Cerro de las Tórtolas
The Veladero deposit (Fig. 1) is predominately hosted in the Formation. The ignimbrites are overlain by essentially unal-
Miocene Cerro de las Tórtolas (16.6 ± 0.3 to 14.9 ± 0.7 Ma; tered dacitic domes or flows of the Vacas Heladas Formation
Bissig et al., 2001; Charchaflié et al., 2007) and Vacas Heladas (Winocur et al., 2015), just west of the Cerro de Vidrio rhyo-
(12.7 ± 0.9 to 11.0 ± 0.2 Ma; Bissig et al., 2001) formations. lite dome (Bissig et al., 2002a).
The Cerro de las Tórtolas Formation is composed of andes- Hydrothermal activity and Au mineralization at the four
itic to dacitic lavas and related volcaniclastic rocks that were mineralized centers in the Veladero area took place episodi-
deposited from large stratovolcanoes in the region, including cally over almost 3 m.y. in the middle to late Miocene, based
the Cerro de las Tórtolas volcano (Fig. 1A). The age-equivalent on 40Ar/39Ar analyses of alunite and jarosite (Holley et al.,
Infiernillo unit (Martin et al., 1999) forms porphyritic andes- 2016). The earliest hydrothermal alteration related to miner-
itic to dacitic domes and intrusions in the region. The Vacas alization in the area is recorded by 13.12 ± 0.18 Ma alunite
Heladas Formation consists of andesitic to dacitic ignimbrite from Argenta. At the Veladero deposit, alteration and min-
deposits and corresponding subvolcanic intrusions. eralization at Filo Federico and Amable formed at different
The youngest rocks in the El Indio-Pascua belt include rhy- times. Alunite alteration at Amable took place at 11.93 ±
olitic tuffs and minor sedimentary rocks of the late Miocene 0.09 Ma (40Ar/39Ar on one alunite sample; T. Thompson,
Vallecito Formation (6.1 ± 0.4 to 5.5 ± 0.1 Ma; Bissig et al., pers. commun., 2003). Postmineralization jarosite altera-
2001). A rhyolitic dome of the Pleistocene Cerro de Vidrio tion at Amable commenced at 11.8 ± 0.3 Ma and continued
Formation (2.1 ± 0.5 to 2.0 ± 0.2 Ma; Bissig et al., 2002a) is until 8.58 ± 0.17 Ma. In contrast, Au mineralization at Filo
located ~6 km east of Veladero. Federico occurred after the inception of alunite alteration at
11.05 ± 0.12 Ma. Alunite from the Fabiana prospect has been
Deposit Geology dated at 10.09 ± 0.08 Ma (Holley et al., 2016).
The Veladero deposit trends north-northwest over a distance
of 3 km at elevations ranging from 3,900 to 4,400 m a.s.l. Materials and Methods
Veladero comprises two partly coalescing, subhorizontal oxide A suite of 140 samples of intensely altered volcanic rocks exhib-
orebodies exploited by open pit mining: Amable in the south iting vuggy textures was collected from surface and diamond
and Filo Federico in the north (Figs. 1, 2). At Amable, ore is drill core, covering the Filo Federico and Amable orebodies,
largely confined to an elevation above 4,000 m. The mineral- as well as the satellite zones at Argenta and Fabiana (Table 1).
ized zone is thicker at Filo Federico, with the ore extending Gold and Ag assays on whole-rock samples were performed
0 400 m
A A’
N
6,751,500
N
Filo Federico
Veladero
6,750,000
Fabiana
6,751,000
6,746,000
6,750,500
Au (g/t)
Argenta 5.0 < < 100
2.0 < < 5.0
6,750,000
1.0 < < 2.0
6,742,000
4,400 m
B’
4,000 m
4,100 m
0 250 m
C 0 250 m
D
406,500 407,000 407,500 407,500 408,000 408,500
Fig. 2. Alteration and grade distribution at Veladero. (A) Satellite image showing the locations of the Veladero deposit and the
satellite zones at Argenta and Fabiana. Areas of intense hydrothermal alteration are highlighted (Holley et al., 2016). (B) Plan
view of gold distribution at the 4,200-m level at Amable and Filo Federico. (C) Cross section of gold distribution at 6,751,725
m north in the Filo Federico pit. (D) Cross section of gold distribution at 6,749,500 m north in the Amable pit. The maps also
show the distribution of samples collected for the present study. Euhedral quartz was typically present in samples collected
from zones having elevated gold grades. Gold distribution maps in B, C, and D are from Barrick Gold Corporation (Roscoe
Postle Associates, 2012), with additional data from Holley (2012).
by Actlabs in Ancaster, Ontario, and ACME in Santiago, Chile mill to <10 µm. Homogenization of the fine powders was
(now Bureau Veritas). Gold grades were determined by fire accomplished in a vibratory mixer mill. Standard powder
assay with a gravimetric finish. Silver assays were conducted by mounts with random orientation were obtained by filling the
dissolving the sample aliquots in aqua regia, followed by induc- sample powders into top-loading sample holders. Step scan
tively coupled plasma-optical emission spectrometry (ICP- data (5 to 80°2Q, Co tube, 0.03°2Q step width, and 8 s/step
OES). Detection limits were 0.03 g/t for Au and 0.2 g/t for Ag. counting time) were collected using a Seifert-FPM URD-6
To determine the mineralogical composition of the samples, diffractometer equipped with a diffracted-beam graphite
the pulps used for assaying were also investigated by X-ray dif- monochromator and a variable divergence slit. The instru-
fraction (XRD). Initially, a 4-g split of material was milled for ment was operated at 40 kV and 30 mA. Quantitative XRD
8 min with 10 g of ethanol in a vibratory McCrone micronizing analyses were performed with the fundamental-parameter
Table 1. Geochemical and Petrographic Characteristics of Veladero Samples Exhibiting Vuggy Textures
Sample Area Easting Northing Elevation (m a.s.l.) Au (g/t) Ag (g/t) Euhedral quartz
Table 1. (Cont.)
Sample Area Easting Northing Elevation (m a.s.l.) Au (g/t) Ag (g/t) Euhedral quartz
Notes: All coordinates are given in UTM Zone 19; - = not analyzed
Rietveld programs BGMN/Profex. The quantification method to a Perking Elmer Elan DRC. The operating conditions
is described in detail by Monecke et al. (2001) and Döbelin included a spot size of 30 mm, a laser pulse frequency of 2 Hz,
and Kleeberg (2015). a laser energy density of 5 J/cm2, and a He carrier gas flow
Optical petrography of thin sections from the 140 samples of 0.8–0.95 l/min. External calibration was conducted using
was conducted using an Olympus BX51 microscope in trans- a basaltic glass (USGS GSD-1G). The georeference mate-
mitted and reflected light. Following carbon coating of the rial was analyzed 10 times at the start of an analytical session
sections, optical cathodoluminescence (CL) microscopy was and monitored throughout for instrumental drift. All time-
conducted to study the different quartz generations pres- resolved signals were screened for inclusions and filtered as
ent in the intensely altered rocks. A HC5-LM hot cathode appropriate. Concentrations were determined using the off-
CL microscope by Lumic Special Microscopes, Germany, line calculation protocol of Longerich et al. (1996). Iron was
was used, allowing inspection of the sections under electron used as an internal standard for the concentration calcula-
bombardment in a modified Olympus BXFM-S optical micro- tions with the assumption that the jarosite contains 30 wt %
scope. The microscope was operated at 14 kV with a current Fe based on EMP analyses. In total, jarosite contained in six
density of ca. 10 µA mm–2 (Neuser, 1995). The CL images samples was analyzed for a total of 50 spots, averaging three
were captured using a high sensitivity, double-stage Peltier spots per grain.
cooled Kappa DX40C CCD camera with acquisition times To evaluate the nature of the fluids responsible for hydro-
ranging from 4 to 10 s for quartz. thermal alteration and oxidation, δD, δ18OSO4, δ18OOH, and
The thin sections of all samples, as well as a large number δ34S stable isotope analyses were conducted on representa-
of doubly polished thick (60 mm) sections, were systematically tive alunite and jarosite samples. In addition, one barite sam-
screened on an x-y stage to study the fluid inclusion character- ple from Amable was found to be of sufficient size to allow
istics of quartz contained in the altered volcanic rocks. Along δ18OSO4 and δ34S analyses. Due to the pervasive oxidation at
the traverses, observations were made at low and high magnifi- Veladero, sulfide minerals suitable for stable isotope analy-
cation (10x and 40x objectives) using an Olympus BX51 micro- sis could not be obtained. All data were collected at the U.S.
scope. Microthermometric data on selected fluid inclusions Geological Survey in Denver, Colorado.
were collected using a FLUID INC.-adapted U.S. Geological Initially, the samples were handpicked, separated, and pre-
Survey gas-flow heating and freezing stage that was calibrated pared using the methods of Wasserman et al. (1992). Slurry
using synthetic fluid inclusions. Freezing temperatures were mounts of the samples were checked for purity by XRD. For
accurate to ±0.5°C. The accuracy of heating measurements samples containing finely intergrown alunite and jarosite that
is approximately ±2°C at 200°C. Data were collected with could not be separated by handpicking, alunite and jarosite
respect to fluid inclusion assemblages (Goldstein and Reyn- were chemically separated for δ18OSO4 analysis by sequential
olds, 1994). Homogenization temperatures were determined extraction using the protocol established by Berry and Breit
and bracketed using the cycling technique with 5°C intervals (2007) and subsequent reprecipitation as BaSO4. Hydrogen
as described in Goldstein and Reynolds (1994). Temperatures and oxygen isotope analyses were run on a Delta Plus XL
of final melting of ice were also determined using the cycling Thermofinnigan mass spectrometer according to the methods
technique with 0.1°C cycling intervals. of Sharp et al. (2001). The samples were introduced into the
The ore mineralogy of the intensely altered samples was mass spectrometer via a zero blank autosampler on a Ther-
initially studied in thin section in transmitted and reflected mofinnigan high-temperature conversion elemental analyzer
light. Minerals too small to be examined optically were stud- at 1,425°C under continuous He flow. Sulfur isotope analy-
ied by field-emission scanning electron microscopy on an FEI ses were conducted on a Delta Plus XP Thermofinnigan con-
Quanta 450 FEG instrument equipped with an EDAX silicon- tinuous flow isotopic ratio mass spectrometer according to
drift energy dispersive X-ray (EDX) spectrometer at the U.S. the methods of Giesemann et al. (1994) and Carmody et al.
Geological Survey in Denver, Colorado. Imaging of the grains (1998). Samples were introduced to the mass spectrometer
was conducted using standard operating conditions of 25 kV through a CE Elantech Flash2000 elemental analyzer. The
at a working distance of 10 mm. To identify all ore minerals element analyzer was held at an operating temperature of
contained in selected sections, trace mineral searches were 1,030°C under continuous He flow.
conducted on a Qemscan automated mineralogy system that Based on analysis of duplicates and international georefer-
combines a Carl Zeiss EVO50 scanning electron microscope ence materials, the precision of the δD measurements was
with four Bruker silicon-drift EDX spectrometers. The sys- better than ±3.0‰. The analytical precision for the δ18OSO4
tem was operated at 25 kV. A step size of 4 µm was chosen and δ18OOH is estimated at ±0.15‰. The d18OOH values were
to identify small ore mineral grains. Quantitative analysis of calculated using the formula of Wasserman et al. (1992) for
Ag-bearing ore minerals was conducted using a JEOL 8900 alunite, which was also applied to jarosite as in Rye and Stof-
electron microprobe (EMP) at the U.S. Geological Survey fregen (1995). The obtained δD, δ18OSO4, and δ18OOH values
in Denver, Colorado. An accelerating voltage of 15 kV and a were standardized to Vienna Standard Mean Ocean Water
nominal beam current of 20 nA were used. Halide minerals (VSMOW). The precision for the δ34S measurements was
were analyzed with a beam that was 5 µm in diameter to mini- determined to be better than ±0.2‰. The δ34S values are
mize volatilization, whereas other phases were analyzed with given in reference to Vienna Canyon Diablo Troilite (VCDT).
a focused electron beam of 1 µm diameter.
The composition of jarosite was determined by laser-abla- Petrography
tion inductively coupled plasma-mass spectrometry (LA-ICP- Samples collected for the present study are intensely altered
MS) using a 193-nm Photon Machines Analyte G2 coupled volcaniclastic and volcanogenic sedimentary rocks that initially
had andesitic, dacitic, or rhyolitic compositions. Hydrother- detectable or low jarosite concentrations, jarosite can occur
mal alteration resulted in the dissolution of former phe- in concentrations of up to 21.7 wt %. Rutile concentrations
nocrysts and differential alteration of the clasts. Many vugs range up to 1.6 wt %. The samples may also contain barite,
observable in hand specimen are casts of lath-shaped feld- goethite, hematite, and native sulfur.
spar phenocrysts or former ferromagnesian phases. Vugs also Samples affected by vuggy quartz-alunite alteration are
formed through alteration of volcanic particles that were sus- characterized by lower quartz (42.8–78.8 wt %) and higher
ceptible to hydrothermal alteration, presumably due to their alunite (10.8–44.3 wt %) abundances. Alunite in these sam-
high initial volcanic glass content. The samples contain up to ples varies compositionally as suggested by broadening of
about 30% vugs, which range from 1 to 5 mm in diameter. the XRD peaks. In some of the samples, best fit of the peaks
The vuggy samples are highly siliceous, and many appear to by the Rietveld method required use of two alunite starting
have been affected by silicification after the leaching. In these structures with different lattice parameters. This suggests that
samples, small euhedral quartz crystals that line void spaces the alunite has variable Na contents, which is consistent with
and fractures are identifiable with a hand lens (Table 1). electron microprobe data (Holley et al., 2016). Many of the
Samples with vuggy texture have highly variable Au and Ag samples showing vuggy quartz-alunite alteration also contain
metal contents (Table 1), despite the fact that sampling was jarosite (up to 19.8 wt %), hematite (up to 6.4 wt %), and
largely restricted to within the ore shells. The Au content of rutile (up to 1.6 wt %). Goethite, kaolinite, and woodhouseite
these samples ranged from <0.03 to 24.8 g/t, with Ag con- were detected in some of the samples.
centrations varying from <0.2 to 206 g/t. Mineralized samples
from Amable have bulk rock Au/Ag ratios ranging from 1:1 to Paragenetic sequence
1:1,000, averaging about 1:10. The Au/Ag ratios of mineral- Textural relationships observed in thin section constrain the
ized samples studied from Filo Federico are generally higher paragenetic relationships among the minerals in intensely
and vary from 1.5:1 to 1:900, with an average of 1:5. altered rocks from Veladero. The same paragenetic sequence
was observed at both orebodies and in the satellite zone at
Mineralogical composition Argenta. At the Fabiana prospect, the paragenetic sequence
Quantitative XRD analysis (Table 2) showed that the Veladero appears to be the same for the minerals present, although
samples with vuggy textures are primarily composed of quartz samples did not contain ore minerals.
and alunite. Samples showing vuggy quartz alteration con- Many of the samples contain quartz phenocrysts that have
tain 71.6 to 99.5 wt % quartz and have alunite concentrations not been affected by the intense alteration based on thin sec-
below 3.5 wt %. Although many of the samples contain no tion observations. All altered samples with vuggy textures
Table 2. Representative Quantitative XRD Analyses of Veladero Samples Exhibiting Vuggy Textures
In some samples, the Na content of alunite is highly variable and two alunite starting models were used to obtain a best-fit during Rietveld refinement; in
these cases the total alunite content is reported
Notes: All data in wt %; errors are given as ±3σ; - = not present or below detection limit (detection limits are phase and sample specific, but typically
0.3–0.5 wt % for most phases)
Abbreviations: Alu = alunite, Brt = barite, Gth = goethite, Hem = hematite, Jrs = jarosite, Kln = kaolinite, Qtz = quartz, R exp = expected error, Rwp =
weighted residual error, Rt = rutile, Sf = native sulfur, Wh = woodhouseite
contain fine-grained groundmass quartz that is host to abun- in mineralized samples, alunite occurs as aggregates of fine-
dant rutile and zircon inclusions. Alunite is intergrown with grained (10–100 mm) laths in the fine-grained groundmass
the fine-grained quartz or occurs in vugs and fractures. In or filling vugs. The SEM analyses reveal that alunite in the
many samples, small euhedral quartz crystals line the vugs or Veladero samples exhibits variations in the K/Na ratio. In
occur along fractures crosscutting the fine-grained groundmass some samples, alunite is intergrown with rare 10- to 50-µm
quartz. All other identified minerals formed late in the parage- crystals of aluminum phosphate-sulfate minerals, including
netic sequence, subsequent to the formation of the euhedral svanbergite and woodhouseite.
quartz. Gold occurs in void spaces, commonly in close textural
association with the euhedral quartz. Rare Ag iodide grains Euhedral quartz
also postdate the euhedral quartz. Barite is locally present in Many of the intensely altered rocks contain abundant fine-
vugs of the altered rocks. Other minerals present in vugs and grained (10–100 mm), fracture-controlled euhedral quartz.
along fractures include Fe oxide/hydroxide and jarosite. This quartz occurs as networks of ~100-µm, narrow veinlets
crosscutting the fine-grained groundmass quartz or filling
Quartz phenocrysts vugs and fractures (Fig. 4). Most samples collected from min-
Many of the samples contain quartz phenocrysts that can eralized zones (>0.2 g/t Au) contain euhedral quartz visible in
range up to 3 mm in size. The abundance of phenocrysts hand sample. Most samples with >0.03 g/t Au are character-
varies between samples, but can be as high as 30 modal %. ized by the presence of euhedral quartz in thin section (Table
The quartz phenocrysts are typically round and are weakly 1). In contrast, euhedral quartz only occurs in trace amounts
to strongly embayed. Internal fracturing is common, with in samples lacking detectable Au (<0.03 g/t Au). Euhedral
conchoidal or irregular fracture surfaces. Some samples quartz is also uncommon in samples with elevated alunite
contain abundant angular quartz phenocryst fragments that concentrations.
have either concave or convex margins (Fig. 3A). The quartz The fracture-controlled quartz is easily distinguished from
phenocrysts have a stable dark blue optical CL color that is the finer-grained groundmass quartz in thin section. Euhedral
typically homogeneous across the crystals. Along crosscutting crystals are mostly devoid of mineral inclusions and appear
fractures, the quartz can have pink to purple CL colors. clear and transparent in plane polarized light, typically exhib-
iting faint oscillatory growth zoning. The euhedral quartz
Fine-grained groundmass quartz overgrows and partially encloses darker, inclusion-rich cores
The groundmass of the intensely altered samples with vuggy of the anhedral, fine-grained groundmass quartz (Fig. 4A,
textures is almost entirely composed of fine-grained quartz B). In rare cases, Fe oxide/hydroxide forms up to 5-µm-thick
(Fig. 3B). This quartz occurs as anhedral grains that are growth zones within the outermost portions of the euhedral
<15 mm in size. In plane polarized light, the fine-grained quartz (Fig. 4B).
groundmass quartz appears cloudy and can be golden brown The euhedral quartz is distinctive in optical CL microscopy
to honey yellow due to a high density of mineral and vapor (Fig. 4C, D), and even volumetrically minor amounts of euhe-
inclusions (Fig. 3C, D). Most mineral inclusions are rutile that dral quartz that are difficult to identify in transmitted light
forms 1- to 15-µm prismatic, euhedral grains or aggregates of are easily detected (Fig. 4C). Under CL, the euhedral quartz
grains, randomly distributed within and among the anhedral has a bright yellow luminescence that fades rapidly to a deep
quartz crystals. Rutile crystals are golden brown and semi- orange or brown during a few seconds of exposure to the elec-
transparent. In addition to rutile, the fine-grained ground- tron beam (Fig. 5). The textures observed in CL confirm the
mass quartz contains euhedral zircon crystals that are up to transmitted light observations that the euhedral quartz forms
50 µm long. Some samples contain rare <2-µm pyrite inclu- networks of veinlets, fills vugs in the fine-grained groundmass
sions in the fine-grained groundmass quartz. quartz, and occurs as an overgrowth along the walls of cross-
The fine-grained groundmass quartz shows a heteroge- cutting fractures.
neous optical CL with colors ranging from bright pink to blue.
In some samples, the CL color is short-lived, and the blue Gold
or pink color of the quartz fades rapidly to muted hues in Gold at Veladero occurs as native Au grains within vugs and
less than a minute. The fine-grained groundmass quartz typi- fractures of the intensely altered volcanic rocks (Fig. 6A, B).
cally appears patchy under optical CL, with adjacent patches These grains are 5 to 25 mm in diameter and are rounded or
having different colors. Individual quartz grains display no irregularly shaped with angular margins. The Au grains do
growth zoning. not typically fill the entire void space in vuggy samples. The
rounded grains have little contact with the vug rims, whereas
Alunite irregularly shaped grains conform to the morphology of the
Veladero samples with vuggy textures contain variable portion of the vug that they occupy. Where the vugs are lined
amounts of alunite. In general, samples with high alunite by euhedral quartz crystals, native Au fills the space between
abundance contain low Au and Ag grades. In low-Au grade the quartz crystals. Grains of native Au were not observed to
samples, alunite forms fine-grained (10–100 µm) laths that be encapsulated by quartz. Jarosite commonly fills parts of
are scattered throughout the fine-grained groundmass quartz the vugs containing native Au. Where native Au and jarosite
(Fig. 3E). In some samples, subhedral or tabular, fine- occur together in void spaces, the Au grains are encapsulated
grained (10–100 µm) alunite replaces feldspar laths or fills by jarosite.
vugs (Fig. 3F). Rare 1- to 5-cm-wide alunite veins consist of Electron microprobe analyses indicate that the Au occurs as
coarse-grained (250 µm–3 cm) alunite laths. Where present native Au at fineness exceeding 980 (Table 3). The generally
A B
Fg qtz Euhedral
qtz
Jrs
Qtz phenocryst
Fg qtz
200 µm 50 µm
C Fg qtz D
Fg quartz
Euhedral qtz
Rt
Rt
Fg qtz
50 µm 50 µm
E F
Fg qtz
Alu+qtz
Alu
Clast
50 µm 200 µm
Fig. 3. Microphotographs of textural relationships characteristic of the groundmass of intensely altered volcanic rocks from
Veladero. (A) Intensely altered volcaniclastic rock from Amable. The dark-colored clast in the upper left part of the image
contains a quartz phenocryst. The clast and the surrounding light-colored matrix are replaced by fine-grained groundmass
quartz containing abundant mineral inclusions (sample EHV-123; plane polarized light). (B) Highly siliceous sample from
Amable containing fine-grained groundmass quartz with euhedral quartz crystals in a vug. The vug is partially filled by jarosite
(sample EHV-105; crossed polarized light). (C) Fine-grained groundmass quartz containing abundant rutile inclusions, giving
the quartz a cloudy appearance. The fine-grained groundmass quartz is crosscut and overgrown by euhedral quartz devoid
of mineral inclusions (sample EHV-105; plane polarized light). (D) Fine-grained groundmass quartz crosscut by myriads of
healed microfractures containing fluid inclusions filled with vapor. The quartz has a cloudy appearance due to the large num-
ber of inclusions (sample EHV-063 from Filo Federico; plane polarized light). (E) Intensely altered volcaniclastic rock from
Amable. The groundmass of the clast in the upper left part of the image is pervasively replaced by finely intergrown alunite
and quartz (sample EHV-018; plane polarized light). (F) Alunite replacing a feldspar lath in an intensely altered rock from
Amable (sample EHV-075; plane polarized light). Abbreviations: Alu = alunite, Fg qtz = fine-grained groundmass quartz, Jrs
= jarosite, Qtz = quartz, Rt = rutile.
A B
Fg qtz
Fg qtz Rt inclusions
Fg qtz
Au
Oscillatory
Fg qtz Growth zone growth zoning
Fg qtz with gth
Euhedral
qtz
40 µm Vug 20 µm
C D
Vug
Euhedral qtz
with oscillatory
growth zoning
Euhedral qtz
with oscillatory
growth zoning
Fg qtz
200 µm 200 µm
Fig. 4. Microphotographs of the different quartz types contained in intensely altered volcanic rocks from Veladero.
(A) Mineralized sample from Amable. The highly siliceous sample contains two distinct quartz generations. The groundmass
is composed of early fine-grained quartz hosting abundant mineral inclusions. A later quartz type that is largely devoid of
mineral inclusions overgrows the early fine-grained groundmass quartz. Euhedral crystals of the late quartz show oscilla-
tory growth zoning. Native gold occurs in textural association with the late quartz (sample EHV-105; plane polarized light).
(B) Mineralized sample from Amable. Small euhedral quartz crystals with oscillatory growth zoning overgrow earlier fine-
grained groundmass quartz. The fine-grained groundmass quartz contains abundant inclusions of rutile. The outermost
growth zone of the euhedral quartz crystals is intergrown with goethite. The vug is largely filled with goethite (sample EHV-
107; plane polarized light). (C) Cathodoluminescence image of a mineralized (0.40 g/t Au and 16.8 g/t Ag) sample from Filo
Federico. The early fine-grained groundmass quartz shows a stable blue to dark purple emission. It is crosscut by a network
of fractures that are lined by euhedral quartz exhibiting oscillatory growth zoning. The cathodoluminescence emission of the
euhedral quartz is short-lived and changes from yellow to brown. Image was taken after about 20 seconds of exposure (sample
EHV-060). (D) Cathodoluminescence image of a highly mineralized (1.87 g/t Au, 87 g/t Ag) sample from Amable. The rock
is pervasively silicified. Small euhedral quartz crystals with a yellow to brown emission occur throughout the groundmass of
the sample. The vugs are lined by euhedral quartz crystals that exhibit oscillatory growth zoning with individual zones ranging
from yellow to brown and black. The luminescence of the quartz is short-lived and changes from yellow to brown. Image was
taken after about 10 seconds of exposure (sample EHV-120). Abbreviations: Au = native gold, Fg qtz = fine-grained ground-
mass quartz, Gth = goethite, Qtz = quartz, Rt = rutile.
low Ag content of these grains indicates that only a small por- native Au grains, the Ag iodide minerals are paragenetically
tion of the total Ag contained in the oxidized Veladero ore is late and postdate the euhedral quartz. Encapsulation of the
contained in electrum. Ag iodide grains by quartz has not been observed.
In general, Ag iodide grains are more common in thin sec-
Silver minerals tions from samples collected at Amable than Filo Federico,
Silver at Veladero occurs as Ag iodide minerals, which form which may explain the overall lower Au/Ag ratios of the ore at
5- to 100-mm clusters of <1-mm particles in vugs and fractures Amable. Electron microprobe analyses showed that the Ag/I
(Fig. 6C, D). Although Ag iodide minerals and native gold ratio of the Ag iodide grains is mostly around unity (Table 3),
commonly occur in the same vugs, they were not observed suggesting that iodargyrite is the dominant Ag iodide mineral
in close textural association and a paragenetic relationship at Veladero. However, because individual Ag iodide grains are
between these phases cannot be determined. Similar to the too small to be analyzed individually, the electron microprobe
A B
Vug Fine-grained
groundmass
qtz
Euhedral qtz
with oscillatory
growth zoning 200 µm 200 µm
C D
200 µm 200 µm
Fig. 5. Series of cathodoluminescence images of an intensely altered volcanic rock from Veladero. The highly siliceous
sample from Filo Federico contains two distinct quartz generations. Early fine-grained groundmass quartz shows a bright
pink or blue luminescence. A later quartz type forms euhedral crystals exhibiting oscillatory growth zoning. The luminescence
of the euhedral quartz crystals rapidly changes during a few seconds of exposure to the electron beam (sample EHV-153). (A)
After 10 seconds of exposure to the electron beam, the euhedral quartz shows a short-lived, bright yellow emission. (B-D)
With continued exposure, the short-lived, yellow luminescence gradually fades to a dark brown (B after 20 seconds; C after
40 seconds; D after 80 seconds). Abbreviations: Qtz = quartz.
analyses represent averages of several adjacent grains. Some present in the altered rocks with vuggy textures, whereas
aggregates showed variability in brightness between particles hematite and goethite are common. The hematite and goe-
in SEM backscatter mode. For those aggregates, the Ag/I thite occur as a filling in vugs and voids, along fractures and
ratio of the Ag iodide aggregates was found to be highly vari- grain boundaries, and as cement (Fig. 7A). These cements
able, and significant amounts of Br, Cl, Fe, Hg, S, and Se predominantly occur around angular to subrounded, 10-
were detected. This variability may suggest that the Ag iodide to 100-µm quartz-rich clasts, completely filling void space
aggregates, at least in some cases, consist of multiple phases. between the clasts. The vug and fracture-filling Fe oxide/
Of more than 600 Ag-bearing opaque grains examined, only hydroxide commonly has irregular morphologies and fills only
one Ag sulfide grain was identified. The 1-mm grain occurred part of the void space. Where the Fe oxide/hydroxide occurs
in a void space in fine-grained groundmass quartz in a sample along grain boundaries, it forms an earthy coating that gives
from Amable, which yielded assay values of 24.8 g/t Au and the rock a dirty, rusty appearance in hand specimen.
62.2 g/t Ag. The grain contained Ag, Fe, and S (Table 3), but The Fe oxide/hydroxide commonly coats quartz, alunite,
its stoichiometry could not be conclusively determined due and barite grains. In many alunite-bearing samples, the
to the small grain size, resulting in an analysis giving a low alunite crystals have 1- to 5-µm-thick Fe oxide/hydroxide
analytical total. coatings that fill the irregularly-shaped interstices between
nearly interlocking alunite crystals or fill fractures where the
Hematite and goethite crystals have been broken. In samples containing euhedral
The Veladero deposit is oxidized, and mining thus far has quartz, the Fe oxide/hydroxide occurs in the void spaces
occurred in oxide ore at Amable, Filo Federico, and the Argenta overgrowing the quartz crystals, as coatings on the quartz
satellite zone. Significant amounts of sulfide minerals are not (Fig. 7A), and as inclusions in the outer growth zones of the
A B
Qtz
Au
Euhedral Jrs
qtz
Vug Au
Vug
20 µm 30 µm
C D
Vug
Iodargyrite
Iodargyrite
Euhedral
qtz
50 µm 1 µm
Fig. 6. Microphotographs of ore minerals contained in intensely altered volcanic rocks from Veladero. (A) Gold grain in a
sample from Amable. The gold grain occurs in a vug that is rimmed by euhedral quartz crystals showing oscillatory growth
zoning. The euhedral quartz postdates the fine-grained groundmass quartz containing abundant mineral inclusions (sample
EHV-106; plane polarized light). (B) Gold grain hosted by a jarosite grain. The jarosite partially fills a small vug in the
intensely altered sample from Amable (sample EHV-105; plane polarized light). (C) Iodargyrite aggregate hosted in a vug
that is lined by euhedral quartz crystals. The red outline highlights the location of high-magnification image shown in D
(sample EHV-119, from Amable; backscattered electron image). (D) High-magnification image of the iodargyrite aggregate
that consists of a large number of very small grains (sample EHV-119; backscattered electron image). Abbreviations: Au =
native gold, Jrs = jarosite, Qtz = quartz.
quartz (Fig. 4B). The Fe oxide/hydroxide is commonly inter- Jarosite also occurs in the Argenta and Fabiana satellite zones.
grown with jarosite. At Argenta, the style of jarosite occurrence is similar to that in
the main Veladero orebodies. However, the jarosite at Fabiana
Jarosite displays different characteristics, within a small (5 × 5 m) zone
Jarosite is abundant within mineralized zones at Amable and of strong jarosite alteration in otherwise unaltered Vacas Hela-
Filo Federico. It forms veinlets, single crystals in vugs, small das dacitic ignimbrite. The jarosite forms 20- to 500-µm bladed
clusters of crystals lining vug margins, or networks of crystals crystals replacing biotite and feldspar crystals, and the formerly
partially lining or completely filling fractures and complexly glassy matrix in the ignimbrite (Holley et al., 2016).
shaped void spaces (Fig. 7B, C). Individual jarosite crystals Most jarosite in the samples from Veladero exhibits growth
are typically 25 to 100 µm and vary from euhedral to subhe- zoning on the 5- to 10-µm scale in backscattered electron
dral morphology. In ore samples containing euhedral quartz, images, with some zones that are <1 µm in width. In some
jarosite fills void spaces rimmed by the quartz crystals, and cases, zoning can be recognized in plane polarized light. Cor-
in some cases, it forms an overgrowth on euhedral quartz. relation with semiquantitative EDX analyses suggests that
Where alunite and jarosite occur together, the jarosite fills zoning visible in optical microscopy primarily coincides with
the interstices between alunite laths. Where native Au and variations in the As and Pb concentrations in jarosite (Fig.
jarosite occur in the same vugs, the native Au grains are encap- 7C); minor variations in Na and K were also observed. Jarosite
sulated by the jarosite (Fig. 6B). Jarosite can be intergrown does not show optical CL.
with hematite and goethite, although the Fe oxide/hydroxide Trace element analysis by LA-ICP-MS indicates that jarosite
predominately forms overgrowths on jarosite or fills fractures. from Veladero contains abundant Ag (Table 4). Silver was
Table 3. Representative Electron Microprobe Analyses of Au and Ag Phases Present in Veladero Samples Exhibiting Vuggy Textures
Sample Ag As Au Br Cl Fe Hg I Te S Sb Se
Detection limit 0.04 0.04 0.19 0.05 0.02 0.12 0.19 0.05 0.05 0.01 0.05 0.04 Total
Native Au
EHV-063 0.18 - 97.9 - 0.04 - - - - 0.03 - - 98.2
EHV-063 - - 99.0 - 0.06 - - - - 0.03 - - 99.1
EHV-106 - - 98.7 - 0.05 - - - - 0.05 0.06 - 98.9
EHV-106 - - 100.3 - 0.08 0.25 - - - 0.03 - - 100.7
EHV-106 - - 99.5 - 0.08 - - - - 0.05 - - 99.6
Ag-S phase
EHV-106 39.8 0.04 - 0.23 0.08 11.0 - - - 12.5 - -
63.7
Ag-Hg-I-Se phases
EHV-106 40.6 - - 0.12 0.13 0.32 20.7 30.2 0.08 2.70 - 2.31
97.2
EHV-106 21.6 0.04 - 0.59 2.48 0.16 32.8 14.6 - 4.18 - 8.38
84.8
Ag-I phases
EHV-119 50.7 - - - 0.02 - - 47.1 0.05 0.02 - - 97.9
EHV-119 48.6 - - 0.25 0.08 - - 44.6 - 0.05 - - 93.6
EHV-119 45.0 - - 0.17 0.06 - - 49.1 0.09 - - - 94.4
EHV-119 53.4 - - - 0.06 - - 44.9 0.05 0.01 - - 98.4
EHV-119 46.9 - 0.19 0.24 0.06 - - 55.0 0.06 - - - 102.5
EHV-119 44.7 - - 0.15 0.05 - - 57.3 0.10 - - - 102.3
EHV-119 46.8 - - 0.21 0.08 - - 56.5 0.06 0.01 - - 103.7
EHV-119 47.4 - - 0.21 0.09 - - 55.0 0.05 0.01 - - 102.8
EHV-119 49.0 - - - 0.06 - - 48.2 - 0.01 - - 97.3
below detection limit (0.98 ppm) in about half of the spot anal- in the three samples with bulk rock Ag concentrations below
yses but ranged up to concentrations of 1,110 ppm in the other 0.4 g/t. Inspection of the time-resolved LA-ICP-MS signal
half of the spots analyzed (Fig. 8). For spots with Ag concen- suggested that Ag is hosted in the jarosite crystal structure,
trations above the detection limit, the average Ag concentra- since there was no evidence for the presence of Ag-rich micro-
tion was 280 ppm. Assay data of the samples were found to be inclusions. However, the 30-mm spot size used for LA-ICP-MS
a good predictor of jarosite Ag content. Silver was detected in analysis precluded resolution of individual growth zones in the
jarosite in the three samples having a bulk rock Ag concentra- jarosite. An Ag iodide grain encapsulated by jarsoite was inter-
tion exceeding 0.4 g/t, whereas no Ag was detected in jarosite sected only once during LA-ICP-MS analysis (Fig. 8B).
Table 4. Representative LA-ICP-MS Analyses of Jarosite Present in Veladero Samples Exhibiting Vuggy Textures
Sample Ag Al As Ba Cu Mn Na P Pb Rb Sr Tl
Detection limit 1.0 626 16 4.6 15 84 27 1,030 4.5 2.1 1.1 0.6
EHV-009 - 649 7,830 676 - - 234 2,770 19,300 35.7 152 5.1
EHV-009 - 3,660 7,040 5,520 - 135 343 4,860 6,380 12.5 858 0.6
EHV-009 - 1,390 8,020 1,440 - - 268 4,520 20,200 30.8 268 4.1
EHV-031 - 1,040 685 2,100 - - 598 1,050 1,840 5.7 31 17
EHV-031 - - 1,750 475 - - 1,900 2,040 631 87.2 122 50
EHV-031 - - 1,230 894 - - 1,170 1,570 821 54.9 170 35
EHV-066 - 9,410 16,600 2,090 - - 461 4,450 71,800 19.0 358 3.6
EHV-066 - 6,620 9,600 2,670 - - 1,040 2,590 33,200 39.6 468 11
EHV-066 - 7,900 13,300 2,250 - - 763 3,640 61,300 25.5 357 4.9
EHV-090 213 4,610 4,640 2,230 1,680 - 798 - 147 14.9 594 6.1
EHV-090 173 6,690 4,410 1,860 1,450 - 499 - 111 8.7 490 7.0
EHV-090 68.0 8,210 4,260 1,700 1,040 - 259 - 102 5.6 436 5.3
EHV-105 176 2,500 2,540 3,990 - - 4,920 2,000 5,180 107 598 76
EHV-105 137 3,400 3,130 3,230 - - 1,420 2,200 9,790 68.2 455 39
EHV-105 104 2,670 3,330 2,620 29 - 1,090 1,550 12,400 54.0 394 34
EHV-106 1,110 2,540 2,720 1,690 - - 4,160 1,600 3,290 102 729 58
EHV-106 54.2 6,150 3,440 2,280 99 258 1,540 - 6,540 23.8 731 14
EHV-106 1,060 1,960 2,510 1,100 - - 3,900 1,610 2,990 77.7 525 45
A B
Vug
Fine-grained
groundmass
Jrs qtz
Fe oxide/hydroxide
Euhedral Vug
qtz Euhedral
qtz
Fine-grained
groundmass
qtz
50 µm 50 µm
C Qtz D
Brt
Jrs
Vug
Qtz Brt
Vug
Euhedral qtz
Qtz Fine-grained
groundmass
200 µm qtz 50 µm
Fig. 7. Microphotographs of paragenetically late minerals filling vugs in intensely altered volcanic rocks from Veladero. (A)
Fe oxide/hydroxide in a sample from Amable. The Fe oxide/hydroxide occurs in a vug and overgrows euhedral quartz, which
exhibits oscillatory growth zoning (sample EHV-083; plane polarized light). (B) Jarosite crystals rimming a vug in a sample from
Filo Federico. The jarosite forms an overgrowth on euhedral quartz. The euhedral quartz exhibits oscillatory growth zoning and
postdates fine-grained groundmass quartz that contains abundant mineral inclusions (sample EHV-031; plane polarized light).
(C) Jarosite within a vug and along a network of fractures crosscutting fine-grained groundmass quartz in a sample from Amable.
The jarosite exhibits oscillatory growth zoning defined by variable concentrations of As and Pb (sample EHV-066; backscattered
electron image). (D) Barite filling a vug in a sample from Amable. The barite overgrows euhedral quartz crystals, which exhibit
oscillatory growth zoning (sample EHV-083; plane polarized light). Abbreviations: Brt = barite, Jrs = jarosite, Qtz = quartz.
A B Ag iodide
Mineral inclusion
Vug intersected during
10 9
ppm ppm analysis
4
ppm
Jrs Jrs Jrs
2
ppm
213
ppm
Qtz
173 Jrs
ppm
Qtz Jrs
8 50 µm 50 µm
ppm
C D
Jrs
Vug Jrs
760
ppm
Euhedral 1,110
qtz ppm
81 Fe oxide/
ppm Qtz
hydroxide 468
Fine-grained ppm
groundmass
qtz
50 µm 100 µm
Fig. 8. Microphotographs of jarosite grains analyzed by LA-ICP-MS. (A) Ag-bearing jarosite located along a fracture cross-
cutting fine-grained groundmass quartz. The jarosite has variable Ag content. The sample from Amable contains 19.5 ppm Ag
(sample EHV-090). (B) Ag-bearing jarosite hosted by fine-grained groundmass quartz. LA-ICP-MS analysis showed that the
Ag content of the jarosite is low. However, the jarosite encapsulated a small Ag iodide grain that was partially ablated during
LA-ICP-MS analysis. The sample from Amable contains 19.5 ppm Ag (sample EHV-090). (C) Ag-bearing jarosite filling a
vug that is lined with euhedral quartz crystals showing oscillatory growth zoning. The euhedral quartz overgrows fine-grained
groundmass quartz containing abundant mineral inclusions. The Ag content of the sample from Amable is 26.0 ppm (sample
EHV-105). (D) Jarosite with high Ag content filling a vug. The sample from Amable contains 62.2 ppm Ag (sample EHV-106;
plane polarized light). Abbreviations: Jrs = jarosite, Qtz = quartz.
growth zones and are interpreted to be primary. Short axes of above 0°C in one primary inclusion suggested the presence
the fluid inclusions are generally 1 to 2 µm and long axes are of CO2.
2 to 3 µm, although in some cases the long axis may be up to
5 µm. The primary fluid inclusions in the euhedral quartz are Stable Isotopes
ubiquitously liquid-rich with a small vapor bubble and con- Isotopic analyses of alunite and jarosite samples are given
sistent liquid-to-vapor ratios (Fig. 9B-D). These inclusions in Table 6. Alunite from Amable and Filo Federico has δ34S
are most abundant in growth zones also containing acicular values ranging from 5.9 to 17.5‰. The alunite samples have
dravite crystals (confirmed by SEM-EDX analysis; Mg > Fe δ18OSO4 values ranging from 2.0 to 9.0‰ and δ18OOH values
in all analyses). The dravite crystals are 1 to 3 µm thick and 5 between 4.0 and 9.8‰. Alunite δD values range from –74
to 20 µm in length (Fig. 9C, D). to –88‰. The isotopic signature of alunite from the nearby
Heating and freezing experiments were conducted on the Argenta satellite zone is nearly identical to alunite from Filo
primary liquid-rich fluid inclusion assemblages contained in Federico (Table 6). Alunite from the Fabiana prospect has
euhedral quartz crystals in two samples from Amable. Homog- δ34S, δ18OSO4, δ18OOH, and δD values within the ranges of
enization of these small inclusions occurred to the liquid at those determined for Amable and Filo Federico samples.
temperatures between 185° and 235°C (Table 5). Freezing Barite from Amable has a δ34S value of 30‰ and a δ18OSO4
experiments showed that the temperature of last ice melting value of 8‰.
of the inclusions ranged from –0.1° to –3.0°C, indicating a Jarosite δ34S values from Amable and Filo Federico range
salinity of ~0.2 to 5 wt % NaCl equiv. Melting of a compound from –3.8 to –0.6‰. Jarosite δ18OSO4 values range from –4.0 to
A Rt
B
inclusions
Primary 2 µm
liquid-rich fluid
inclusion
Fine-grained
groundmass
qtz
Euhedral qtz
trail of secondary
vapor-rich inclusions
C Oscillatory D
growth zoning Primary
liquid-rich fluid
inclusions
Drv
inclusions
Drv
inclusions
20 µm 10 µm
Fig. 9. Fluid inclusion characteristics of quartz in intensely altered rocks exhibiting vuggy textures. (A) Secondary trail of
vapor inclusions crosscutting the fine-grained groundmass quartz in a sample from Amable. The fine-grained groundmass
quartz also contains abundant euhedral rutile inclusions (sample EHV-126; plane polarized light). (B) Primary liquid-rich
fluid inclusion in a euhedral quartz grain in a sample from Amable. The euhedral quartz grain forms an overgrowth on the
earlier fine-grained groundmass quartz, which contains abundant rutile inclusions. The euhedral quartz shows oscillatory
growth zoning. The primary inclusion is located within the growth zone. The euhedral crystals line a vug that is filled with
goethite. The inset shows a higher magnification image of the liquid-rich inclusion that is approximately 2 µm in diameter
(sample EHV-126; plane polarized light). (C) Euhedral quartz containing dravite inclusions in a sample from Amable. The
dravite crystals likely served as nuclei for primary liquid-rich fluid inclusions. The quartz exhibits well-developed oscillatory
growth zoning (sample EHV-108; plane polarized light). (D) Higher magnification image of the same group of primary liquid-
rich fluid inclusions contained in a growth zone of the euhedral quartz crystal. Abbreviations: Drv = dravite, Qtz = quartz,
Rt = rutile.
0.7‰, and δ18OOH values vary from –10.3 to –2.1‰. Jarosite acidic alteration, Au-Ag mineralization, and pervasive oxida-
δD values range from –137 to –228‰. There are no system- tion in the epithermal environment.
atic differences between Amable and Filo Federico jarosite
samples. In comparison, one sample of jarosite that replaces Acidic alteration
biotite and feldspar at the Fabiana prospect has a distinctly Intense hydrothermal alteration in high-sulfidation epi-
higher δ34S value of 8.2‰, with a δ18OSO4 value of 6.0‰, a thermal deposits is caused by acidic sulfate-chloride waters
δ18OOH value of 5.8‰, and a δD value of –156. that are formed through condensation of magmatic vapor into
groundwater (Stoffregen, 1987; Giggenbach et al., 1990; Rye
Discussion et al., 1992; Hedenquist et al., 1994b; Hedenquist and Taran,
Although the styles of hydrothermal alteration and mineral- 2013). During acid leaching, most chemical components are
ization at Veladero are similar to other high-sulfidation epi- mobile, except for silica. Quartz solubility is low under these
thermal deposits (cf. Stoffregen, 1987; Muntean et al., 1990; conditions (Fournier, 1985). The fine-grained groundmass
Hedenquist et al., 1994a; Arribas et al., 1995; Longo et al., quartz observed in altered volcanic rocks having vuggy tex-
2010; Chang et al., 2011; Cerpa et al., 2013), the detailed tures is interpreted to have formed through recrystallization
petrographic and mineralogical study summarized here pro- of the siliceous residue. During acid leaching, Ti and Zr were
vides critical new constraints on the processes leading to largely immobile. The rutile that is disseminated throughout
Table 5. Fluid Inclusion Data Obtained from Primary Inclusions the fine-grained groundmass quartz is also interpreted to have
Hosted by Euhedral Quartz Contained in Veladero Samples formed through recrystallization, incorporating Ti originally
Exhibiting Vuggy Textures
contained in ferromagnesian minerals or volcanic glass. Zir-
Number of Temperature con inclusions in the fine-grained groundmass quartz prob-
Homogenization inclusions in of last ice wt % ably represent relict igneous grains.
temperature (°C) assemblage melting (°C) NaCl equiv Alunite is formed as a result of the condensation of mag-
Sample EHV-108
matic vapor into meteoric water (Rye, 1993; Hedenquist and
Lowenstern, 1994). The d34S values of Veladero alunite are
200-210 2 –1.5 2.57
205-210 2 –1.4 2.41 heavier than the d34SSS value expected for magmatic vapor
200-205 7 –1.4 2.41 (Fig. 10A), presumably due to alunite forming from the dis-
200-205 3 –1.4 2.41 proportionation of magmatic SO2 to H2S and H2SO4 (cf. Rye
200-210 3 –1.3 2.24 et al., 1992; Rye, 1993). The d34SSS values of magmatic vapor
205-210 1 –2.6 4.34
185-195 8 –0.1 0.18
at Veladero cannot be determined since there are no sulfide
185-190 1 –1.8 3.06 minerals in the oxidized ore. However, studies on other high-
220-225 3 -1 - sulfidation epithermal deposits of the El Indio-Pascua metal-
185-190 3 -1 - logenic belt, including Pascua-Lama (Deyell et al., 2005a) and
190-195 4 -1 - Tambo (Deyell et al., 2005b), showed that magmatic vapor
200-205 3 –1.4 2.41
200-205 3 0.02 0.00 forming the acidic alteration had d34SSS values of 1 to 4‰
185-190 2 –1.0 1.74 (Fig. 10A).
190-195 2 -1 - The dD and d18O values of fluids in equilibrium with alu-
210-215 8 -1 - nite were calculated using the isotopic composition of the
190-195 6 –1.2 2.07
175-180 3 –0.5 0.88
alunite (Table 6) and equations of Stoffregen et al. (1994).
225-235 2 –2.1 3.55 Because alunite depositional temperatures could not be esti-
175-180 4 –1.9 3.23 mated due to the lack of coexisting pyrite, the fluid calcula-
185-190 2 –2.3 3.87 tions were based on alunite δ18OSO4 values at an assumed
temperature of 250°C (Deyell et al., 2005a, b). The calcu-
Sample EHV-126
lated compositions of the hydrothermal fluids plot on a mix-
215-220 1 –3.0 4.96
220-225 1 -3 -
ing trend between paleometeoric water and magmatic vapor
(Fig. 10B).
Notes: - = not determined Only premineralization alunite was identified at Veladero,
1 Last ice melting could not be determined due to small size of the where it forms fine laths in the fine-grained groundmass
inclusions quartz and in void spaces. Although magmatic-hydrothermal
2 Another inclusion in the same growth zone had a temperature of the last
ice melting of –1.6°C activity in the four alteration centers at Veladero extended
3 Temperature of last ice melting could not be determined due to the forma- over a period of approximately 3 m.y. (Holley et al., 2016),
tion of a compound melting above 0°C the centers of alteration and mineralization were sufficiently
20
A
δ34SΣS Tambo
Pascua Lama
ore-stage alunite
15
-5
-10 -5 0 5 10 15 20 25 30 35
δ S (‰)
34
50
alunite SO4
alunite OH
B
Volcanic Pascua Lama
jarosite SO 4
0 li ne vapor ore-stage
jarosite OH
ter alunite
wa
alunite fluids Felsic
ic magmatic
jarosite fluids
e or fluids
-50 et
M
δD (‰)
Paleo-meteoric
-100 water
Fabiana
e
-150 jarosite lin
te
i ni
ol
Ka
-200 Pascua Lama
e
late jarosite lin
e
sit
ro
Ja
-250
-30 -25 -20 -15 -10 -5 0 5 10 15 20
δ18O (‰)
Fig. 10. Stable isotopic compositions of minerals from the Veladero deposit. (A) Alunite, jarosite, and barite δ34S and δ18OSO
values. Analytical error is smaller than the symbol size. Estimated δ34S∑S values of the magmatic-hydrothermal fluids from
Pascua-Lama and Tambo (Deyell et al., 2005a, b) and the compositions of Pascua-Lama ore stage alunite (Deyell et al.,
2005a) are given for comparison. (B) Alunite and jarosite δ18OSO4, δ18OOH , and δD values plotted in reference to the volcanic
vapor field (Giggenbach, 1992), the composition of felsic magmatic fluids (Taylor, 1992), the meteoric water line (Craig,
1961), the jarosite line (Rye and Alpers, 1997), and the kaolinite line (Savin and Epstein, 1970). The isotopic compositions
of ore-stage alunite and late jarosite at Pascua-Lama (Deyell et al., 2005a) and the estimated composition of El Indio-Pascua
belt paleometeoric waters (Deyell et al., 2005a) are also given. The alunite and jarosite isotope data were used to calculate the
isotopic composition of the fluids in equilibrium with alunite (calculated from Stoffregen et al., 1994) and jarosite (Alpers et
al., 1988; Rye and Alpers, 1997). See text for details.
separated so that alteration did not overprint earlier formed the southern end of the El Indio-Pascua belt, where alunite
ore minerals. This contrasts with the Pascua-Lama deposit has been reported to occur in pre-, syn-, and postore assem-
located 10 km from Veladero and with the Tambo deposit at blages (Deyell et al., 2005a, b).
Quartz precipitation could explain the observed variations in the salinities of the
In high-sulfidation epithermal deposits, acidic alteration of the primary fluid inclusion assemblages measured in the euhedral
host rocks generally predates ore formation (Arribas, 1995). quartz, although the limited number of measurements does
Steven and Ratté (1960) and Stoffregen (1987) recorded not allow establishment of a mixing trend (Table 5).
this relationship in their seminal studies on the Summitville Hypogene Au-Ag mineralization
deposit in southwestern Colorado. They showed that ore min-
The nature of hypogene mineralization at Veladero is diffi-
erals primarily occur in vugs in the intensely altered rocks
cult to discern due to the pervasive oxidation of the deposit.
and thus must have formed after acidic alteration. However,
Although native Au is present in hypogene ores in some high-
in some high-sulfidation epithermal deposits, the ore and
sulfidation epithermal deposits (Stoffregen, 1987; Jannas
gangue minerals are locally intergrown, which has been inter-
et al., 1990; Arribas et al., 1995; Moritz et al., 2004; Choui-
preted as evidence for the contemporaneous occurrence of
nard et al., 2005a; Longo et al., 2010), the high fineness of
mineralization and acidic alteration (Chouinard et al., 2005a;
the native Au (cf. Mann, 1984; Webster and Mann, 1984) and
Mavrogenes et al., 2010; Voudouris, 2011; King et al., 2014). the textural association with Fe oxide/hydroxide and jarosite
At Veladero, early acidic leaching of the host rocks was fol- indicate that most, if not all, of the native Au at Veladero
lowed by deposition of euhedral quartz grains in vugs and formed from oxidation of a precursor sulfide mineral such as
along fractures. Hypogene mineralization mostly took place pyrite. The occurrence of Au-bearing pyrite as a hypogene ore
after the euhedral quartz formation. For this reason, acidic mineral has been documented at high-sulfidation epithermal
alteration and mineralization could not have been contempo- deposits that have not been pervasively oxidized (Chouinard
raneous at Veladero. The formation of the euhedral quartz et al., 2005b; Deditius et al., 2009; King et al., 2014; Franchini
marks the transition from the alteration to the mineralization et al., 2015; Tanner et al., 2016).
stage. Assuming that Fe oxide/hydroxide and jarosite occupy the
The euhedral quartz at Veladero could not have formed same textural setting as their hypogene precursors, pyrite
during leaching of the volcanic rocks. The leaching was originally present in hypogene ores would have been located
caused by sulfate-chloride waters resulting from condensation primarily within vugs and fractures of the leached volcanic
of magmatic vapor into groundwater, and quartz precipitation rocks, overgrowing the euhedral quartz. However, in rare
is inhibited in acidic conditions (Fournier, 1985). Quartz pre- samples, the outermost growth zones of the euhedral quartz
cipitation requires silica polymerization and could only take crystals contain bands of Fe oxide/hydroxide (Fig. 4B), which
place after a shift to slightly acidic to near-neutral conditions. is assumed to be the product of sulfide oxidation. The textural
Planes of secondary vapor inclusions are absent in the euhe- observations thereby imply that euhedral quartz deposition
dral quartz and ubiquitous in the fine-grained groundmass overlapped with the onset of sulfide formation.
quartz, suggesting that magmatic vapor was not present dur- The Ag in Veladero ore is contained in Ag iodides and Ag-
ing euhedral quartz precipitation. The fine-grained ground- bearing jarosite. The origin of the Ag iodides, similar to that
mass quartz formed from the recrystallized siliceous residue of native Au, cannot be ascertained in the absence of deep
that was produced by acid leaching, whereas euhedral quartz drill holes sampling the ore below the base of oxidation. At
precipitation records the addition of silica to the previously Pascua-Lama, chlorargyrite and iodargyrite are the domi-
leached rocks. Limited fluid inclusion data also suggest that nant ore minerals and occur in enargite-bearing ores, which
the euhedral quartz precipitated from liquid-phase hydro- led Chouinard et al. (2005a) to propose that the Ag halides
thermal fluids. The yellow CL emission of the euhedral quartz are of hypogene origin and that these minerals formed dur-
is indicative of rapid precipitation in a reduced environment ing the waning stages of the hydrothermal activity. Similarly,
(Götze et al., 2015). iodargyrite at Rodalquilar in Spain has been interpreted as
The boiling point-depth curve for H2O-NaCl solutions a possible hypogene phase (Arribas et al., 1995). However,
(Driesner and Heinrich, 2007) can be used to constrain mini- it is well known that Ag halides are also common in super-
mum pressures that were present during precipitation of the gene-enriched zones of high-sulfidation epithermal deposits
euhedral quartz. A 5 wt % NaCl equiv liquid at 175°C would (Oviedo et al., 1991; Hedenquist et al., 2000; Sillitoe, 2009),
boil at 8.6 bar, whereas the same liquid at 235°C would boil particularly in arid climates (cf. Gołȩbiowska et al., 2010). In
at 29.8 bar. Consequently, quartz precipitation likely occurred contrast to the Ag iodides, the Ag-bearing jarosite at Veladero
at least 90 to as much as 300 m below the paleowater table is clearly of secondary origin, based on textural evidence and
at hydrostatic conditions. This is consistent with an estimated the stable isotope data discussed below. Incorporation of Ag
mineralization depth of less than 300 m based on geomorpho- into Ag-bearing jarosite during oxidation of the hypogene ore
logical constraints (Bissig et al., 2002b). Quartz precipitation suggests that much of the Ag at Veladero was originally con-
would have occurred as a result of ascent and cooling of the tained in Ag sulfides, such as acanthite/argentite, Ag-bearing
liquid (Fournier, 1985). At a temperature of 235°C and a pres- pyrite, or galena. Sulfide precursors would also explain the
sure of 30 bar, a liquid of the H2O-NaCl system containing enrichment of other metals in the jarosite, including As, Cu,
5 wt % NaCl equiv has a silica solubility of 357 mg/kg SiO2. At Pb, and Tl (Table 4).
175°C and 9 bar, quartz solubility in the liquid is only 175 mg/ The fluid inclusion data at Veladero demonstrate that the
kg SiO2 (calculated according to Akinfiev and Diamond, 2009, euhedral quartz present in siliceous samples was formed from
with thermodynamic data from Driesner, 2007). Cooling of moderately saline (<5 wt % NaCl equiv) liquid-phase hydro-
the liquid at shallow depths may have in part resulted from thermal fluids at temperatures of ~200°C within a few hun-
mixing with near-surface waters (cf. Hedenquist, 1991). This dred meters below the paleowater table. Because the euhedral
quartz crystals are not crosscut by trails of vapor inclusions and the estimated paleometeoric water composition (Fig. 10B). In
show no evidence for a high-temperature hydrothermal over- contrast, the dD and d18O values of fluids in equilibrium with
print in optical CL, precious metal mineralization at Veladero the jarosite from Fabiana are consistent with mixing between
could not have formed from a magmatic vapor. The occur- paleometeoric water and magmatic vapor (Fig. 10B), support-
rence of Fe oxide/hydroxide bands in the outer growth zones ing a hypogene origin for this jarosite.
of the euhedral quartz suggests that the liquid-phase hydro- The stable isotope data of jarosite from Amable and Filo
thermal fluids forming the quartz were also responsible for Federico also can be used to estimate the paleoelevation of
sulfide precipitation. Most of the sulfide deposition occurred the Veladero area at the time of the oxidation event. Given the
after the quartz precipitation, presumably during continued strongly negative hydrogen fractionation between jarosite and
cooling of the liquid-phase hydrothermal fluids. This is con- water (~–60‰ at 25°C; Alpers et al., 1988), Veladero jarosite
sistent with observations made at Rodalquilar, Spain, where δD values correspond to a meteoric water composition of –96
Au mineralization is associated with pyrite and interpreted to to –168‰. Poage and Chamberlain (2001) reported empiri-
have occurred from reduced, liquid-phase hydrothermal flu- cal relationships between elevation and present δ18O compo-
ids at temperatures <180°C (Arribas et al., 1995). sitions of meteoric water. Using their curve for Central and
South America, δ18O values of meteoric water were computed
Pervasive oxidation for elevations between 1,000 and 6,000 m. Expected δD val-
The Veladero deposit and satellite zones at Amable and Fabi- ues for the meteoric water at different elevations were cal-
ana are pervasively oxidized. Sulfosalt minerals have not been culated using the meteoric water line for northern Chile by
recognized and sulfide minerals are extremely uncommon. Aravena et al. (1999). An adjustment was made as deep-sea
Rare, <2-µm pyrite inclusions occur in the cores of fine- sediment cores indicate that late Miocene deep-sea δ18O val-
grained groundmass quartz, and one sample containing Ag ues were roughly 2‰ less than today (Zachos et al., 2001).
sulfide was documented. The calculated δD values for meteoric water correspond
Iron oxide/hydroxide and jarosite are the most abundant to late Miocene elevations for the Veladero area between
minerals formed during the pervasive oxidation of the ore- approximately 4,000 and 5,200 m a.s.l., similar to the eleva-
bodies, filling vugs and fractures in the altered rock. Rye tion of the deposit today.
et al. (1992) showed that secondary sulfate minerals formed Alunite and jarosite 40Ar/39Ar dating (Holley et al., 2016)
through sulfide oxidation have δ34S values similar to those showed that jarosite formation at Veladero commenced dur-
of the precursor sulfide phases. Although no δ34S data are ing the waning stages of the magmatic-hydrothermal activity,
available for sulfide minerals from Veladero, the Amable and or immediately thereafter, but continued for as much as 3 m.y.
Filo Federico jarosite δ34S values cluster near, or are slightly Pervasive oxidation of the orebody during the waning stages
lighter than, those of sulfide minerals from Pascua-Lama of the hydrothermal activity could have occurred in the steam-
(Deyell et al., 2005a) and Tambo (Deyell et al., 2005b). This heated environment as proposed in other high-sulfidation
suggests that the sulfur in the jarosite was probably largely deposits (Stoffregen, 1987; Hedenquist et al., 1994a; Bethke
derived from preexisting sulfide minerals (Fig. 10A). et al., 2005). Subsequent valley incision and climate dessica-
In contrast to samples from Amable and Filo Federico, the tion exposed the deposit to supergene weathering, resulting in
jarosite sample Fabiana has a heavier δ34S value and is textur- the complete conversion of sulfide to oxide ore (Bissig et al.,
ally distinct, occurring as a replacement of biotite and feldspar 2002b, 2015).
crystals and the formerly glassy matrix in the host ignimbrite.
The possibility of hypogene jarosite at Fabiana is intriguing, Implications for the deposit model
but the jarosite alteration is spatially restricted, precluding High-sulfidation epithermal deposits typically form contem-
meaningful follow-up sampling. Few examples of hypogene poraneously with volcanism and related intrusions (Sillitoe
jarosite have been reported in the literature. John et al. (2008) and Hedenquist, 2003). At Veladero, Holley et al. (2016)
suggested a possible magmatic-steam origin for an occurrence demonstrated that magmatic-hydrothermal activity occurred
of jarosite at Mount Rainier in Washington based on stable from 13.12 ± 0.18 to 10.09 ± 0.08 Ma, which broadly over-
isotope values. Jarosite at Pascua-Lama is crosscut by mineral- laps with the deposition of the volcanic rocks of the Vacas
ized stockwork veins and can be overgrown by coarse alunite, Heladas Formation (Bissig et al., 2001). Dacite lavas at the
which Chouinard et al. (2005a) interpreted as evidence of Fabiana prospect, dated at 11.0 ± 0.2 Ma (Bissig et al., 2001),
either a magmatic-hydrothermal origin of the jarosite or inter- were emplaced between the mineralization events at Amable
mittent precipitation of supergene jarosite between multiple and Filo Federico, and hydrothermal alteration at Fabiana
events of hydrothermal activity. Stoffregen et al. (2000) sug- occurred after the dome emplacement (Holley et al., 2016).
gested that jarosite is unlikely to form at high temperatures, A self-potential anomaly suggests the presence of a large
although hydrothermal jarosite can form in the temperature unexposed intrusion between Veladero and Pascua Lama,
range from ~100° to ~300°C and has been identified at sev- approximately 6 km to the northwest of Filo Federico (Choui-
eral localities (e.g., Martinez-Frias et al., 2004; Lueth et al., nard et al., 2005a). Diatreme facies volcanic rocks at Amable
2005). contain rare clasts of porphyry quartz veinlets (Holley, 2012),
The compositions of fluids in equilibrium with jarosite (Fig. providing additional evidence for an association between
10B) were calculated using the equations of Rye and Stof- magmatic-hydrothermal activity at Veladero and igneous
fregen (1995) based on the jarosite δ18OOH values (e.g., Rye activity at depth.
and Alpers, 1997), at an assumed temperature of 25°C. The The observations at Veladero are consistent with the model
calculated Amable and Filo Federico jarosite fluids plot near proposed for the Far Southeast-Lepanto deposits in the
Mankayan district in the Philippines, where phase separa- in contrast to dense hypersaline liquid (cf. Hedenquist et al.,
tion of magmatic-hydrothermal fluids at depth produced a 1998; Heinrich, 2007). Over time, cooling causes the fluid
high-salinity liquid responsible for potassic alteration in the flow to be dominated by liquid, although conditions might be
porphyry environment and a buoyant magmatic vapor that very close to the boiling point for depth. The resulting liquid
ascended into the epithermal environment (Hedenquist likely transports precious metals (Hedenquist et al., 1998),
et al., 1998). Similar to the laterally extensive lithocap altera- and economic mineralization might result upon cooling and
tion at Lepanto (Hedenquist et al. 1998; Chang et al., 2011), dilution with near-surface waters (cf. Mancano and Campbell,
early acidic leaching of the volcanic host rocks at Veladero 1995). Although magmatic vapors might transport significant
was caused by acidic sulfate-chloride waters, which formed amounts of metals, much of the metal may be lost into the
through condensation of magmatic vapor into groundwater. atmosphere as demonstrated for the fumarolic discharge at
At Veladero, a magmatic source for the vapor is confirmed by White Island, New Zealand (Hedenquist et al., 1993).
the δD and δ18O values of alunite formed during this process.
Early workers suggested that hypogene Au-Ag mineraliza- Implications for Ore Processing
tion in high-sulfidation epithermal deposits forms from liquid- Veladero is an open-pit, heap leach Au and Ag mine. The ore
phase hydrothermal fluids precipitating ore minerals within undergoes a two-stage crushing process with precious metals
previously altered rocks (Stoffregen, 1987; Arribas et al., 1995; extracted from the crushed ore in a valley-fill cyanide heap
Hedenquist et al., 1994a, 1998). However, more recently it leach pad. Approximately 250,000 m3 of ore is being leached
has been proposed that high-sulfidation epithermal deposits at any given time. Pregnant solution is collected and pumped
can be formed by magmatic vapor and that high-temperature to a Merrill-Crowe Zn cementation plant for Au recovery.
vapor condensation into ambient groundwater is responsible Gold doré produced by this process is shipped off site for
for both alteration and mineralization (Vennemann et al., further refining. The Au recovery ranges from 70 to 80%,
1993; Chouinard et al., 2005a; Williams-Jones and Heinrich, whereas less than 10% of the Ag is recovered (Roscoe Postle
2005; Scher et al., 2013; King et al., 2014). For example, Associates, 2012).
Mavrogenes et al. (2010), Henley and Berger (2011, 2012), To account for the low Ag recovery of the cyanidation pro-
Henley et al. (2012), and Berger et al. (2014) proposed that cess, previous workers suggested that Ag-bearing minerals in
magmatic vapor could deposit ore minerals directly by isen- Veladero ore are encapsulated by quartz (Barrick Gold Cor-
thalpic decompression at temperatures above 500°C. Experi- poration, press release, September 19, 2007). However, the
mental investigations confirm that metals such as Ag, Au, and present study demonstrates that precious metal mineraliza-
Cu can indeed be transported in the vapor phase (Archibald tion postdated silicification.
et al., 2001, 2002; Zezin et al., 2011; Migdisov and Williams- The microanalytical data presented herein indicate that
Jones, 2013; Hurtig and Williams-Jones, 2014; Migdisov et al., much of the Ag in Veladero ore is locked up in Ag-bearing
2014). jarosite, not in native Ag and/or Ag sulfide minerals that are
The observations of the present study argue against the role readily soluble in cyanide solutions. In ore samples, jarosite
of magmatic vapors as mineralizing fluids at Veladero. Acidic occurs at concentrations of up to ~20 wt %. Because the Ag
leaching of the volcanic rocks was followed by a shift from content of jarosite averages tens to hundreds of ppm, Ag-bear-
a vapor-dominated to a liquid-dominated magmatic-hydro- ing jarosite likely contains a significant portion, if not most, of
thermal system, when vugs and fractures were overgrown by the Ag in Veladero ore. To recover Ag from ore containing
euhedral quartz. Hypogene sulfide formation commenced Ag-bearing jarosite, a different extraction process is required.
during the late stages of quartz precipitation, probably result- For instance, a two-step process could be employed, whereby
ing in the precipitation of mostly pyrite. Quartz and hypo- the Ag-bearing jarosite is dissolved through alkaline decom-
gene mineralization formed from liquid-phase hydrothermal position followed by cyanidation to allow complexation of
fluids under slightly acidic to near-neutral and reduced con- the Ag from the decomposition solids (Patino et al., 1998).
ditions. Texturally similar quartz, commonly referred to as Simple bench-scale laboratory experiments confirmed that
drusy quartz, has been described from other high-sulfidation a significant portion of Ag contained in Veladero ore can be
epithermal deposits, including El Indio in Chile (Mavrogenes brought into solution through leaching of the crushed mate-
et al., 2010; Henley et al., 2012; Tanner et al., 2013), Lepanto rial in NaClO solution (E. Holley, T. Monecke, and T. Bissig,
in the Philippines (Chang et al., 2011), Martabe in Indonesia unpub. data, 2012).
(Sutopo, 2013), Summitville in Colorado (Stoffregen, 1987; Oxidized high-sulfidation epithermal deposits containing
Mavrogenes et al., 2010; Tanner et al., 2013), and Yanacocha Ag-bearing jarosite may become an attractive exploration tar-
in Peru (Longo et al., 2010). The petrographic investigations get for Ag if an economic recovery process could be devised.
at Veladero show for the first time that this quartz type marks As jarosite represents a common oxidation product in high-
an important stage in the evolution of high-sulfidation ore- sulfidation epithermal deposits, significant value could be
forming environments. unlocked in many Ag-rich deposits by implementing strate-
The observed transition from vapor-dominated to liquid- gies for Ag recovery from jarosite. The Veladero deposit alone
dominated magmatic-hydrothermal fluid flow conditions is is estimated to contain nearly 200 Moz of Ag (Barrick Gold
likely linked to downward cooling and crystallization of the Corporation, 2016).
intruding magma, coupled with deepening levels of fluid exso-
lution (e.g., Hedenquist et al., 1998; Pudak et al., 2009). The Conclusions
early presence of vapor-dominated fluids producing acidic The Miocene Veladero high-sulfidation epithermal deposit
alteration implies phase-separation, in which vapor is buoyant in the El Indio-Pascua metallogenic belt was produced by
an evolving magmatic-hydrothermal system. Early in the discussions that improved an earlier version of the manuscript.
development of the ore-forming environment, highly acidic The manuscript has also benefited from comments made by
sulfate-chloride waters were produced through condensa- John Mavrogenes and David Cooke. Jeff Hedenquist and
tion of magmatic vapor into groundwater. Acid leaching of David John provided insightful reviews. This study was part of
the volcanic host rocks formed an extensive zone of intense a Ph.D. project by EAH, who was also supported by the Orlo
hydrothermal alteration, grading from vuggy quartz and E. Childs Fellowship and the Stewart Wallace Endowment in
quartz-alunite alteration in the core outward through zones Economic Geology at Colorado School of Mines.
of advanced argillic through argillic into propylitic alteration.
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