Ore Geology Reviews 34 (2008) 304–316

Contents lists available at ScienceDirect

Ore Geology Reviews

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

Geology, geochemistry and 40Ar/39Ar ages of the Cerro Millo epithermal

high-sulfidation gold prospect, southern Peru
Daniel Hennig a,⁎, Bernd Lehmann a, Ray Burgess b, Mohammad Ali Nekouvaght Tak a
a
Technical University of Clausthal, Institute of Mineralogy and Mineral Resources, Adolph-Roemer-Straße 2A, 38678 Clausthal-Zellerfeld, Germany
b
University of Manchester, School of Earth, Atmospheric and Environmental Sciences, Oxford Road, Manchester M13 9PL, United Kingdom

A R T I C L E I N F O A B S T R A C T

Article history: The high-sulfidation system of Cerro Millo is hosted in a Late Miocene andesitic paleo-stratovolcano in the
Received 24 November 2005 High Andes of southern Peru. Very pronounced advanced-argillic (alunite), silicic, and argillic (kaolinite and
Received in revised form smectite) alteration characterizes the central part of the hydrothermal system. Propylitic alteration is
Accepted 28 February 2008
developed in a 3 to 4 km wide outer halo.
Available online 28 March 2008
Abundant alunite occurs as hypogene, acicular crystals, and very fine-grained aggregates; the latter formed
Keywords:
during near-surface steam-heated overprinting. Hypogene alunite has an Ar–Ar plateau age of 10.8 ± 0.9 Ma
High-sulfidation (2σ), and is synchronous with the andesitic volcanism (Ar–Ar on biotite: 11.0 ± 0.5 Ma). A second ill-defined
Epithermal gold alunite age plateau of 8.0 ± 0.9 Ma is probably related to steam-heated overprint and points to major erosion
Alunite in between both hydrothermal events.
Peru Telescoping is also evident by a series of silicified horizons which mark the paleo-groundwater table. These
40Ar/39Ar units have elevated mercury, antimony and arsenic levels. Late-phase barite occurs in some structurally
controlled advanced-argillic altered envelopes.
The hypogene alteration mineralogy points to temperatures at ≤250 °C. Hydraulic fracturing and steam-
heated overprinting suggest a shallow boiling environment. Slight gold enrichment is observed in the
lowermost exposed parts of the system.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
The Cerro Millo gold prospect lies within the southern Peruvian
trend of high-sulfidation epithermal gold deposits (Noble et al., 1989;
Noble and Vidal, 1994) which includes the recent mine developments
of Rescatada (120 km NW), Aruntani (50 km SE) and Mazo Cruz
(100 km SE) (Fig. 1). This trend also hosts numerous polymetallic vein
systems (Palacios et al., 1993) (Fig. 2). About 200 km to the northwest
of Cerro Millo is the southern Peruvian low/intermediate sulfidation
silver district which includes Arcata, Ares, Caylloma, Orcopampa and
Shila (Gibson et al., 1995; Chauvet et al., 2006; Echavarria et al., 2006).
The large hydrothermal halo of the Cerro Millo area, expressed in a
prominent color anomaly in satellite imagery, was recently explored
by Buenaventura Mines, Newmont and several other mining compa-
nies. We here describe the geological and hydrothermal framework of
the surficial part of this system, which may have potential for a deeper
porphyry-style Cu–Au deposit. The results are based on detailed
geological and hydrothermal alteration mapping of a 12 km2 large
area at Cerro Millo (Figs. 3, 4). Concomitant with mapping, samples of
⁎ Corresponding author. Fax: +49 5323 722511.
E-mail address: Daniel.Hennig@tu-clausthal.de (D. Hennig).
the different lithologies, alteration facies and mineralized areas were
taken at 55 sample points and were analyzed by multielement
techniques for rock classification, decoding of element mobilities in
the hydrothermal evolution and economic evaluation of the gold
prospect (Hennig, 2005). Two samples from least-altered rock and
from intensively advanced-argillic altered rock of the central part of
the system were dated by the stepped heating 40Ar/39Ar technique on
biotite and alunite, respectively.
2. Regional geological setting
The Cerro Millo prospect is in the Cordillera Barroso of the Western
Cordillera of southern Peru. The volcanic sequence in the Cerro Millo
area was grouped by Jenks (1946) as Sillapaca Volcanics. This suite is
separated by the Quechua II unconformity (8 Ma) into the Miocene
Sillapaca Sequence and the Late Miocene to Pliocene Barroso Group
(Benavides-Cáceres, 1999) (Fig. 2).
K–Ar ages of the trachytic to andesitic lava flows of the Sillapaca
sequence range between 16.9 and 8.0 Ma (McKee and Noble, 1989). The
uppermost part of the Sillapaca sequence in southern Peru is considered
to include the stratigraphically equivalent Maure Group (10 to 8 Ma),
which consists of lavas, ignimbrites and tuffs of dacitic to trachyandesitic
composition up to 1500 m in thickness (Benavides-Cáceres, 1999).

0169-1368/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.oregeorev.2008.02.001
 D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316 305

3. Local geology of the Cerro Millo area

Detailed geological mapping of the Cerro Millo area defined at least

six volcanic events separated by angular unconformities (Figs. 3a and
4a). A detailed lithologic/petrographic description and genetic inter-
pretation of the volcanic setting is shown in the stratigraphic table
(Fig. 5). The main volcanic events are here summarized from oldest to
youngest:
A. The “Huancarane event” (named after the village of Huancarane,
southwest of Cerro Millo) correlates by extent approximately with
the Maure Group mapped by Hawkins et al. (1984). This event
comprises NE dipping latitic porphyro-aphanitic and andesitic
porphyritic lava (Figs. 3a and 4a; southwestern part).
B. The “Millo event”, with its postulated volcanic center at Cerro Millo
was hitherto regarded – due to its extent and lithology – as part of
the Barroso Group. The suite is composed of pervasively altered,
thick latitic, unwelded to partly welded ignimbrite and latitic, fine-
to medium-grained ash-fall tuff. These units are overlain by a suite
of andesitic to trachytic, porphyritic lava flows and andesitic
Fig. 1. Regional location map of the Cerro Millo epithermal high-sulfidation gold coarse-grained block-lava flows (Figs. 3a and 4a; central part).
prospect in southern Peru. Triangles show major epithermal deposits. C. The “Quebrada Sallaoqueña event” (Barroso Group?) has its center
in the northern Quebrada Sallaoqueña and includes dacitic
porphyritic lava and medium- to very-coarse-grained block-lava
The Barroso Group consists of andesite lavas and pyroclastic flows. The lavas dip to the southeast (Fig. 3a; east of Cerro Millo
deposits (Benavides-Cáceres, 1999) with ages ranging from 6.7 to Norte).
5.6 Ma (Palacios et al., 1993) (Fig. 2). The Barroso volcanism D and E. The “Colpacachi events” (Barroso Group?) are named after
corresponds to an extensional regime within the eastern Central the settlement of Colpacachi, northeast of the study area. They
Andean main arc (6.7 to 5.0 Ma) (Carlier et al., 1996). encompass andesitic, latitic and dacitic flows and block-lava flows.
The Mapa Geológico del Cuadrángulo de Pichacani of Hawkins et The two events are separated by an erosional phase evident from
al. (1984) shows mainly andesitic lavas and tuffs of the Pliocene reworked, weathered lava boulders at the base of the lava flow of
Barroso Group for the Cerro Millo area. Miocene Maure Group rocks the Colpacachi event II. Both units dip to the southwest (Figs. 3a
are indicated in the southwestern part of the mapping area. and 4a; eastern and southeastern part).

Fig. 2. Simplified geological map of the Puno region in southern Peru. Cerro Millo and neighbouring vein deposits are shown (geology and deposits adapted from Palacios et al., 1993;
vein location from Chauvet et al., 2006).
306 D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316

Fig. 3a. Detailed geological map of Cerro Millo with stratigraphic column. Tectonic features (faults and layering data) are strongly reduced for clarity. The topographic map base was a
georeferenced air photograph at a scale of 1:10,000.

Fig. 3b. Hydrothermal alteration and mineralization, Cerro Millo, SE Peru.

 D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316
Fig. 4a. Detailed cross-sections ABCD and EFGH illustrating geometry and erosional level of the Cerro Millo stratovolcano plus under- and overlying rock units. Cross-section lines shown in Fig. 3a. This figure includes all tectonic data.

Fig. 4b. Sections through the hydrothermal system at Cerro Millo. Cross-section lines shown in Fig. 3b.

307
 308
D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316
Fig. 5. Detailed stratigraphic table of Cerro Millo. Abbreviations (order as in text): phcr = phenocrysts, plg = plagioclase, bio = biotite, amph = amphibole, cpx = clinopyroxene, qtz = quartz, aug = augite, gm = groundmass, lim = limonite, opqs =
opaques, san = sanidine, hbl = hornblende, ap = apatite, zrc = zircon, tit = titanite, mag = magnetite, hem = hematite, accs = accessories. For more details see Hennig (2005).
 D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316 309

F. The “Chichupunt event” (Barroso Group?) includes latitic por-
phyritic lava flows derived from preserved volcanic edifices located
to the southeast of the mapping area, as evident from remote
sensing analysis and tectonic field data (Figs. 3a and 4a; southern
and southeastern part).
A small debris flow/lahar deposit with insecure stratigraphic age
was mapped in the W–E striking valley south of Cerro Millo. This unit
is covered by the strata of the Chichupunt event, and its western
contact to the lavas of the Cerro Millo event indicates genetic
affiliation to the Cerro Millo event (Fig. 3a). The variably colored
rock fragments of the debris deposit are advanced-argillic, argillic and
propylitically altered.
Remote sensing analysis of a N250 km2 wide area enclosing Cerro
Millo defined four main lineaments: NE-SW, NW-SE, N–S and E–W.
Predominantly NE-SW to NNE-SSW and NW-SE striking normal faults
and strike-slip faults with dextral movement were mapped in the field
(Figs. 3a and 4a). Kinematic indicators are found in the form of
slickensides, slickolites, grooves and second-order splays. However,
the lack of displaced strata and major offsets indicates that fault
movement was minor.
4. Hydrothermal alteration and mineralization
The study area displays the zonal pattern of alteration of a typical
high-sulfidation system (Figs. 3b and 4b): The inner, intensively
advanced-argillic altered zone (“A” in Figs. 3b and 4b) west of Cerro
Millo Norte is mainly hosted by pyroclastic rocks, in which small, m- to
dm-scale structurally controlled halos of vuggy silica alteration are
incorporated. The advanced-argillic alteration grades outwards (to N,
E and S) into an argillic altered halo which is also in pyroclastites. The
argillic alteration changes from kaolinite (“K”) to smectite (“SM”) in
the outer parts of the mapping area (Cerro Millo Norte, Cerro Chunco).
The argillic mineral assemblage grades outward into the propylitic
altered rocks, mainly hosted by lava material. In some peripheral parts
of the study area (Cerro Supa, Cerro Sallaoqueña, Cerro Chunco) fresh
rock material is preserved. The contact between advanced-argillic and
propylitic altered rocks on the west-slope of Cerro Millo traces nearly
perfectly the lithological contact between pyroclastites and lavas of
the “Millo event” (Figs. 3a,b). Silicified veins and horizons are
ubiquitous at Cerro Millo (Figs. 3b and 4b). The veins are exposed in
ridges of variable thickness. The horizons vary in thickness from 5 to
75 m and occur persistently at the elevations of 4700, 4800, 4850 and
4900 m above sea level. Especially at Cerro Millo Norte, this rock type
is often brecciated.
Pervasive advanced-argillic alteration is characterized at Cerro
Millo by the mineral assemblage of alunite–kaolinite–quartz. Two
types of alunite occur:
(1) Euhedral (acicular) alunite is characteristic for hypogene acid-
sulfate alteration (Rye et al., 1992). In thin section, this type is
up to 0.3 mm large, often zoned, locally occurs as veinlets, and
selectively replaces plagioclase. Crystals may form seams or
frostwork-like agglomerates in vugs (Fig. 6a).
(2) Anhedral, fine-grained alunite (commonly b10 µm) intermixed
with kaolinite was typically mapped in the summit region of
Cerro Millo Norte (Fig. 6b), and is characteristic of a near-
surface steam-heated environment in the vadose zone (cf.
Thompson and Thompson, 1996).
Tabular barite occurs locally at Cerro Millo in veins and vugs within
zones of hypogene advanced-argillic alteration (Fig. 6c).
Residual quartz alteration in pyroclastic rocks at Cerro Millo shows
vugs up to 8 cm in diameter which is due to dissolved pumice, similar
to the descriptions of Rye et al. (1992). In hand specimen, vuggy quartz
is grey and microcrystalline; vugs are lined by quartz, hematite and
limonite (mainly goethite). In thin section, quartz forms a dense
mosaic texture. Fine-grained rutile occurs as ragged, subhedral grains
and as euhedral, prismatic grains and clusters.
Argillic (kaolinite–smectite–quartz) altered outcrops at Cerro Millo
are typically white or tan in color and may have a brown to orange
oxidized surface due to weathering of pyrite. The rock hardness
increases with increasing silica content. In hand specimen, kaolinite
selectively replaces plagioclase phenocrysts and occurs as pervasive
blue shady groundmass alteration. In thin section, kaolinite occurs in

Fig. 6. (a) Photomicrograph of euhedral, acicular alunite in veins and vugs. This type is characteristic for hypogene acid-sulfate alteration. al = Alunite, kao = kaolinite, qu = quartz. (b)
Photomicrograph of anhedral, very fine-grained alunite intermixed with kaolinite, quartz, and rutile. This type is characteristic of near-surface steam-heated advanced-argillic
alteration. (c) Large tabular crystals of barite as infill of a vug in silicified andesite. ba = Barite. (d) Three different types of hydrothermal quartz: (1) Very fine-grained intergrown with
kaolinite in altered phenocrysts, (2) fine-grained in groundmass and (3) coarse grained (buck quartz) as open-space infill.
 310
Table 1
XRF, ICP, ICP-CV, ICP-MS and INAA whole rock data of the Cerro Millo samples

Sample Rock type SiO2 TiO2 CaO Na2O K2O Sr Zr Nb Sb Ba Bi ICP-CV Hg ICP S Zn Co Ni Y Ag Pb INAA As Au

wt.% wt.% wt.% wt.% wt.% ppm ppm ppm ppm ppm ppm Standard ppb Standard wt.% ppm ppm ppm ppm ppm ppm Standard ppm ppb

XRF XRF XRF XRF XRF XRF XRF XRF XRF XRF XRF ICP- ICP ICP ICP- ICP- ICP- ICP- ICP- INAA INAA
CV MS MS MS MS MS

D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316

77275 Latite (lava) 62.20 0.83 3.39 3.77 3.37 573 178 11 b5 854 b3 b5 b 0.001 96 13.4 20.5 10.8 b 0.05 17.0 2.5 4
77276 Andesite–latite (lava) 62.04 0.82 2.63 3.49 3.40 518 161 13 b5 830 b3 b5 b 0.001 130 11.9 15.8 5.0 b 0.05 36.3 b0.5 b2
77277 Trachyte–dacite (lava) 63.04 0.78 3.89 3.83 3.36 573 163 13 b5 848 b3 b5 b 0.001 98 12.8 15.4 9.3 b 0.05 15.7 b0.5 b2
77279 Trachyte–dacite (lava) 63.47 1.03 2.14 3.44 3.30 734 205 19 b5 940 b3 b5 0.56 46 2.8 5.0 9.2 b 0.05 16.8 2.3 4
77284 Andesite–trachyte (lava) 63.32 0.83 2.53 3.84 3.72 826 177 16 b5 1135 b3 5 0.02 90 5.8 13.6 5.1 b 0.05 13.2 2.2 3
77285 Andesite–trachyte (lava) 63.18 0.88 2.59 3.62 3.45 725 166 15 b5 908 b3 b5 0.00 81 5.5 10.2 8.7 b 0.05 17.7 b0.5 3
77288 Andesite–trachyte (lava) 61.27 0.80 4.19 3.50 3.26 623 151 10 b5 801 b3 b5 0.00 103 14.0 13.4 9.5 b 0.05 15.3 2.4 4
77289 Andesite–trachyte (lava) 62.46 0.74 3.86 3.07 3.36 448 153 13 b5 739 5 b5 0.02 71 11.2 11.5 8.3 b 0.05 15.1 b0.5 4
77290 Latite–dacite (aph. Lava) 64.17 0.64 3.46 3.61 3.43 502 158 7 b5 1133 b3 b5 b 0.001 78 9.1 31.9 4.1 b 0.05 15.0 b0.5 b2
77291 Latite–dacite (aph. Lava) 61.93 0.73 4.41 3.28 3.53 572 151 6 b5 1075 b3 b5 b 0.001 115 14.2 33.2 5.4 b 0.05 17.2 b0.5 5
77296 Andesite–latite (dike) 61.24 0.81 3.38 3.28 3.31 556 161 13 b5 751 4 b5 0.26 88 13.2 14.0 13.4 b 0.05 16.4 2.9 b2
77297 Andesite–latite (dike) 62.27 0.84 3.62 3.34 3.57 538 165 12 5 820 b3 b5 0.51 137 13.1 12.0 11.1 b 0.05 23.9 2.8 b2
77299 Dacite (lava) 65.73 0.82 1.43 2.94 3.69 322 170 15 b5 752 b3 b5 0.41 47 2.4 1.3 5.1 b 0.05 17.6 1.7 5
77950 Dacite (block-lava) 65.88 0.79 1.89 3.24 3.60 420 169 15 b5 825 b3 b5 0.23 55 1.9 1.9 4.4 b 0.05 18.3 1.7 b2
77951 Dacite (lava) 64.41 0.74 3.03 3.71 3.47 502 168 13 b5 829 b3 b5 0.01 73 8.3 8.5 8.2 b 0.05 16.3 b0.5 b2
77952 Andesite–latite (block-lava) 65.51 0.83 1.70 3.18 3.75 403 172 15 b5 863 b3 b5 0.12 71 1.9 1.7 6.8 b 0.05 17.1 2.7 b2
77953 Andesite (dome) 62.22 0.74 3.57 3.45 3.30 481 160 15 b5 719 b3 b5 b 0.001 68 11.6 10.9 9.3 b 0.05 17.1 1.2 b2
77954 Andesite (Hbl-dike) 62.20 0.74 3.57 3.40 3.33 484 150 11 b5 723 b3 b5 0.01 66 12.7 12.4 10.4 b 0.05 17.3 b0.5 b2
77958 Andesite–trachyte (lava) 59.98 0.90 4.06 2.84 3.11 490 178 15 b5 798 b3 b5 0.74 77 15.2 23.2 8.7 b 0.05 16.6 b0.5 b2
77965 Andesite (lava) 59.92 0.90 4.42 3.49 2.50 793 185 15 b5 891 b3 b5 0.01 128 11.1 6.9 8.5 b 0.05 16.0 2.5 b2
77966 Andesite–trachyte (lava) 59.51 0.96 4.85 3.29 3.04 556 169 10 11 804 b3 b5 0.34 83 15.9 11.4 9.0 b 0.05 17.1 2.3 3
77968 Andesite (block lava) 62.04 0.80 3.18 2.69 3.45 671 187 13 b5 822 b3 b5 0.36 108 10.1 22.6 15.6 b 0.05 16.9 1.8 b2
77270 Latite (pyroclastic rock. 57.06 0.74 0.25 1.19 2.08 1029 158 14 b5 872 b3 556 7.35 4 1.2 3.2 6.5 b 0.05 27.0 4.9 b2
undiff.)
77955 Andesite–trachyte (lava) 56.79 0.68 0.12 1.05 2.60 622 129 10 b5 548 b3 622 7.01 5 0.1 b 0.5 2.9 b 0.05 9.3 2.2 b2
77282 Latite (pyroclastic rock. 60.43 0.76 0.25 1.18 1.70 496 146 13 b5 717 b3 127 6.30 3 0.3 b 0.5 5.4 b 0.05 27.9 3.5 b2
undiff.)
77272 Andesite–trachyte (lava) 67.10 0.76 0.13 0.52 2.12 825 147 17 b5 653 b3 429 5.31 4 0.3 1.1 6.3 b 0.05 15.3 6.9 b2
77268 Latite (pyroclastic rock. 64.34 0.65 0.14 0.66 1.81 1264 129 10 26 832 b3 501 5.11 5 0.3 0.7 8.5 b 0.05 39.8 6.3 b2
undiff.)
77967 Andesite–trachyte (lava) 59.47 0.74 0.27 0.26 1.58 1466 171 14 b5 1318 b3 479 3.80 5 1.0 1.6 10.1 b 0.05 25.0 1.7 b2
77283 Latite (subvolcanic 77.35 0.95 0.03 0.24 1.61 287 165 17 b5 275 b3 133 3.59 7 0.4 0.8 1.1 b 0.05 8.5 1.9 b2
pyroclastic rock)
77298 Andesite–trachyte (lava) 64.05 0.66 0.18 0.50 1.02 1334 141 13 b5 769 b3 1243 2.94 4 0.3 b 0.5 9.4 b 0.05 21.4 5.2 2
77963 Latite (pyroclastic rock. 81.07 1.16 0.02 0.21 1.43 298 221 17 b5 1018 b3 41 2.88 5 b0.1 0.1 1.9 b 0.05 14.3 3.5 b2
undiff.)
77294 Latite (Amph.-olivine- 68.12 0.91 0.15 0.10 0.63 816 184 15 b5 525 b3 11 2.59 6 3.6 3.0 6.4 b 0.05 14.1 4.7 b2
bearing lava)
77280 Andesite (lava) 88.10 0.86 0.09 b0.01 0.07 3494 172 17 217 494 b3 985 2.46 9 3.8 2.6 9.4 b 0.05 198.0 49.8 b2
77971 Latite (ignimbrite. partly welded) 67.24 0.73 0.04 0.11 0.99 521 149 13 b5 902 b3 26 1.88 6 0.5 0.7 0.4 b 0.05 13.1 3.8 b2
77961 Andesite–trachyte (lava) 97.27 0.88 0.01 b0.01 0.01 4 121 13 b5 60 b b3 7 0.02 7 b0.1 b0.5 0.7 b 0.05 b 0.5 13.7 b2
77972 Latite (ashtuff) 97.23 1.52 0.01 b0.01 0.02 23 174 26 b5 101 b3 28 0.06 6 0.4 0.9 0.1 b 0.05 2.2 17.4 b2
77292 Andesite–trachyte (lava) 96.97 0.14 0.01 b0.01 0.01 10 19 3 b5 190 b3 b5 0.02 9 0.3 0.6 0.4 b 0.05 1.4 4.5 b2
77957 Latite (pyroclastic rock. undiff.) 96.40 1.08 0.01 b0.01 0.01 b2 215 18 b5 10 b3 38 0.02 6 0.1 b0.5 0.6 b 0.05 b 0.5 2.0 b2
77281 Latite (ignimbrite unwelded) 96.24 0.88 0.01 b0.01 0.03 53 114 13 b5 39 b3 24 0.08 5 b0.1 b0.5 2.2 b 0.05 1.2 3.1 2
77287 Latite (pyroclastic rock. undiff.) 96.17 0.64 0.01 b0.01 0.02 18 135 10 b5 1457 b3 786 0.08 5 b0.1 b0.5 2.2 b 0.05 0.8 7.7 b2
77964 Andesite (lava) 95.38 1.04 0.01 0.02 0.02 107 241 19 34 2222 4 1472 0.22 4 1.2 1.8 1.3 b 0.05 33.5 25.4 b2
77959 Andesite–trachyte (lava) 94.72 0.96 0.02 b0.01 0.02 63 179 15 b5 43 b3 90 0.04 6 0.1 0.6 10.9 b 0.05 1.4 3.8 2
77295 Latite (pyroclastic rock. undiff.) 94.45 0.98 0.01 b0.01 0.02 6 172 17 b5 1265 b3 545 0.05 5 0.3 0.6 0.9 b 0.05 0.7 6.3 b2
77269 Latite (subvolcanic pyroclastic 91.71 1.02 0.06 0.03 0.40 207 182 19 b5 228 b3 76 0.85 9 0.2 0.6 1.6 b 0.05 2.3 3.4 b2
rock)
77969 Andesite (lava) 91.15 0.24 0.12 0.05 0.18 518 43 6 b5 262 b 3 92 0.18 8 0.2 1.0 1.9 b 0.05 37.3 0.7 2
77273 Latite (subvolcanic pyroclastic 87.92 0.99 0.05 b0.01 0.05 438 203 17 b5 288 b 3 95 0.26 3 0.5 0.9 8.5 b 0.05 12.5 12.7 b2
rock)
77970 Andesite (lava) 86.52 1.31 0.02 0.03 0.08 789 304 24 152 20217 42 12486 0.35 2 1.5 1.5 0.8 0.11 87.7 300.0 81
77274 Andesite–latite (lava) 82.35 0.79 1.00 0.93 2.01 145 169 15 b5 436 b3 148 0.30 22 4.3 3.9 11.0 b 0.05 14.5 7.1 b2
77960 Andesite–trachyte (lava) 81.07 0.08 0.24 2.31 3.78 8 78 13 b5 22 b3 b5 0.09 14 0.2 b0.5 12.9 b 0.05 35.4 35.4 b2
77271 Latite (ignimbrite unwelded) 74.15 0.84 0.01 0.12 0.22 61 151 18 b5 210 b3 7024 0.83 b1 0.6 1.4 0.7 b 0.05 30.2 7.5 b2
77956 Latite (subvolcanic pyroclastic 59.79 0.84 4.52 3.38 3.12 528 160 14 b5 794 b3 b5 0.16 78 15.9 17.9 9.1 b 0.05 17.5 b 0.5 b2

D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316

rock)
77278 Latite (block-lava) 58.40 1.06 1.36 1.60 2.64 315 189 15 b5 803 b3 b5 0.39 117 5.3 3.1 6.9 b 0.05 15.8 5.1 b2
77286 Andesite (block-lava) 61.34 0.86 0.88 1.10 2.91 378 167 15 b5 716 b3 b5 0.28 51 2.3 2.2 10.6 b 0.05 20.5 2.0 b2
77293 Latite (debris flow. lahar) 46.46 0.68 0.33 0.46 1.32 511 150 13 b5 776 b3 90 1.94 13 1.1 1.2 4.0 b 0.05 17.3 20.6 b2
77962 Andesite (porphyro-aphanitic 68.60 0.46 2.04 4.25 4.29 377 251 17 b5 1026 b3 b5 0.00 63 2.5 1.8 8.1 b 0.05 17.9 2.0 b2
lava)
40– 0.1– 0.01– 0.01– 0.05– b 4000 b200 b30 n. b2200 n.d. SO-2 72–91 GXR- 0.26 760 8.2 41.0 32.0 31.00 730.0 DMMAS-5- 3200.0 650
100 1.5 5 5 5 d. 1 1
1 2 2 2 1 5 10 15 n. 10 n.d. SO-2 75 GXR- 0.26 738 9.1 42.1 32.1 29.81 767.3 DMMAS-5- 3360.0 631
d. 1 2
GXR- 3900 GXR- 0.03 530 8.6 21.0 17.0 17.00 690.0 DMMAS-5- 3590.0 604
1 2 3
GXR- 4013 GXR- 0.02 544 7.9 20.7 8.1 11.33 686.6 DMMAS-5- 3330.0 649
1 2 4
GXR- 2900 GXR- 1.77 73 14.6 42.0 14.0 4.00 52.0 DMMAS-5- 3210.0 582
2 4 5
GXR- 2907 GXR- 1.79 74 14.6 42.2 11.2 0.61 50.0
2 4
GXR- 110 GXR- 0.02 118 13.8 27.0 14.0 1.30 101.0 DMMAS-5 3280 552
4 6 ± 200 ± 146
GXR- 107 GXR- 0.02 123 14.3 26.3 4.8 0.05 96.2
4 6

311
312 D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316
Fig. 7. Classification of altered rocks according to Winchester and Floyd (1977). Dashed
area marks compositional range of least-altered rock samples. Some highly silicified
rocks with Nb/Y N 10 plot outside of the diagram. Zr, Ti and Nb by X-ray fluorescence
analysis (XRF), Y by inductively coupled plasma mass spectrometry (ICP-MS).
replacement masses and as vein infill. It is typically fine-grained
(b0.05 mm) and occurs as anhedral crystals, platy flakes, and crystals
with hexagonal, square and triangular outlines. Very fine-grained
smectite (b0.01 mm) replaces volcanic glass and appears as open-
space filling.
Pyrite, the main ore mineral at Cerro Millo, is predominantly
related to argillic altered clusters in propylitically altered rock units at
the western and eastern slope of Quebrada Sallaoqueña (Fig. 3b).
Pyrite is commonly intergrown with rutile. The pyrite crystals are
subhedral (0.005–0.5 mm), but typically exhibit holes and bay-like
habit due to silicification and corrosion/oxidation. A slight zoning is
due to varying As contents (qualitative microprobe analysis). Limonite,
which fills cubic holes in the gangue, indicates its origin from
supergene decay of pyrite.
The propylitically altered lavas are characterized by a greenish
groundmass. Propylitization is indicated by chlorite, calcite, epidote
and quartz. Mafic minerals are altered to chlorite. Calcite is restricted
to some plagioclase and amphibole crystals. It occurs in subhedral
crystals up to 0.1 mm, as dark, fine-grained, anhedral crystals and as
fine-grained, patchy dark aggregates in the groundmass due to
plagioclase breakdown. Subhedral epidote is located along veinlets
and vugs. Quartz occurs in veins, veinlets and vugs.
Fig. 8. S-K2O variation diagram: Least-altered and propylitic altered rocks have
distinctly lower S/K2O ratios than advanced-argillic altered rocks. Advanced-argillic
alteration is located in between the K-alunite and Na-alunite mixing lines. S determined
by inductively coupled plasma emission analysis (ICP), K by XRF.
Fig. 9. Ba–K2O variation diagram: This plot illustrates the immobility of Ba during
advanced-argillic alteration. Ba and K by XRF.
Silicification ranges from patches of quartz flooding the ground-
mass to pervasive silicification and textural destruction. In thin
section, fine-grained quartz replaces both phenocrysts and ground-
mass. Coarser crystals occur in vugs and fractures (b1 mm) (Fig. 6d).
Chalcedony is typically blue-grey to dark-grey colored and shows in
hand specimen waxy luster. In thin section, chalcedony appears as a
fine-grained phase with disseminated pyrite. Its wavy distribution and
variation of the optical axes leads to undulatory extinction.
5. Geochemistry
Sampling at Cerro Millo was done by chips, with about 3 to 4 kg of
chip material and a hand specimen. The hand specimens served for
preparation of thin and polished sections. The rock chips were
crushed, divided and about 300 g of the split was pulverized in an
agate mill.
The rock powder was analyzed by X-ray fluorescence spectrometry
(XRF) at the Bundesanstalt für Geowissenschaften und Rohstoffe
(BGR) in Hannover, Germany and by Actlabs in Canada using the
Ultratrace 3 package, which combines instrumental neutron activa-
tion analysis (INAA), ICP and inductively coupled mass spectrometry
(ICP-MS) analysis (Au + 63 elements), plus mercury analysis by cold
vapor atom absorption spectrometry. The data are given in Table 1.
Fig. 10. Sr–CaO variation diagram: Kaolinite or ASPs immobilize Sr in advanced-argillic
altered rocks. Sr and Ca by XRF.
 D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316 313

Table 2
40
Ar/39Ar stepped heating data of the Cerro Millo samples (error is 2σ)
36
Temp. Ar Cla Cab c
K 40
Ar 40
Ar⁎d 39
Ar Cum. 39
Ar 40
Ar⁎/39Ar Agee

°C (×10− 18 mol) (×10− 9 mol) (×10− 9 mol) (×10− 9 mol) (× 10− 15 mol) (%) (%) (%) (Ma)

77272 Alunite mass = 0.03514 g

500 184 ± 30 Nd 1.5 ± 0.5 0.7 ± 0.1 61.6 ± 0.1 11.8 0.0 0.0 nd nd
600 172 ± 30 0.04 ± 0.02 1.5 ± 0.4 1.6 ± 0.1 47.9 ± 0.1 0.0 0.0 0.0 nd nd
650 58 ± 30 0.02 ± 0.04 1.8 ± 0.3 2.1 ± 0.1 31.9 ± 0.1 45.8 0.0 0.0 nd nd
700 87 ± 28 0.05 ± 0.01 1.8 ± 0.4 4.9 ± 0.2 33.5 ± 0.1 23.0 0.1 0.1 nd nd
750 205 ± 49 0.08 ± 0.02 5.0 ± 0.6 43.6 ± 0.3 54.8 ± 0.1 0.0 0.5 0.5 0.33 ± 0.03 10.8 ± 2.0
800 252 ± 29 Nd 53.2 ± 0.5 1285.3 ± 7.2 168.7 ± 0.1 55.8 13.3 13.9 0.33 ± 0.02 10.6 ± 1.5
810 286 ± 26 Nd 64.7 ± 0.5 1552.2 ± 8.6 196.6 ± 0.1 57.0 16.1 30.0 0.34 ± 0.02 11.0 ± 1.4
820 355 ± 36 1.46 ± 0.45 119.8 ± 2.0 2295.4 ± 12.8 277.2 ± 0.2 62.2 23.8 53.8 0.25 ± 0.01 8.0 ± 0.9
830 1149 ± 39 2.77 ± 0.36 309.1 ± 6.0 3965.5 ± 22.1 555.9 ± 0.2 38.9 41.1 94.9 nd nd
835 409 ± 32 0.42 ± 0.03 60.2 ± 0.7 133.6 ± 1.0 89.8 ± 0.1 0.0 1.4 96.2 nd nd
900 3583 ± 48 1.46 ± 0.04 349.7 ± 2.6 139.9 ± 0.9 1007.7 ± 0.8 0.0 1.4 97.7 1.91 ± 0.37 61.0 ± 23.3
1100 2202 ± 24 1.32 ± 0.03 323.8 ± 1.9 87.1 ± 0.5 687.4 ± 0.5 5.3 0.9 98.6 1.67 ± 0.31 53.4 ± 19.4
1600 5986 ± 31 25.63 ± 0.43 169.8 ± 1.0 136.1 ± 0.8 1818.9 ± 1.4 2.8 1.4 100.0 nd nd
Total 14929 ± 123 33.2 ± 0.72 1461.9 ± 7.3 9645.6 ± 28.0 5031.9 ± 1.7 0.30 ± 0.01 9.6 ± 0.6

77285 Biotite mass = 0.00757 g

500 348 ± 39 Nd 2.2 ± 0.3 0.3 ± 0.1 112.9 ± 0.1 8.8 0.0 0.0 nd nd
600 223 ± 27 0.04 ± 0.02 2.6 ± 0.4 0.9 ± 0.1 54.1 ± 0.1 0.0 0.0 0.0 nd nd
700 122 ± 37 0.08 ± 0.03 4.0 ± 0.5 6.5 ± 0.2 37.8 ± 0.1 4.4 0.1 0.1 0.60 ± 7.66 19.5 ± 492.9
800 100 ± 28 0.30 ± 0.02 12.2 ± 0.4 43.7 ± 0.3 36.3 ± 0.1 18.3 0.5 0.5 0.62 ± 0.87 20.1 ± 55.9
900 174 ± 31 0.61 ± 0.02 22.6 ± 0.3 146.9 ± 0.9 61.2 ± 0.1 15.8 1.5 2.1 0.26 ± 0.28 8.5 ± 18.4
1000 335 ± 36 1.60 ± 0.04 77.6 ± 0.6 463.0 ± 2.6 129.9 ± 0.1 23.8 4.8 6.9 0.28 ± 0.11 9.1 ± 6.8
1100 67 ± 31 8.97 ± 0.16 143.1 ± 0.9 646.0 ± 3.7 79.0 ± 0.1 75.0 6.7 13.5 0.41 ± 0.07 13.4 ± 4.2
1200 191 ± 39 61.34 ± 1.03 116.2 ± 0.8 1963.1 ± 11.1 204.0 ± 0.2 72.4 20.3 33.9 0.34 ± 0.03 11.0 ± 1.8
1400 462 ± 33 202.94 ± 3.41 136.7 ± 1.2 6297.6 ± 36.2 608.5 ± 2.1 77.6 65.3 99.2 0.34 ± 0.01 10.9 ± 0.5
1600 308 ± 36 2.70 ± 0.05 15.3 ± 0.3 81.3 ± 0.5 108.4 ± 0.2 16.0 0.8 100.0 0.85 ± 0.60 27.6 ± 38.4
Total 2331 ± 107 278.6 ± 3.57 532.5 ± 2.01 9649.4 ± 38.2 1432.1 ± 2.2 0.34 ± 0.01 11.2 ± 0.9

77285 Feldspar mass = 0.05036 g

500 1802 ± 37 0.02 ± 0.02 3.4 ± 1.1 1.3 ± 0.1 523.1 ± 0.2 0.0 0.0 0.0 nd nd
600 390 ± 31 0.10 ± 0.03 4.8 ± 1.0 2.8 ± 0.0 110.8 ± 0.1 0.0 0.0 0.0 nd nd
700 312 ± 32 0.39 ± 0.01 24.9 ± 1.1 18.5 ± 0.1 92.4 ± 0.1 0.1 0.1 0.2 0.03 ± 2.32 0.9 ± 151.0
800 636 ± 33 1.28 ± 0.03 120.5 ± 0.9 150.1 ± 0.8 189.1 ± 0.1 0.6 1.1 1.2 0.03 ± 0.29 1.1 ± 19.0
900 399 ± 33 0.69 ± 0.02 213.3 ± 1.8 489.3 ± 2.7 155.8 ± 0.1 24.3 3.5 4.7 0.35 ± 0.09 11.4 ± 5.9
950 401 ± 35 0.17 ± 0.01 304.1 ± 1.8 725.9 ± 4.0 164.7 ± 0.1 28.0 5.1 9.8 0.29 ± 0.06 9.3 ± 4.2
1000 164 ± 27 Nd 809.1 ± 4.7 1376.0 ± 7.6 143.9 ± 0.1 66.3 9.7 19.6 0.31 ± 0.03 10.2 ± 1.7
1050 145 ± 38 Nd 1826.4 ± 10.3 1601.1 ± 8.9 152.3 ± 0.1 71.9 11.3 30.9 0.31 ± 0.03 10.1 ± 2.0
1100 246 ± 30 0.16 ± 0.03 3800.8 ± 21.2 1755.0 ± 9.7 183.0 ± 0.2 60.3 12.4 43.3 0.29 ± 0.02 9.2 ± 1.5
1150 192 ± 32 1.19 ± 0.04 4201.1 ± 23.4 1637.1 ± 9.1 172.3 ± 0.1 67.0 11.6 54.9 0.32 ± 0.03 10.4 ± 1.7
1250 545 ± 27 3.75 ± 0.07 6338.6 ± 42.5 1973.0 ± 11.7 271.0 ± 0.4 40.6 14.0 68.8 0.25 ± 0.02 8.2 ± 1.2
1400 494 ± 32 2.18 ± 0.04 6344.9 ± 41.6 1292.4 ± 7.6 218.7 ± 0.2 33.2 9.1 78.0 0.25 ± 0.03 8.3 ± 2.2
1600 702 ± 28 3.22 ± 0.06 12713.6 ± 70.8 2164.4 ± 12.0 372.4 ± 0.2 44.3 15.3 93.3 0.35 ± 0.02 11.2 ± 1.1
1800 1205 ± 33 1.16 ± 0.03 5637.0 ± 31.4 947.1 ± 5.3 411.1 ± 0.1 13.4 6.7 100.0 0.26 ± 0.05 8.5 ± 3.0
Total 7634 ± 121 14.3 ± 0.12 42342.6 ± 103.3 14134.1 ± 26.6 3160.6 ± 0.6 0.30 ± 0.01 9.7 ± 0.6
38
 38 
a 37 38 4 Ar K Ar
Determined from Cl (n,γ,β) Ar: Cl = 9.0159 × 10 · b
J · (mole/mole); β = Cl
39 ; (K/Cl)Hb3gr = 5.242; β = 3.46 ± 0.06.
Ar
37
 37  Hb3gr
b Ar K Ar
Determined from 40Ca (n,α,)37Ar: Ca = 8.042 × 104 · a
J · (mole/mole); α = Ca
39 ; (K/Ca)Hb3gr = 0.1674; α = 0.52 ± 0.02.
Ar Hb3gr
39
Ar
c
Determined from 39K (n,p)39Ar: K = J
K K
k · (mole/mole); λ = λe = 0.581; K/40K = 1.167 × 10− 4; J = 0.01803 ± 0.00010.
d d40 40 ke
Ar⁎ = 40Artotal − 295.5 × 36Ar.
e
Two standard deviation error includes uncertainties on the J value.

The least-altered volcanic rocks at Cerro Millo (22 samples) range
from andesite, trachyandesite, trachyte to dacite with high-K affinity
(TAS plot, not shown). The trachyandesite is latite (Na2O-2 bK2O;
LeBas et al., 1986). The trachyandesite or latite composition of the
altered volcanic rocks is confirmed by immobile element plots
(Winchester and Floyd, 1977) (Fig. 7).
The altered rocks can be distinguished in the K2O-S plot (Fig. 8).
Potassium and sulfur concentrations clearly distinguish the fresh and
propylitically altered rock samples from both the silicified and the
advanced-argillic altered rock samples. The samples with alunite plot
in between the mixing lines of stoichiometric Na-alunite (K2O/S = 0)
and K-alunite (K2O/S = 0.7). The variable alunite content in the sample
set is expressed by the positive correlation of potassium and sulfur
concentrations. Alunite is by far the dominant potassium mineral at
Cerro Millo.
Even though biotite and K-feldspar, the main igneous Ba carriers
are totally altered in the advanced-argillic altered rocks, Ba concen-
tration remains similar to the least-altered rock suite (Fig. 9). It
appears likely that the high SO2−4 content in the high-sulfidation fluids
responsible for alunite formation immobilizes barium because of the
low solubility of barite.
Similarly to Ba, the Sr content remains constant during acid
alteration while plagioclase, the main igneous Sr carrier breaks down
and CaO is drastically depleted (Fig. 10). Sr fixation could be due to
kaolinite or alumino-phosphate-sulfate minerals (ASP). Sr correlates
weakly with both Al and P, but not with S, i.e., no correlation with
alunite (Table 1).
Zinc, Co and Ni are remarkably depleted in the altered rocks
compared to their unaltered rock equivalents, probably due to the
high solubility of the transition metals in acidic fluids. Arsenic, Sb and
314 D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316
Fig. 11. Ar–Ar age spectra; (a) igneous biotite of the fresh Cerro Millo host rock (sample
77285) shows a plateau age of 10.97 + 0.47 Ma. (b) Alunite from sample 77272 shows
two different ages, the older age is interpreted as hypogene advanced-argillic alteration
and the younger age as steam-heating in the vadose zone. All error boxes are shown at
the 2σ level of uncertainty.
Hg are enriched in the altered rocks, both relative to the unaltered
rocks and relative to the reference values for the upper continental
crust (Taylor and McLennan, 1995; Wedepohl, 1995). Local enrichment
is up to 300 ppm As, 220 ppm Sb and 12,500 ppb Hg, respectively, and
about one third of all samples show detectable but weak gold
enrichment of ≥2 ppb Au. The highest Au content of 81 ppb was
measured in the lowermost Quebrada Millo, in close contact to the
mapped Maure/Barroso unconformity of Hawkins et al. (1984). These
rocks are silicified, have been subjected to advanced-argillic alteration,
and also display enrichment in Ag, Ba, As, Sb and Hg (Table 1).
40
6. Ar/39Ar dating
Biotite from fresh, andesitic to dacitic porphyritic lava of the Millo
stratovolcano (NW-slope of Cerro Millo Norte, sample 77285) and
alunite from advanced-argillic alteration from the W-slope of Cerro
Millo Norte (sample 77272) were analyzed by the Ar–Ar stepped
heating technique (Fig. 3b). The rock samples were lightly crushed and
sieved down to 100 µm. The mineral fractions were hand-picked by
tweezers under a binocular microscope. The separates were weighed
and wrapped in Al foil and were vacuum encapsulated in quartz vials
with the neutron fluence monitor Hb3gr (t = 1073.6 ± 5.3 Ma; Jourdan
et al., 2006). Nuclear irradiation was carried-out in position B2W of
the SAFARI-1 reactor at Pelindaba, South Africa using a fast neutron
flux of ∼ 2 × 1018 n cm2. The J value determined from Hb3gr was
0.01803 ± 0.00010 (2σ).
The Ar isotopes were measured using the MS1 mass spectrometer
at the University of Manchester, equipped with a Baur-Signer ion
source. The irradiated samples were step-heated in a Ta-resistance
furnace over the temperature interval of 500 to 1600 °C, using 30 min
heating steps. During heating, Ar was purified using a Zr–Al getter at
450 °C. Raw isotopic data were corrected for mass discrimination
(calibrated using atmospheric argon), radioactive decay and neutron
interference corrections. Further experimental details are given by
Burgess et al. (2004). Ar–Ar ages were determined from age spectrum
diagrams, using the ISOPLOT/Ex 3.23 software (Ludwig, 2003), and all
data are reported at the 2 σ level of uncertainty. The isotopic data are
shown in Table 2. The age spectra are plotted in Fig. 11.
The biotite sample defines an integrated plateau age of 11.2 ±
0.9 Ma. The major 39Ar release of 65% was from the heating step at
1400 °C with an age of 10.9 ± 0.5 Ma. On a 36Ar/40Ar versus 39Ar/40Ar
diagram (not shown) the data form a linear correlation indicating a
mixture of radiogenic and atmospheric Ar components. The age
obtained from the 39Ar/40Ar intercept is 10.9 ± 0.7 Ma indistinguishable
from the plateau age.
The alunite sample shows two distinctly different apparent ages.
The temperature steps between 800 and 820 °C gave 54% of 39Ar
release and an age of 10.8 ± 0.9 Ma. This dataset meets the criteria of an
age plateau (≥3 temperature steps overlapping at the 2 sigma level, and
representing N50% of the 39Ar release) and is within the age range of
the volcanic host rock. A remarkably younger alunite age of 8.0 ± 0.9 Ma
was obtained from the temperature interval at 830 °C with about 41%
39
Ar released. The total age over all temperature steps (i.e., the K–Ar
age) is 9.6 ± 0.6 Ma.
7. Discussion
7.1. Age constraints on volcanism and hydrothermal activity
The new 40Ar/39Ar plateau age on biotite of 11.0 ± 0.5 Ma and the
alunite ages in between 8 and 11 Ma require revision of the current
lithostratigraphy of the Mapa Geológico del Cuadrángulo de Pichacani
(Hawkins et al., 1984). The Cerro Millo rock units cannot be correlated
with the Barroso Group, commonly considered to range from 6.7 to
5.6 Ma (Palacios et al., 1993). It is therefore more likely that the Cerro
Millo area belongs stratigraphically to the Maure Group or to the
Miocene Sillapaca sequence.
The two alunite ages within one sample (10.8 ± 0.9 Ma and 8.0 ±
0.9 Ma) may reflect the two different genetic types of alunite. The older,
euhedral, baguette-like alunite is of hypogene origin and the younger
type, i.e., the very fine-grained alunite is generated by steam-heating in
the vadose zone. Whatever the exact reason for this age discrepancy, the
Ar–Ar data on igneous biotite and hydrothermal alunite suggest a direct
temporal link between volcanic activity and the high-sulfidation
hydrothermal system, with formation of some alunite possibly up to
3 Ma after the main phase volcanism. Similarly long-lived hydrothermal
systems have been reported from Steamboat Springs, Nevada, and
Toyoha, Japan (Silberman et al., 1979; Sawai et al., 1989), and probably
require multiple intrusions at depth (e.g., Cathles, 1981).
7.2. Abundance of alunite (deep and shallow)
The hypogene nature of the pronounced acid-sulfate alteration at
Cerro Millo is illustrated by the distinct zonation of the alteration
haloes, with well-crystallized acicular alunite (marked with “A” on
Figs. 3b and 4b).
Hypogene acid-sulfate alteration is probably connected to volatile
release from an underlying magma chamber. Magmatic SO2 dispropor-
tionates in the presence of water to sulfuric acid (H2SO4) and H2S gas
and results in the development of sulfuric acid with pH b2 in the fluid;
sufficiently acid to leach Al from the host rocks (Henley and Ellis, 1983).
Fluid temperatures for efficient acid leaching are between 200 and
300 °C (Stoffregen, 1987). The remaining siliceous residue recrystal-
lizes to quartz (vuggy quartz) ± alunite (Sillitoe, 1993). This style of
acid-sulfate alteration is characteristic of high-sulfidation epithermal
systems, which can contain economic gold (Stoffregen, 1987).
Boiling of the ascending fluid is the consequence of pressure
release either due to upward fluid percolation or due to rock failure in
over-pressured domains. Steam and other volatile phases (mainly H2S,
SO2 and CO2) are released and migrate further upwards (Sillitoe, 1993).
In contact with the atmosphere, i.e., just above the paleo-water table
 D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316
(vadose zone), sulfuric acid is generated by oxidation of H2S (Henley
and Ellis, 1983; Hayba et al., 1985; Craw, 2006). The sulfuric acid
percolates down and acidifies the oxidizing steam-heated ground-
water. The resulting steam-heated acidic fluids with pH N2 and
temperatures around 100 °C cause advanced-argillic alteration with
cavitation and deposition of secondary acid-sulfate minerals (Heden-
quist et al., 2000; Craw, 2006). The crater region of Cerro Millo Norte
displays such features of acid leaching by steam-heated overprint near
the paleo-surface, i.e., secondary porosity in the ash-fall tuff, very fine-
grained alunite and absence of vuggy silica alteration due to Al
solubility above pH 2 (Figs. 3a,b).
7.3. Shallow zones of silicification
The horizontal lying zones of silicification at Cerro Millo imply
control by paleohydrology. They are a typical feature of shallow high-
sulfidation systems and are believed to be generated at paleo-water
tables (Sillitoe, 1993). The massive and dense silica seals fractures,
permitting a build-up of pressure which results in the formation of
hydrothermal breccias, as locally observed at Cerro Millo Norte
(Cunningham et al., 1984).
Sulphur, Nevada, and Wau, Papua New Guinea (Sillitoe et al., 1984)
are analogous examples of silicified horizons overlain by acid-leached
rock. “Silica caps” are observed in the valleys around Cerro Millo and
represent silicified horizons stripped of their acid-leached zones.
Based on our detailed mapping the horizons of chalcedony at Cerro
Millo seem to be flat, persistent levels which cross the topographic
high of the ancient stratovolcano and do not follow the (former)
topography (Figs. 3b and 4b). This is inter-alia in contrast to the
models of Henley and Ellis (1983), but can be easily explained:
1. The predominantly unwelded pyroclastic rocks at Cerro Millo are a
thick homogeneous package with high hydraulic conductivity;
2. The highly faulted Cerro Millo acts in addition as joint aquifer.
3. The footwall following sub-horizontal lavas of the assumed Maure
Group represent an aquitard and fortify the sub-horizontal lateral
groundwater flow (Figs. 3 and 4).
One huge aquifer in pyroclastic rocks and several horizons of
chalcedony, which are believed to form at the paleo-water table point
to a significant drop of the paleo-water table during the hydrothermal
activity at Cerro Millo. The uppermost horizon of dense silica on top of
Cerro Millo Sur at 4900 m above sea level is expected to be the oldest.
The lowermost horizon of dense silica in Quebrada Millo/Quelluire at
4700 m above sea level is expected to be the youngest and coincides
roughly with the present-day swamp location, discharge systems and
lake locations around Cerro Millo. The recent features give a present-
day water table of roughly 4675 m above sea level, which indicates a
drop of at least 200 m (Figs. 3b and 4b).
7.4. Telescoping
The both deep and shallow alteration features at Cerro Millo, as well
as the two distinctly different alunite types with ages of 11 and 8 Ma
document a primary phase of hypogene acid-sulfate alteration
followed by steam-heated overprinting. Major erosion must have
taken place in between both hydrothermal events. The Cerro Millo
stratovolcano appears to have suffered at least one sector collapse
between 11 and 8 Ma, indirectly documented by the debris flow or
lahar deposit south of Cerro Millo (cf. Siebert, 1984; Begét and Kienle,
1992; López and Williams, 1993). Sector collapse is a widespread
phenomenon in the Central Andes, in spite of low denudation rates
since the mid-Miocene onset of aridity (Francis and Wells, 1988).
Continued paleosurface lowering during hydrothermal activity results
in a concomitant drop of paleo-water tables and overprinting of steam-
heated acid-leached zones onto originally deeper epithermal zones
(Sillitoe, 1994).
315
7.5. Exploration potential
The Cerro Millo prospect has many features in common with other
high-sulfidation epithermal gold systems. The observed extensive altera-
tion zoning characterizes better understood deposits such as Summitville,
Colorado (Stoffregen, 1987; Bruha and Noble, 1983), Marysvale, Utah
(Cunningham et al., 1984), or Rodalquilar, Spain (Sänger-von Oepen et al.,
1990; Arribas et al., 1995). These systems also have barium enrichment in
the alunite zone, which indicates at Summitville a late-stage gold
mineralization (Hayba et al., 1985). Temperature estimates during the
main stage of acidic wall rock alteration are 200 to 280 °C (Bruha and
Noble, 1983; Stoffregen, 1987; Arribas et al., 1995).
In particular, Cerro Millo has many features in common with
Marysvale, e.g., vertical zoning of massive silica and alunite, absence of
pyrophyllite, pyrite as the only ore mineral in the periphery of the
hydrothermal system, flat lying hydrothermally brecciated silica
horizons with weak gold enrichment and precious and base metal
mineralization in the proximity (Cunningham et al., 1984).
The Cerro Millo prospect has an age similar to several other
epithermal deposits in Peru. Colquijirca in central Peru has alunite ages
of 11.6 to 11.3 Ma related to epithermal high-sulfidation Au–Ag
mineralization in the volcanic center at Marcapunta, and a second alunite
generation of 10.8–10.6 Ma related to vein-style base metal mineraliza-
tion (Bendezú et al., 2003). The epithermal low-sulfidation system of Shila
has an age of 10.8 to 11.4 Ma; Chauvet et al., 2006). The Caylloma low/
intermediate sulfidation vein district has an age of 18 Ma (Echavarria et al.,
2006), but the eastward continuation into the Chonta caldera with the
epithermal deposits of Sukuytambo, Chonta and Corimina has ages
between 12 and 10.5 Ma (Peterson et al., 1983; Noble et al., 1989).
Hypogene alunite and local vuggy silica alteration define the center
of the Cerro Millo system. Evidence of boiling and a steam-heated
overprint is given by the locally brecciated horizons of silicification,
fine-grained alunite, porous ash-fall tuff and absence of vuggy silica
alteration at the top of Cerro Millo Norte. The numerous shallow
horizons of silica metasomatism are a unique feature at Cerro Millo
and point to significant steam-heated overprinting. The overprint(s)
appears to have erased economic mineralization in the uppermost
levels, but there is exploration potential in deeper parts, as observed
for the lowermost levels at Cerro Millo.
8. Conclusions
The chlorite–calcite–epidote–quartz assemblage, abundance of
kaolinite and absence of pyrophyllite define temperatures of ≤250 °
C for the hypogene acid-sulfate alteration (Hemley et al., 1980; Henley
and Ellis, 1983). Steam-heated alunite overprint and hydraulic
fracturing indicate shallow boiling and, in combination with the
suite of silicified horizons at Cerro Millo, point to telescoping.
The most pronounced anomalies of Au, Ag, Ba, Hg, As and Sb lie in
the topographically lowermost parts of the hydrothermal system, in
close contact to the presumed Maure/Barroso unconformity. Previous
shallow drilling campaigns (b200 m) were unsuccessful, but were
focussed on the steam-heated top of Cerro Millo, 350 m above this
unconformity.
The erratic volatile metal values at the surface in combination with
intensive faulting suggest leakage from a metal anomaly below, which
may represent a porphyry environment (Arribas, 1995; Sillitoe, 1995;
Sillitoe, 1999).
Acknowledgements
Dr Andreas Dietrich and Dr César E. Vidal of Buenaventura Mines
are thanked for logistic support at Cerro Millo. Dr Thomas Oberthür
and Frank Korte at BGR Hannover provided the XRF analyses.
Constructive comments on the manuscript by Greg Arehart, Nigel
Cook and John Muntean resulted in substantial improvement.
316 D. Hennig et al. / Ore Geology Reviews 34 (2008) 304–316
References
Arribas Jr., A., 1995. Characteristics of high-sulfidation epithermal deposits, and their
relation to magmatic fluid. In: Thompson, J.F.H. (Ed.), Magmas, Fluids, and Ore
Deposits. Mineralogical Association of Canada Short Course, vol. 23, pp. 419–454.
Arribas Jr., A., Cunningham, C.G., Rytuba, J.J., Rye, R.O., Kelly, W.C., Podwysocky, M.H.,
McKee, E.H., Tosdal, R.M., 1995. Geology, geochronology, fluid inclusions, and
isotope geochemistry of the Rodalquilar gold alunite deposit, Spain. Economic
Geology 90, 795–822.
Begét, J.E., Kienle, J., 1992. Cyclic formation of debris avalanches at Mount St. Augustine
volcano. Nature 356, 701–704.
Benavides-Cáceres, V., 1999. Orogenic evolution of the Peruvian Andes: the Andean
cycle. In: Skinner, B.J. (Ed.), Geology of Ore Deposits of the Central Andes. Society of
Economic Geologists, Boulder, Colorado, pp. 61–107.
Bendezú, R., Fontboté, L., Cosca, M., 2003. Relative age of Cordilleran base metal lode
and replacement deposits, and high sulfidation Au–(Ag) epithermal mineralization
in the Colquijirca mining district, central Peru. Mineralium Deposita 38, 683–694.
Bruha, D.I., Noble, D.C., 1983. Hypogene quartz–alunite +/− pyrite alteration formed by
moderate saline, ascendant hydrothermal solutions. Geological Society of America,
Abstracts with Programs 15, 325.
Burgess, R., Kiviets, G.B., Harris, J.W., 2004. 40Ar/39Ar age determinations of eclogitic
clinopyroxene and garnet inclusions in diamonds from the Venetia and Orapa
kimberlites. Lithos 77, 113–124.
Carlier, G., Lorand, J.-P., Bonhomme, M., Carlotto, V., 1996. A reappraisal of the Cenozoic
inner arc magmatism in Southern Peru: consequences for the evolution of the
Central Andes of the past 50 Ma. 3rd International Symposium of Andean
Geodynamics. ISAG, Paris, pp. 551–554.
Cathles, L.M., 1981. Fluid flow and genesis of hydrothermal ore deposits. Economic
Geology 424–457 75th Anniversary Volume.
Chauvet, A., Bailly, L., André, Anne-Sylvie, Monié, P., Cassard, D., Llosa Tajada, F., Rosas
Vargas, J., Tuduri, J., 2006. Internal vein texture and vein evolution of the epithermal
Shila–Paula district, southern Peru. Mineralium Deposita 41, 387–410.
Craw, D., 2006. Pressure–oxidation autoclave as an analogue for acid-sulphate
alteration in epithermal systems. Mineralium Deposita 41, 357–368.
Cunningham, C.G., Rye, R.O., Steven, T.A., Mehnert, H.H., 1984. Origins and exploration
significance of replacement and vein-type alunite deposits in the Marysvale
Volcanic Field, West Central Utah. Economic Geology 79, 50–71.
Echavarria, L., Neson, E., Humphrey, J., Chavez, J., Escobedo, L., Iriondo, A., 2006. Geologic
evolution of the Caylloma epithermal vein district, Southern Peru. Economic
Geology 101, 843–863.
Francis, P.W., Wells, G.L., 1988. Landsat thematic mapper observations of debris-
avalanche deposits in the central Andes. Bulletin of Volcanology 50, 258–278.
Gibson, P.C., McKee, E.H., Noble, D.C., Swanson, K.E., 1995. Timing and interrelation of
magmatic, tectonic, and hydrothermal activity at the Orcompampa district.
Southern Peru. Economic Geology 90, 2317–2325.
Hawkins, M.P., de la Cruz, N.S., de la Cruz, J., Palacios, O., 1984. Mapa Geológico del
Cuadrángulo de Pichacani. INGEMMET, Lima, Peru.
Hayba, D.O., Bethke, P.M., Heald, P., Foley, N.K., 1985. Geologic, mineralogic, and
geochemical characteristics of volcanic-hosted epithermal precious-metal deposits.
In: Berger, B.R., Bethke, P.M. (Eds.), Geology and Geochemistry of Epithermal
Systems. Society of Economic Geologists, Chelsea, Michigan, pp. 129–167.
Hedenquist, J.W., Arribas, M.A., Gonzalez-Urien, E., 2000. Exploration of epithermal gold
deposits. In: Hagemann, S.G., Brown, P.E. (Eds.), Gold in 2000. REVIEWS IN ECON.
GEOL., vol. 13, pp. 245–277.
Hemley, J.J., Montoya, J.W., Marinenko, J.W., Luce, R.W., 1980. Equilibria in the system
Al2O3–SiO2–H2O and some general implications for alteration/mineralization
processes. Economic Geology 75, 210–228.
Henley, R.W., Ellis, A.J., 1983. Geothermal systems ancient and modern: a geochemical
review. Earth Science Reviews 19, 1–50.
Hennig, D., 2005. Geology and geochemistry of the Cerro Millo gold prospect, southern
Peru. Diploma thesis. Technical University of Clausthal, 146 pp. [http://home.tu-
clausthal.de/~gedh/]
Jenks, W.F., 1946. Preliminary note on geologic studies of the Pacific slope in southern
Peru. American Journal of Science 244, 367–372.
Jourdan, F., Verati, C., Féraud, G., 2006. Intercalibration of the Hb3gr 40Ar/39Ar dating
standard. Chemical Geology 231, 77–189.
LeBas, M.J., LeMaitre, R.W., Streckeisen, A., Zanettin, B., 1986. A chemical classification of
volcanic rocks based on the total alkali-silica diagram. Journal of Petrology 27, 745–750.
López, D.L., Williams, S.N., 1993. Catastrophic volcanic collapse: relation to hydro-
thermal processes. Science 260, 1794–1796.
Ludwig, K., 2003. Isoplot/Ex, version 3: A Geochronological Toolkit for Microsoft Excel.
Geochronology Center, Berkeley, USA.
McKee, E.H., Noble, D.C., 1989. Cenozoic tectonic events, magmatic pulses, and base-
and precious-metal mineralization in the Central Andes. In: Ericksen, G.E., Canas
Pinochet, M.T., Reinemund, J.A. (Eds.), Geology of the Andes and Its Relation to
Hydrocarbon and Mineral Resources, vol. 11. Circum-Pacific Council for Energy and
Mineral Resources Earth Sciences Series, Houston, Texas, pp. 189–194.
Noble, D.C., Vidal, C.E., 1994. Gold in Peru. Society of Economic Geologists Newsletter 17
(1), 7–13.
Noble, D.C., Eyzaguirre, V.R., McKee, E.H., 1989. Precious-metal mineralization of
Cenozoic age in the Central Andes of Peru. In: Ericksen, G.E., Canas Pinochet, M.T.,
Reinemund, J.A. (Eds.), Geology of the Andes and its relation to hydrocarbon and
mineral resources, vol. 11. Circum-Pacific Council for Energy and Mineral Resources
Earth Science Series, Houston, Texas, pp. 207–212.
Palacios, O., De La Cruz, J., De La Cruz, N., Klinck, B.A., Allison, R.A., Hawkins, M.P., 1993.
Geologia de la Cordillera Occidental y Altiplano al oueste del Lago Titicaca — Sur del
Peru. Editorial Allamanda S.R.L., Lima, Peru. 258 pp.
Peterson, P.S., Noble, D.C., McKee, E.H., Eyzaguirre, V.R., 1983. A resurgent mineralized
caldera in southern Peru. American Geophysical Union Transactions 64, 884–898.
Rye, R.O., Bethke, P.M., Wasserman, M.D., 1992. The stable isotope geochemistry of acid
sulfate alteration. Economic Geology 87, 225–262.
Sawai, O., Okada, T., Itaya, T., 1989. K–Ar ages of sericite in hydrothermally altered rocks
around the Toyoha deposits, Hokkaido, Japan. Mining Geology 39, 191–204.
Sänger-von Oepen, P., Friedrich, G., Kisters, A., 1990. Comparison between the fluid
characteristics of the Rodalquilar and two neighbouring epithermal gold deposits in
Spain. Mineralium Deposita 25, 36–41.
Siebert, L., 1984. Large volcanic debris avalanches: characteristics of source areas,
deposits, and associated eruptions. Journal of Volcanology and Geothermal
Research 22, 163–197.
Silberman, M.L., White, D.E., Keith, T.E.C., Dockter, R.D., 1979. Duration of Hydrothermal
Activity at Steamboat Springs, Nevada, from Ages of Associated Volcanic Rocks. U.S.
Geological Survey Professional Paper 458-D. 14 pp.
Sillitoe, R.H., 1993. Epithermal models: genetic types, geometrical controls and shallow
features. In: Kirkham, R.V., Sinclair, W.D., Thorpe, R.I., Duke, J.M. (Eds.), Mineral
Deposit Modeling. Geological Association of Canada, pp. 403–417.
Sillitoe, R.H., 1994. Erosion and collapse of volcanoes: causes of telescoping in intrusion-
centred ore deposits. Geology 22, 945–948.
Sillitoe, R.H., 1995. Exploration of porphyry copper lithocaps. In: Mauk, J.L., St. George, J.
D. (Eds.), Pacific Rim Congress 1995, Auckland. Proceedings: Parkville. Australasian
Institute of Mining and Metallurgy, pp. 527–532.
Sillitoe, R.H., 1999. Styles of high-sulfidation gold, silver and copper mineralization in
the porphyry and epithermal environments. In: Weber, G. (Ed.), Pacrim '99
Congress, Bali, Indonesia. Proceedings: Parkville. Australasian Institute of Mining
and Metallurgy, pp. 29–44.
Sillitoe, R.H., Grauberger, G.L., Elliot, J.E., 1984. Gold deposits and hydrothermal eruption
breccias associated with a maar volcano at Wau, Papua New Guinea. Economic
Geology 79, 638–655.
Stoffregen, R., 1987. Genesis of acid-sulfate alteration and Au–Cu–Ag mineralization at
Summitville, Colorado. Economic Geology 82, 1575–1591.
Taylor, S.R., McLennan, S.M., 1995. The geochemical evolution of the continental crust.
Reviews in Geophysics 33, 241–265.
Thompson, A.J.B., Thompson, F.J.H., 1996. Atlas of alteration. A field and petrographic
guide to hydrothermal alteration minerals. Alpine Press, Vancouver. 120 pp.
Wedepohl, K.H., 1995. The composition of the continental crust. Geochimica et
Cosmochimica Acta 59, 217–239.
Winchester, J.A., Floyd, P.A., 1977. Chemical discrimination of different magma series
and their differentiation products using immobile elements. Earth and Planetary
Science Letters 133, 227–237.