Mineralium Deposita (2004) 39: 173–188
DOI 10.1007/s00126-003-0390-z
A RT I C L E
Viorica Milu Æ Jean-Pierre Milesi Æ Jacques Léon Leroy
Rosia Poieni copper deposit, Apuseni Mountains, Romania: advanced
argillic overprint of a porphyry system
Received: 1 July 2003 / Accepted: 31 August 2003 / Published online: 10 October 2003

Springer-Verlag 2003
Abstract The Rosia Poieni deposit is the largest por-
phyry copper deposit in the Apuseni Mountains,
Romania. Hydrothermal alteration and mineralization
are related to the Middle Miocene emplacement of a
subvolcanic body, the Fundoaia microdiorite. Zonation
of the alteration associated with the porphyry copper
deposit is recognized from the deep and central part of
the porphyritic intrusion towards shallower and outer
portions. Four alteration types have been distinguished:
potassic, phyllic, advanced argillic, and propylitic.
Potassic alteration affects mainly the Fundoaia subvol-
canic body. The andesitic host rocks are altered only in
the immediate contact zone with the Fundoaia intru-
sion. Mg-biotite and K-feldspar are the main alteration
minerals of the potassic assemblage, accompanied by
ubiquitous quartz; chlorite, and anhydrite are also
present. Magnetite, pyrite, chalcopyrite and minor
bornite, are associated with this alteration. Phyllic
alteration has overprinted the margin of the potassic
zone, and formed peripheral to it. It is characterized by
the replacement of almost all early minerals by abun-
dant quartz, phengite, illite, variable amounts of illite-
smectite mixed-layer minerals, minor smectite, and
kaolinite. Pyrite is abundant and represents the main
sulfide in this alteration zone. Advanced argillic alter-
ation affects the upper part of the volcanic structure. The
Editorial handling: B. Lehmann
V. Milu
Geological Institute of Romania, 1 Caransebes Str.,
78344 Bucharest, Romania
J.-P. Milesi
BRGM, DR/RM, BP 6009, 45060 Orléans cedex 2, France
J. L. Leroy (&)
Université Henri Poincaré-Nancy 1, UMR G2R, BP 239,
54506 Vandoeuvre-les-Nancy cedex, France
E-mail: jacques.leroy@g2r.uhp-nancy.fr
Tel.: +33-3-83684702
Fax: +33-3-83684701
mineral assemblage comprises alunite, kaolinite, dickite,
pyrophyllite, diaspore, aluminium-phosphate-sulphate
minerals (woodhouseite-svanbergite series), zunyite,
minamyite, pyrite, and enargite (luzonite). Alunite forms
well-developed crystals. Veins with enargite (luzonite)
and pyrite in a gangue of quartz, pyrophyllite and dia-
spore, are present within and around the subvolcanic
intrusion. This alteration type is partially controlled by
fractures. A zonal distribution of alteration minerals is
observed from the centre of fractures outwards with: (1)
vuggy quartz; (2) quartz + alunite; (3) quartz + kaol-
inite ± alunite and, in the deeper part of the argillic
zone, quartz + pyrophyllite + diaspore; (4) illite +
illite-smectite mixed-layer minerals ± kaolinite ± alu-
nite, and e) chlorite + albite + epidote. Propylitic
alteration is present distal to all other alteration types
and consists of chlorite, epidote, albite, and carbonates.
Mineral parageneses, mineral stability fields, and alter-
ation mineral geothermometers indicate that the differ-
ent alteration assemblages are the result of changes in
both fluid composition and temperature of the system.
The alteration minerals reflect cooling of the hydrother-
mal system from >400 C (biotite), to 300–200 C
(chlorite and illite in veinlets) and to lower temperatures
of kaolinite, illite-smectite mixed layers, and smectite
crystallization. Hydrothermal alteration started with an
extensive potassic zone in the central part of the system
that passed laterally to the propylitic zone. It was fol-
lowed by phyllic overprint of the early-altered rocks.
Nearly barren advanced argillic alteration subsequently
superimposed the upper levels of the porphyry copper
alteration zones. The close spatial association between
porphyry mineralization and advanced argillic alter-
ation suggests that they are genetically part of the
same magmatic-hydrothermal system that includes a
porphyry intrusion at depth and an epithermal envi-
ronment of the advanced argillic type near the surface.
Keywords Porphyry copper ore deposit Æ
Hydrothermal alteration Æ Mineral chemistry Æ
Romania Æ Rosia Poieni
174

with an average grade of 0.36% Cu and 0.29 g/t Au

Introduction
More than 50% of the estimated total metal resources of
Romania consist of Neogene deposits located in the East
Carpathians and South Apuseni Mountains. The most
important metals related to this late Tertiary minerali-
zation event are gold, copper, lead and zinc.
Rosia Poieni is one of 14 porphyry copper (± Au ±
Mo) deposits and occurrences associated with Neogene
magmatic rocks from the South Apuseni Mountains,
Romania (Fig. 1). It is located in the Alba district,
approximately 8 km southeast of the town of Abrud.
Discovery resulted from local geological, geochemical
and geophysical research programs carried out in
the1960s and 1970s. Exploration by adits (exploration
galleries at several levels) and drillings were performed
in order to calculate the resources. Open-pit mining
started in 1986 and the deposit is currently in produc-
tion. The present vertical extension of the open pit is
300 m (between altitude of +910 and +1,210 m). Rosia
Poieni is the largest copper deposit from the Apuseni
Mountains. The calculated resources are 350 Mt of ore
(Borcos et al. 1998).
Ionescu (1974) and Ionescu et al. (1975) carried out a
mineralogical and petrographic study of rocks from the
Rosia Poieni area. They identified the disseminated
character of the copper mineralization and the zonal
alteration pattern. Bostinescu (1984) presented new data
regarding the geology of the deposit and compared it to
other porphyry copper deposits from the Apuseni
Mountains. Fluid inclusion techniques have also been
applied to Rosia Poieni (Pintea 1993, 1995, 1996;
Damman et al. 1996).
The purpose of this paper is to report new investi-
gations on the hydrothermal alteration of the Rosia
Poieni ore deposit, including the nature and chemical
characterization of the mineral assemblages, the spatial
zoning of alteration and mineralization products, and
the relationships between alteration, mineralization, and
host rocks. The chemistry of alteration minerals is used
to provide information concerning the nature of the
hydrothermal fluids and the evolution of alteration
processes.

Fig. 1 A Sketch map of the

Apuseni Mountains (western
Romania) showing generalized
exposures of Neogene igneous
rocks (dark grey areas). The
inset delimits the area of
Fig. 1B. B Simplified geological
map of part of South Apuseni
Mountains, showing the
location of porphyry Cu-(Mo)-
(Au) ore deposits and
occurrences (after Dumitrescu
and Sandulescu 1978, and
Bostinescu 1984)

Regional geology
The Apuseni Mountains (western Romania) represent
an isolated massif inside the Carpathian arc (Sandule-
scu 1984). They are composed of two different units,
the North Apuseni Mountains and the South Apuseni
Mountains. The North Apuseni Mountains are char-
acterized by an almost complete Permo-Mesozoic sed-
imentary sequence overlying an Upper Precambrian
crystalline basement. The South Apuseni Mountains
are geologically very complex consisting of Palaeozoic
and even older metamorphic rocks, Mesozoic ophiolites
and sedimentary rocks, and Tertiary igneous and sed-
imentary rocks (Fig. 1). The Tertiary evolution of the
South Apuseni Mountains is characterized by the for-
mation of small sedimentary basins associated with
significant volcanic activity of calk-alkaline type
(Ianovici et al. 1969, 1976; Borcos et al. 1986). Magma
genesis has long been considered as being subduction
related, but recent research has suggested that it is
associated to extension within a strike-slip regime in
the Carpatho-Pannonian realm (Balintoni 1994; Rosu
et al. 1997, 2000a).
The intersection points of the major pre-Laramian
tectono-magmatic alignments, trending E–W and
NE–SW, and Laramian alignments, trending NW–SE,
constituted zones of maximum Neogene volcanic and
metallogenic activity (Borcos 1976).
The K-Ar and biostratigraphic data show that the
Neogene volcanic activity evolved in three main epi-
sodes. The first one (ca. 15 Ma old), poorly developed, is
represented by rhyodacitic to dacitic tuffs hosted by
marls with Globigerina (Langhian) (Cioflica et al. 1966;
Rosu et al. 2000b). The second episode is represented by
large calk-alkaline, medium to high-K quartz andesites
with amphibole, pyroxene ± biotite, and dacite. It
started around 15 Ma with explosive activity producing
widespread volcano-sedimentary sequences and contin-
ued with intrusive activity (between 14.8 and 7.4 Ma)
forming complex volcano-plutonic structures (Borcos
et al. 1986; Rosu et al. 1997, 2000b). After a gap of
about 6 Ma, a third episode of alkaline affinity
(trachyandesites) is recorded at Uroiu Hill (1.6 Ma).
The two first volcanic episodes were accompanied by
metallogenic processes resulting in the following met-
allogenic districts: Brad-Sacaramb, Deva, Zlatna-Stani-
ja, Rosia Montana-Bucium, and Baia de Aries. The first
metallogenic activity of Mid Miocene age (Badenian)
was of local importance and consists of Au-Ag epi-
thermal deposits (e.g. Rosia Montana). The most
important metallogenic activity took place in Middle to
Late Miocene (Sarmatian, Pannonian) and is repre-
sented by Au-Ag-(Te) epithermal ore deposits (e.g.
Sacaramb, Stanija, Baia de Aries), or Pb-Zn-Cu-(Au,
Ag) (e.g. Troita, Coranda, Hanes) and porphyry Cu-
(Au-Mo) deposits (e.g. Rosia Poieni, Deva, Bolcana).
Mineralization occurs as veins, lenses, hydrothermal
breccias and stockworks (Ghitulescu and Socolescu
175
1941; Ianovici et al. 1969; Borcos 1976). There are sit-
uations in which epithermal and porphyry systems are
associated (e.g. Valea Morii, Bolcana).
The porphyry Cu-(Au-Mo) ore deposits and occur-
rences (Fig. 1) from the South Apuseni Mountains were
identified and described as a genetic entity during the
last decades of the 20th century (e.g. Borcos 1976;
Ianovici et al. 1977; Vlad 1981; Borcos and Berbeleac
1983; Bostinescu 1984). The porphyry copper systems
are centred on shallow subvolcanic intrusions that,
according to geophysical data, are located on protu-
berances of deep-seated dioritic plutons. The alteration
products display a well-expressed zonality, which ap-
pears to be mainly controlled by the distance from the
intrusion axis rather than the structural elements; the
lithologic control is less important (Bostinescu 1984).
Geology of the Rosia Poieni deposit
The Rosia Poieni subvolcanic structure (Fig. 2) is the
result of the regional calk-alkaline magmatic activity
that took place in the Apuseni Mountains from Middle
to Late Miocene (Ianovici et al. 1976; Borcos et al. 1986;
Rosu et al. 1997). The ages of Neogene magmatic rocks
were obtained combining K-Ar dating, palaeomagnetic
and biostratigraphic data. The Rosia Poieni subvolcanic
structure is located in the Rosia Montana-Bucium
metallogenic district. In the area of Rosia Poieni, the
basement consists of pre-Mesozoic metamorphic rocks
covered by Cretaceous and Tertiary sedimentary for-
mations.
The oldest Neogene igneous rocks (intrusions, lavas,
and pyroclastics) are the Poieni andesites (Fig. 2) char-
acterized by common hornblende, plagioclase, and
quartz phenocrysts (40 vol%), and a groundmass of
plagioclase and amphibole. Magnetite and apatite are
accessory minerals. The texture of Poieni andesite varies
from microgranular to microcrystalline.
The Poieni andesites were intruded by a subvolcanic
body characterized by a porphyritic texture, the Fund-
oaia microdiorite (Middle Miocene in age). Hornblende,
plagioclase, and minor rounded quartz phenocrysts (ca.
55 vol%) occur together with magnetite, apatite and
zircon as accessory minerals. The groundmass, micro-
granular in the core and in the deepest parts of the
intrusive body, and progressing to a microcrystalline
texture towards the periphery, consists of plagioclase,
hornblende, quartz, magnetite, and apatite. The intru-
sion is <1 km in diameter. Both igneous rock types
(Poieni andesite and Fundoaia microdiorite) are affected
by hydrothermal alteration and are exposed in the open
pit. The top of the Fundoaia intrusion is at the medium
level of the open-pit mine. Cretaceous sedimentary rocks
adjacent to the Fundoaia intrusion are thermally meta-
morphosed to hornfels (Ionescu 1974). Around the
subvolcanic body, especially at its upper part, there are
intrusive breccias that appear to be associated with the
emplacement of the Fundoaia body.
176

Fig. 2 A Geology of Rosia

Poieni area (modified from
Bordea et al. 1979). The inset
delimits the area of Fig. 2B. B
Open-pit map with location of
drill-holes from Fig. 3. The
height of each bench is 15 m.
The whole-rock geochemistry
profiles are also shown. Only
the location of samples from
Tables 2, 3, 4, 5, and Figs. 4
and 5 is shown. Pit outline as in
1999

At the periphery, amphibole-bearing andesite and

quartz andesite (bodies and lava) crop out; these
andesites are also considered to be of Middle Miocene
age (Fig. 2A). They lack mineralization and are only
propylitized (Bostinescu 1984). Pyroclastics, lavas and
small bodies of brown hornblende (± pyroxene)
andesite represent the youngest volcanic products (Late
Miocene: 9.3±0.5 Ma, K-Ar method; Rosu et al.
1997).
Methods
Geologic information comes mainly from the open-pit mine and
also from outcrops, galleries, and some exploration drill-holes.
More than 200 thin and polished thin sections were examined by
optical microscopy in both reflected and transmitted light.
Chemical analyses of alteration minerals were carried out using a
Camebax-SX50 with a wavelength dispersive spectrometer. The
acceleration voltage was 15 kV with a counting time of 6 s per
element and an excitation current of 12 nA. Elements routinely
analyzed were Si, Al, Fe, Mg, Mn, K, Na, Ca, Ti, and Cr (± Sr,
Cl). The analyses were made on minerals in polished thin sections.
X-ray diffraction analyses on whole-rock samples and on argillic
fractions were performed using a Siemens D5000 diffractometer.
Rock samples collected from the open-pit mine were analyzed by
inductively coupled plasma (ICP) methods (major and trace ele-
ments) and by atomic absorption spectrophotometry (gold) after
HCl-HF-HNO3 digestion and MIBK extraction (gold detection
limit: 0.02 ppm; analytical error: 10%). For lower gold content,
extraction of elements such as Fe is performed prior to analysis
(detection limit: 0.005 ppm). Only data on Cu, Mo, and Au
content are given in this paper. All analyses were carried out at
BRGM, Orléans, and at Henri Poincaré University, Nancy,
France.
Hydrothermal alteration
The majority of igneous rocks in the Rosia Poieni area
display at least weak hydrothermal alteration. Intense
hydrothermal alteration is restricted to the Fundoaia
microdiorite and Poieni andesites. The alteration and
mineralization assemblages and the relationships between
alteration and mineralization are summarized in Table 1.
Four alteration types have been distinguished: potassic,
phyllic, advanced argillic, and propylitic (Milu 1999).
These alteration zones vary from a potassic core through
an annular phyllic alteration to a well-developed ad-
vanced argillic zone. The propylitic zone occurs as a broad
halo around the other alteration types. Vertically, the
alteration products change from advanced argillic, to
phyllic, and then to potassic-altered rocks at depth.
Figure 3 represents a north–south trending cross-
section through the Rosia Poieni deposit, showing
relationships between igneous rocks and alteration types
and zones.
Potassic alteration
Potassic alteration minerals either replace the pre-exist-
ing igneous phenocrysts and groundmass or crystallize
in fine veinlets (Table 1). Primary mafic minerals are
partially to totally consumed.
Overall, the limit of occurrences of secondary biotite
generally corresponds to the limits of the Fundoaia
 177

Table 1 Hydrothermal mined assemblages in the Rosia Poieni
subvolcanic system. ab albite; anh anhydrite; alu alunite; ASP
aluminium-phosphate-sulphate minerals (woodhouseite-svanberg-
ite series); bt biotite; bn bornite; carb carbonates; cc chalcocite; chl
chlorite; cp chalcopyrite; dg digenite; dik dickite; dsp diaspore; enr
enargite; ep epidote; Fe-Tiox Fe-Ti oxides; gn galena; hm hematite;
hbl hornblende; ill illite; IS illite/smectite; ISII illite/smectite/illite/
illite; kao kaolinite; kfs K-feldspar; luz luzonite; mo molybdenite;
min minerals; mr marcasite; mt magnetite; phg phengite; or ortho-
clase; po pyrrhotite; py pyrite; prl pyrophyllite; qtz quartz; ser
sericite; sl sphalerite; sm smectite; td tetrahedrite; tn tennantite

Alteration style and mineral assemblage

Potassic Phyllic Advanced argillic Propylitic

A. Main primary minerals

1. Feromagnesian bt, chl, anh, ep, qtz, phg, ill, chl, ab, qtz, alu, kao chl, ep, carb
minerals (mainly hnb) carb, or py, Fe-Tiox
2. Feldspars kfs, ab, bt, chl ill, phg, mixed-layer qtz, kao, dik, prl, alu ep, ab, ser, carb
min (ISII, IS)
3. Quartz Stable Stable Corroded Stable
B. Veins and veinlets qtz, bt, kfs, ab, qtz, ill, phg, mixed-layer qtz, kao, alu, dsp, prl, -
chl, anh min (ISII, IS), chl, py APS, py, enr, (luz)
C. Opaque minerals cp, py, mt, hm, py, cp, bn, mo, mt, hm, py, enr (luz), mr, cc -
bn, mo td-tn, sl, gn, dg
Cu gradea >0.3% 0.1–0.3% <0.02% Unmineralized
a
Overall Cu grade related to alteration type

Fig. 3 North–south cross

section A-A
through the Rosia
Poieni system, showing the
porphyritic intrusion and host
rocks, alteration types and
zones (reconstructed from data
in Ionescu 1974, and Milu
1999). For the location of drill
holes and section profile A-A¢,
refer to Fig. 2. The inset
presents an east–west cross
section at the top of the open
pit (+1,210 m level), showing
the alteration zonality.
Location of sample R49 (see
Fig. 2B) is also shown

subvolcanic body. We distinguished three types of sec- 1978). Replacement biotite resulted from the alteration of
ondary biotite in the altered igneous rocks: replacement primary hornblende and plagioclase. It is reddish-brown
biotite, disseminated biotite, and veinlet biotite (Chivas to light brown in unpolarized light and is strongly
178
pleochroic in plane polarized light. This biotite com-
monly contains rutile inclusions, occurs as anhedral to
subhedral grains, both in pseudomorphous aggregates
after pre-existing mafic minerals and as flakes and
irregular patches in the rock (Fig. 4A). Hydrothermal
disseminated biotite crystals form fine-grained aggregates
in the groundmass. Their color varies from brownish to
green (Fig. 4B). Veinlet biotite occurs as well-developed
flakes or fine-grained euhedral to subhedral crystals
associated with quartz ± K-feldspar, chlorite, anhy-
drite, magnetite, chalcopyrite, and pyrite. It is light
brown to green colored (Fig. 4C). During later phyllic
alteration, hydrothermal biotite was largely converted to
chlorite and sericite. Primary plagioclase was variably
altered to albite, K-feldspar, phengite, illite, illite-smec-
tite mixed-layer minerals, smectite, kaolinite, and
quartz. Orthoclase replaced both plagioclase pheno-
crysts and, together with biotite and quartz, amphiboles.
The rock is entirely permeated with patches of micro-
perthite and intergrown orthoclase and quartz.
Phyllic alteration
A zone of phyllic alteration occurs peripheral to the
potassic alteration core and overprints it. Within the
Fundoaia porphyritic intrusion, phyllic alteration is
superimposed on marginal zones of potassic alteration
(Fig. 3). Within the Poieni andesites, this type of alter-
ation is superimposed on the outer part of the potassic
alteration zone and on the inner part of the propylitic
alteration zone.
Phyllic alteration (Fig. 4D) is characterized by the
replacement of almost all rock-forming minerals and
earlier alteration minerals by abundant illite (+
phengite), quartz, pyrite, variable amounts of illite-
smectite mixed-layer minerals (ISII and IS), minor
smectite, and kaolinite (Table 1). Generally, the origi-
nal rock textures are preserved. The presence of K-
mica (phengite, illite) together with quartz gives a
bleached white color to the altered rocks. This change
in color from dark grey of potassic alteration to white
reflects a complete depletion in ferromagnesian miner-
als such as hornblende and biotite. The rocks are en-
riched in pyrite, which occurs as veins and
disseminations. Feldspar is partially to completely
obliterated (Fig. 4E).
In rocks with early potassic alteration, phyllic alter-
ation occurs preferentially along fissures and veinlets.
There is a relationship between the frequency and widths
of fissures and the extent of phyllic alteration. Where an
interconnecting network of veins was formed, phyllic
alteration invaded the entire rock. Such situations can be
readily observed in the lower half portion of the open-pit
between +910 and +1,160 m. Phyllic veins contain
quartz, sericite, and pyrite ± chlorite. In wall rocks, the
mineral assemblage contains secondary biotite and
hydrothermal alkali feldspar (as relict minerals), albite,
chlorite, and sericite. Albite replaces a more An-rich
c
Fig. 4A–F Photomicrographs in transmitted light showing alter-
ation minerals from the Rosia Poieni system. A Replacement
biotite associated with alkali feldspar, quartz, and pyrite in rocks of
potassic alteration (Sample R8 from +925 m level). B Fine-
disseminated biotite in Fundoaia microdiorite (Sample R259 from
+925 m level); C Veinlet with biotite in Fundoaia intrusion
affected by potassic alteration (Sample R8 from +925 m level). D
Sericite in microdiorite affected by phyllic alteration (Sample
R257A from +925 m level). E Sericite formed on a twinned and
zoned crystal of plagioclase (Sample R66 from +955 m level). F
Alunite crystallized in open space formed by acid leaching of a
phenocryst in the Poieni andesite (Sample R60 from +1,165 m
level). G Well-developed crystals of alunite (Sample R36 from
+1,000 m level). H Two generations of alunite in a zone of
advanced argillic alteration. Large crystals of alunite (alu1) replaced
by extremely fine-grained alunite (alu2) (Sample R276A from
+1,060 m level). For the location of samples, refer to Fig. 2B. alu
alunite; bt biotite; kfs alkali feldspar; plag plagioclase; py pyrite; qtz
quartz; ser sericite
plagioclase and forms albite rims on plagioclase partially
replaced by sericite, chlorite, and pyrite. In most rock
samples from underground mining and the lower part of
the open-pit that have been subjected to potassic alter-
ation, secondary biotite is transformed into chlorite
(usually accompanied by rutile) with sericite or chlorite
+ sericite + quartz ± calcite.
Advanced argillic alteration
In the upper part of the Rosia Poieni volcanic structure,
advanced argillic alteration overprints the earlier
potassic, phyllic and propylitic alteration. The advanced
argillic mineral assemblage consists of alunite, kaolinite,
dickite, pyrophyllite, diaspore, zunyite, and minamiite,
with sulfides including pyrite, enargite and luzonite
(Table 1). This association is typical of advanced argillic
alteration (Meyer and Hemley 1967). The primary rock
textures are partially to totally destroyed.
The advanced argillic alteration is partially controlled
by fractures that are convergent on the cupola of the
subvolcanic body. Intense leaching has produced a
vuggy quartz rock surrounded by an alteration envelope
consisting from centre to rim of: (a) quartz + alunite;
(b) quartz + kaolinite + alunite or quartz + pyro-
phyllite + diaspore (in the deeper part of the argillic
zone); (c) illite + illite-smectite mixed-layer minerals
(ISII, IS) ± kaolinite ± alunite, and d) chlorite + albite
+ epidote. The contacts between these zones are rela-
tively sharp. An entire succession is generally a few
meters to tens of meters wide. If two fractures are close
to each other, there is commonly superposition of the
inner alteration zones, and the external zones are absent.
The inset in Fig. 3 shows the zonality of the alter-
ation assemblages in an E-W cross-section at the up-
permost bench of the open-pit: quartz + alunite,
kaolinite + quartz + alunite, illite + mixed-layer
minerals + kaolinite + quartz ± alunite.
Such a zonation is typical of advanced argillic alter-
ation in magmatic- hydrothermal environments (Meyer
179
180
Fig. 5 Photomicrographs in
reflected light of a vein of high-
sulfidation epithermal
mineralization within the
Fundoia porphyritic intrusion
at the lowest level of the open
pit (Sample R254 from +910 m
level; see Fig. 2B). The mineral
assemblage consists of: A
Diaspore (dsp), luzonite (luz),
and pyrite (py); B The diaspore
contains a mineral of the
svanbergite (sv)-woodhouseite
(wd) series
and Hemley 1967; Hemley et al. 1969, 1980; Hayba et al.
1985; Arribas 1995).
Vugs up to 2.5–3.0 cm wide formed where early
phenocrysts were completely dissolved. Only the habit of
the phenocrysts is left. Alunite crystallized in veinlets
and open spaces formed by acid leaching of amphibole
and feldspar phenocrysts and groundmass (Fig. 4F).
Only the habit of the phenocrysts can be recognized.
Alunite appears as well developed tabular to columnar
crystals up to 2 mm across, and intergrown with quartz
± pyrite (Fig. 4G). According to the classification of
Rye et al. (1992), the alunite from Rosia Poieni has the
features of alunite from the hydrothermal-magmatic
environment. Alunite was detected between the
+1,000 m level (in the open pit) and +1,256 m level
(surface prior to mining). The presence of alunite in the
top of the intrusion suggests a shallow level of
emplacement for the Fundoaia porphyritic body.
Pyrophyllite and diaspore occur in the advanced
argillic assemblage, particularly at deeper levels. Zunyite
[Al13Si5O20F2(OH,F)16Cl] was found associated with
quartz, pyrophyllite, alunite, and minamiite [(Na,Ca,-
K)Al3(SO4)2(OH)6]. The presence of zunyite also is
consistent with a magmatic-hydrothermal environment
(Reyes 1990).
Disseminated pyrite is common in the advanced
argillic alteration zone and native sulfur is also present.
Rare veins with enargite (luzonite) occur both within
and outside the porphyry intrusion. For example, within
the top of the intrusion there are veins (cm to dm in
width) with luzonite and pyrite associated with quartz,
pyrophyllite, and diaspore (Fig. 5A). The diaspore
contains a mineral of the svanbergite-woodhouseite
series [(Sr,Ca)Al3(SO4)(PO4)(OH)6] (Fig. 5B), which
forms under acid conditions (Stoffregen and Alpers
1987).
In the open pit, hydrothermal breccias (pebble dikes),
up to 1 m in width, cut rocks that show advanced arg-
illic alteration. Both the fragments (andesite) and the
matrix of these breccias are highly argillized and silici-
fied and impregnated with small pyrite and iron oxide
crystals.
Propylitic alteration
Propylitic alteration occurs distal to all other alteration
zones, extending beyond the open pit boundary. Pro-
pylitization occurs on a broad scale; all magmatic rocks
in the area, including the younger ones, are more or less
affected. From the core of the Fundoaia intrusion out-
ward, the spatial association is: potassic fi phyllic fi
advanced argillic fi propylitic alteration.
Propylitic alteration is pervasive and is represented
mainly by chloritization of the primary amphibole
phenocrysts (common hornblende) and groundmass
material. Feldspars are fresh or are partially replaced by
albite, carbonate, epidote, and sericite.
At Rosia Poieni, supergene alteration is relatively
poorly developed at the present-day surface. In strongly
silicified rocks, in the upper part of the open pit, oxi-
dation of pyrite to goethite produced a red-brown rock
that passes laterally to a yellow-brown rock due to the
presence of jarosite in advanced argillic altered rocks.
Locally, greenish coatings probably represent the
weathering of enargite and luzonite to scorodite (Fe-
AsO4Æ2H2O). Extremely fine-grained alunite formed on
well-developed crystals of alunite may have a supergene
origin (Fig. 4H).
Mineral composition
Biotite: Biotite is a characteristic silicate mineral in the
potassic alteration zone of the Fundoaia porphyritic
intrusion. In the altered rocks, biotite coexists with al-
kali feldspar, weakly sericitized plagioclase, quartz, and
rutile. The analyzed samples were collected in the deeper
levels of the Rosia Poieni open pit in the Fundoaia
subvolcanic body (elevation +925 and +955 m)
(Fig. 2B).
A total of 33 microprobe analyses of trioctahedral
micas were carried out. Only the analyses with S oxides
>93% and octahedral occupancy >2.5 atoms per
O10(OH)2 were taken into consideration. The chemical
 181

compositions (average values) and structural formulas types of biotite: replacement biotite, disseminated bio-
of the biotites are given in Table 2. There are no large tite, and veinlet biotite.
differences between chemical composition of the three Biotite contains sufficient (Si + Al) to fill the tetra-
hedral positions; additional Al contributes up to 0.48
atoms per O10(OH)2 to the octahedral layers. The SiIV/
AlIV ratio is less than 3 (the value for ideal phlogopite or
Table 2 Electron microprobe analyses (average values, wt%) and
structural formulas of hydrothermal biotite from potassic and annite). This difference is due to AlIV occupancies that
phyllic alteration assemblages (samples R6, R8, R9 and R66 in are higher than 1 (per 4 tetrahedral positions) as a result
Fig. 2B). n Number of microprobe analyses averaged; TET tetra- of the replacement of Mg and/or Fe2+ by Al3+ in
hedral occupancy; OCT octahedral occupancy; INT interlayered octahedral positions (Al-Tschermak type substitution).
occupancy; XMg=100 Mg/(Mg+Fe)
Deficiencies are also noted in the totals for octahedral
Replacement biotite Disseminated biotite Veinlet biotite and 12-coordinated atoms. Mg and Fe fill at least 81%
of the octahedral sites (average=91%). Calculated cat-
n 16 13 4 ionic 100 Mg/(Mg+Fetotal) ratios range from 57 to 76,
SiO2 38.08 37.95 37.78 with an average value of 71.
Al2O3 15.04 16.41 14.98
Cr2O3 0.02 0.01 0.02 Values of Mg/(Mg+Fe) and AlIVfor all analyzed
TiO2 2.69 1.55 3.20 biotites are plotted on the biotite classification diagram
FeOa 12.91 12.57 13.90 of Guidotti (1984) (Fig. 6A). The AlIV values corre-
MgO 16.40 16.58 16.49 spond to the structural formula calculated on the basis
MnO 0.12 0.13 0.25
K2O 9.43 9.45 9.02
of 22 oxygens. All data are grouped in the biotite plane,
Na2O 0.20 0.32 0.25 being Mg-biotite. Replacement and veinlet biotites
CaO 0.01 0.06 0.01 contain less AlVIthan disseminated biotite (Table 2),
Total 94.90 95.04 95.90 being concentrated in the lower half of the biotite plane,
Stuctural formula calculated on the basis of 11 oxygens closer to the annite-phlogopite line.
SiIV 2.82 2.80 2.78 A negative correlation between AlVI and TiVI con-
AlIV 1.18 1.20 1.22 tents was noted. Early biotite is first transformed into a
TET 4.00 4.00 4.00
AlVI 0.13 0.22 0.08 paler biotite and then into white mica with small crystals
Cr 0.00 0.00 0.00 of rutile along mica cleavages. There is a correlation
Ti 0.15 0.09 0.18 between the color of biotite and its TiVI content; the Ti
Fe 0.80 0.78 0.86 content of green biotite is lower than that of brown or
Mg 1.81 1.82 1.81
Mn 0.01 0.01 0.02
reddish-brown biotite. This relationship is commonly
OCT 2.90 2.92 2.94 observed in secondary biotites (Hayama 1959), including
K 0.91 0.91 0.85 those associated with porphyry type deposits (Chivas
Na 0.03 0.04 0.04 1978).
Ca 0.00 0.00 0.00 Feldspar: The calculated structural formula of feld-
INT 0.94 0.96 0.89
XMg 69.00 70.00 67.92 spar from the Fundoaia porphyry intrusion and Poieni
andesite is summarized for 26 microprobe analyses
a
SFe determined as FeO (Table 3). The analyzed samples were collected in the
open pit at +925, +955, +1,000 and +1,195 m levels.
The less altered plagioclase from the Fundoaia micro-
Fig. 6 A Plot of trioctahedral micas from the Rosia Poieni deposit diorite corresponds to andesine (Ab54.4An43.9Or1.7).
on Mg/(Mg+Fe2+) vs. AlVI diagram (Guidotti 1984). Ann annite; With progressive alteration, plagioclase phenocrysts
East eastonite; Phl phlogopite; Sid siderophyllite; B Plot of
chlorites from the Fundoaia porphyritic intrusion on a SiIV vs.
become Na-enriched (Ab87.6An9.9Or2.5 to Ab99.9
Fe/(Fe+Mg) diagram (after Foster 1962, Bayliss 1975, and An0.0Or0.1).
McLeod and Stanton 1984)
182

Table 3 Electron microprobe analyses (average values, wt%) and Table 4 Electron microprobe analyses (wt%) and structural for-
structural formulas of feldspars from potassic and phyllic alterated mulas of chlorites from the Fundoaia intrusion (samples R8 and
rocks (samples R6, R8, R9, R22, R49 and R66 in Fig. 2B). R252 in Fig. 2B). XMg=100 Mg/(Mg+Fe)
n Number of analyses averaged; Pl plagioclase; Or orthoclase; Ab
albite; An anorthite Analysis no. Replacement chlorite Veinlet chlorite

Plagioclase Albite Microperthite in Microperthite 1 2 3 4 5 6 7

(Unaltered) (on Pl) groundmass in veinlets
SiO2 27.47 28.21 28.05 27.60 32.39 30.41 30.44
Or Ab Or Ab Al2O3 19.57 19.95 19.64 19.29 18.74 19.85 18.61
Cr2O3 0.04 0.00 0.00 0.05 0.00 0.00 0.00
n 6 5 2 3 7 3 TiO2 0.11 0.17 0.37 0.04 0.13 0.24 2.37
SiO2 56.52 67.81 65.53 67.79 65.01 68.33 FeOa 19.08 19.99 20.48 21.18 10.27 11.28 10.45
Al2O3 26.98 19.75 18.36 19.79 18.87 19.81 MgO 18.17 18.68 18.29 17.82 24.30 23.90 23.67
Cr2O3 0.00 0.00 0.01 0.00 0.03 0.03 MnO 0.72 0.60 0.65 0.78 0.34 0.34 0.35
TiO2 0.01 0.01 0.01 0.02 0.01 0.00 K2O 0.04 0.01 0.14 0.01 0.06 0.17 0.24
FeOa 0.29 0.09 0.44 0.18 0.10 0.25 Na2O 0.01 0.00 0.00 0.03 0.00 0.02 0.05
MgO 0.01 0.01 0.01 0.04 0.01 0.00 CaO 0.04 0.18 0.05 0.05 0.05 0.02 0.03
MnO 0.02 0.02 0.01 0.00 0.01 0.05 Total 85.26 87.78 87.68 86.85 86.32 86.22 86.23
K2O 0.29 0.17 12.61 0.51 12.52 0.49
Na2O 6.22 11.28 3.00 11.17 3.08 10.84 Structural formula calculated on the basis of 14 oxygens
CaO 9.08 0.29 0.00 0.28 0.01 0.30 SiIV 2.88 2.88 2.88 2.87 3.16 3.00 3.00
Total 99.43 99.43 99.99 99.78 99.64 100.11 AlIV 1.12 1.12 1.12 1.13 0.84 1.00 1.00
AlVI 1.30 1.27 1.25 1.24 1.32 1.31 1.17
Structural formula calculated on the basis of 32 oxygens Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Si 10.22 11.92 11.99 11.90 11.92 11.94 Ti 0.01 0.01 0.03 0.00 0.01 0.02 0.18
Al 5.74 4.09 3.96 4.09 4.07 4.08 Fe 1.67 1.71 1.76 1.84 0.84 0.93 0.86
Ti 0.00 0.00 0.00 0.00 0.00 0.00 Mg 2.84 2.84 2.80 2.77 3.54 3.52 3.48
Fe 0.04 0.01 0.07 0.03 0.01 0.04 Mn 0.06 0.05 0.06 0.07 0.03 0.03 0.03
Cr 0.00 0.00 0.00 0.00 0.00 0.00 K 0.01 0.00 0.02 0.00 0.01 0.02 0.03
Mn 0.00 0.00 0.00 0.00 0.00 0.01 Na 0.00 0.00 0.00 0.01 0.00 0.00 0.01
Mg 0.00 0.00 0.00 0.01 0.00 0.00 Ca 0.01 0.02 0.01 0.01 0.01 0.00 0.00
Ca 1.76 0.05 0.00 0.05 0.00 0.06 XMg 62.94 62.48 61.43 60.00 80.83 79.06 80.15
Na 2.18 3.84 1.07 3.80 1.10 3.67
a
K 0.07 0.04 2.94 0.11 2.93 0.11 SFe determined as FeO
An 43.93 1.36 0.00 1.33 0.03 1.47
Ab 54.40 97.68 26.65 95.80 27.27 95.67
Or 1.67 0.96 73.35 2.87 72.70 2.83 replacement chlorites; veinlet chlorites have higher ratios
a
S Fe determined as FeO (approximately 80). The secondary disseminated biotite
has 100 Mg/(Mg+Fe) ratios that are intermediate be-
tween those of the two other types of chlorite (Tables 2
The bulk composition of the potassic feldspar phe- and 4). The silicon and aluminum occupancy in the
nocrysts is Or72.84Ab27.13An0.02. In the potassic alter- tetrahedral sites of chlorites varies from Si2.87Al1.13 to
ation zone, the entire rock is permeated by patches Si3.16Al0.84 .
of microperthite and intergrown orthoclase and Phengite, illite, illite-smectite mixed-layer minerals,
quartz ± opaque minerals. In the microperthite, and smectite: We here use the term ‘‘sericite’’ according
the host composition varies from Or69.9Ab30.1An0.0 to Leroy and Cathelineau (1982), Hayba et al. (1985),
to Or76.8Ab23.2An0.0 and the albite lamellae from Heald et al. (1987) and Eberl et al. (1987). The X-ray
Ab93.2An1.1Or5.6 to Ab98.3An0.7Or1.1. Microperthite also powder diffraction analyses show the presence of min-
occurs in veinlets with a composition from Or61.5- erals that are quite variable in their crystallochemical
Ab38.5An0.0 to Or82.4Ab17.6An0.0 for the host and from nature: phengite, illite, and illite-smectite mixed-layer
Ab94.1An2.1Or3.7 to Ab97.0An1.5Or1.5 for the albite minerals. Selected microprobe analyses of these types
lamellae. of minerals are presented in Table 5. Their structural
Chlorite: Using X-ray diffraction analyses on whole formulas were calculated on the basis of 11 oxygens.
rocks from the potassic ± phyllic alteration zone in the The analyzed phengite formed by alteration of plagio-
lower level of the open pit, 1MIb clinochlore was iden- clase phenocrysts (Phg a) and by pervasive alteration
tified. Microprobe analyses of chlorite from samples of of the groundmass (Phg b). Its interlayer charge is
potassic alteration, variably affected by phyllic alter- mostly balanced by potassium and varies from 0.90 to
ation, are given in Table 4. Data show that they are all 0.95 for O10(OH)2; Na and Ca are not present or their
clinochlore with a restricted compositional range participation is extremely low (<0.6 atoms). Four ca-
(Fig. 6B). Both the replacement chlorite (alteration of tegories of illites were analyzed: illite formed by al-
mafic minerals) and veinlet chlorite were analyzed. The teration of plagioclase in the Fundoaia porphyry
latter has a higher Mg content (3.48–3.54 octahedral intrusion (I a), illite formed by alteration of plagio-
sites) and a lower Fe content (0.84–0.93 octahedral sites) clase in the Poieni andesites (I b), illite formed by
than chlorites crystallized in destabilized mafic minerals. groundmass alteration in the Fundoaia intrusion (I c),
The 100 Mg/(Mg+Fe) ratio varies from 60.0 to 62.9 for and illite deposited in veinlets (I d). The last two illite
 183

Table 5 Representative electron microprobe analyses (wt%) and
structural formulas of phengite, illite, illite-smectite mixed layer
minerals (IS) and smectite. Phengite (Phg): Phg a plagioclase
alteration in Fundoaia porphyry intrusion; Phg b pervasive alter-
ation of groundmass in porphyry intrusion; Illite (I): I a plagioclase
alteration in Fundoaia porphyry intrusion; Ib plagioclase alteration
in Poieni andesites; I c groundmass alteration in Fundoia poprhyry
intrusion; I d veinlets; IS (mixed layered illite-smectite): IS a pla-
gioclase alteration; IS b amphibole alteration; IS c groundmass
alteration; Smectite (S):S a plagioclase alteration in porphyry
intrusion. INT sum of interlayer cations, OCT sum of tetrahedral
cations, TET sum of tetrahedral cations, XMg=100 Mg/(Mg+Fe)

Mineral Phengite (Phg) Illite (I) IS Smectite (S)

Phg a Phg b Ia Ib Ic Id IS a IS b IS c Sa

Sample no. R66 R66 R257A R257A R66 R22 R22 R49 R9 R8 R22 R47 R16 R49 R8
SiO2 46.60 48.49 46.16 46.09 51.11 50.68 51.18 49.30 48.05 49.26 51.00 46.14 52.48 48.39 50.37
Al2O3 34.77 29.84 32.58 33.79 31.03 32.91 31.81 33.52 30.43 30.37 32.02 30.87 35.56 35.93 30.53
Cr2O3 0.00 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.15 0.05 0.00 0.00 0.00 0.00
TiO2 0.00 0.03 0.49 0.49 0.02 0.00 0.02 0.08 0.00 0.03 0.02 0.02 0.02 0.02 0.01
FeOa 2.21 2.52 1.86 1.39 1.65 1.11 2.13 0.84 3.21 2.98 2.05 0.27 0.79 0.62 2.06
MgO 0.23 1.81 1.06 0.73 1.73 0.87 1.40 0.96 2.80 1.83 1.33 0.81 0.00 0.75 0.61
MnO 0.24 0.00 0.00 0.00 0.11 0.04 0.00 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.06
K2O 9.99 9.78 10.38 10.00 8.20 8.62 7.80 7.86 8.97 9.04 7.33 6.36 2.08 1.57 1.26
Na2O 0.20 0.10 0.32 0.45 0.28 0.18 0.17 0.80 0.16 0.23 0.18 0.49 3.07 1.30 0.20
CaO 0.02 0.11 0.00 0.00 0.29 0.00 0.02 0.14 0.18 0.40 0.00 0.01 0.32 0.00 1.09
Total 94.26 92.69 92.84 93.01 94.45 94.41 94.53 93.59 93.79 94.29 93.97 84.97 94.32 88.56 86.21
Structural formula calculated on the basis of 11 oxygens
SiIV 3.13 3.31 3.16 3.13 3.36 3.33 3.36 3.26 3.24 3.3 3.35 3.32 3.33 3.24 3.47
AlIV 0.87 0.69 0.84 0.87 0.64 0.67 0.65 0.74 0.76 0.7 0.65 0.68 0.67 0.76 0.53
TET 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
VI
Al 1.88 1.71 1.79 1.84 1.77 1.87 1.81 1.87 1.66 1.70 1.83 1.93 1.99 2.08 1.95
Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00
Ti 0.00 0.00 0.03 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Fe2+ 0.12 0.14 0.11 0.08 0.09 0.06 0.12 0.05 0.18 0.17 0.11 0.02 0.04 0.04 0.12
Mg 0.02 0.18 0.11 0.07 0.17 0.09 0.14 0.10 0.28 0.18 0.13 0.09 0.00 0.07 0.06
Mn 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
OCT 2.04 2.04 2.03 2.02 2.04 2.02 2.07 2.02 2.13 2.06 2.08 2.04 2.04 2.19 2.14
K 0.88 0.87 0.91 0.87 0.70 0.74 0.67 0.68 0.79 0.79 0.63 0.60 0.17 0.14 0.11
Na 0.03 0.01 0.04 0.06 0.04 0.02 0.02 0.10 0.02 0.03 0.02 0.07 0.38 0.17 0.03
Ca 0.00 0.01 0.00 0.00 0.02 0.00 0.00 0.01 0.01 0.03 0.00 0.00 0.02 0.00 0.08
INT 0.90 0.89 0.95 0.93 0.76 0.76 0.69 0.79 0.82 0.85 0.65 0.67 0.57 0.31 0.22
XMg 16.00 56.00 50.37 48.21 65.00 58.00 54.00 67.00 61.00 52.00 54.00 84.00 0.00 68.00 34.51
a
SFe determined as FeO

categories seem to be richer in S(Fe+Mg) (from 0.35

to 0.46 atoms) than the others (from 0.15 to 0.26
atoms).
Two types of illite-smectite mixed-layer minerals have
been determined by X-ray diffraction: randomly int-
erstratified illite-smectite (R=0) whose percentage in the
smectite component ranges from 100% (pure smectite)
to 75%, and type R3 interlayered illite-smectite (ISII)
with 90–95% illite. The illite/smectite mixed-layer min-
erals (Table 5) correspond to minerals formed by alter-
ation of plagioclase (IS a), amphibole (IS b) and
groundmass (IS c). No clear distinction can be made
between the IS a and IS b categories. In the IS c cate-
gory, Na is the dominant interlayer element (0.38
atoms). The analyzed smectite (S a) formed by plagio-
clase alteration.
The K content in interlayer sites and the interlayer
charge values were plotted in a discrimination diagram
(after Hower and Mowatt 1966) for white micas, mixed-
layer minerals and smectites (Fig. 7). The crystal
chemical variations of illite-smectite mixed-layer miner-
als can be due to variations of temperature and also to
chemical factors such as K+/H+ ratio (Helgeson et al.
1978).
Porphyry mineralization
Mineralization and hydrothermal alteration are spatially
related to the Fundoaia intrusion. The Poieni andesites
show a general lack of porphyry-style mineralization,
except in the contact zone with the porphyritic intrusion.
Mineralization occurs as dissemination in pervasively
altered rocks and within veins and fractures forming a
well-developed stockwork best developed in the potassic
zone.
The ore mineralogy: pyrite, chalcopyrite, magnetite,
hematite, molybdenite, and bornite with subordinate
tetrahedrite-tennantite, enargite, luzonite-stibioluzonite,
and digenite, and minor pyrrhotite, sphalerite, galena,
covellite, and chalcocite (Table 1). Chalcopyrite, the
dominant hypogene copper-mineral, occurs as dissem-
inations or in stockwork veinlets. Its abundance de-
creases towards the margin of the Fundoaia intrusion.
Pyrite is ubiquitous throughout the ore body and is the
main sulfide mineral in the upper part of the volcanic
structure, especially in the advanced argillic zone.
Pyrite in quartz veins is coarser grained than dissemi-
nated pyrite. Molybdenite, mainly as disseminated
184

Fig. 7 (K+Na+2Ca) vs. K diagram (according to Hower and

Mowatt 1966). For mineral type abbreviations, see Table 5

flakes, has been observed in few polished thin sections

of rock samples from the lower part of the open pit.
Minerals from the tetrahedrite-tennantite series and
enargite (luzonite) are rare. Gold is present with chal-
copyrite, and is concentrated in the central part of the
deposit.
The porphyry copper deposit was explored down to
1,200 m in depth (Fig. 3). Drill and underground data
define an elliptical ore body with a maximum extension
at the +550 m level. Figure 8 presents three horizontal
maps with copper grade contours (>0.1, >0.2, >0.3
and >0.4% Cu) at 925, 770, and 550 m above sea level.
At least 90% of the disseminated porphyry copper grade
mineralization is located in the Fundoaia subvolcanic
body, only locally extending beyond it. Copper grades
are roughly concentric in pattern, decreasing toward the
margins of the intrusion. The Cu-richest zone (0.7–1.4%
Cu) was observed between the altitude of +200 and
+800 m. The drilling program (6 drill holes originated
at the bottom of the open pit and consisting of 4,176 m
of drilling), operated in 2002 by Gabriel Resources Ltd.
to test the extent and the metal grades of the potassic
zone, confirmed the extent of the mineralization down
to depth with average grades of 0.64% Cu and 0.29 g/t
Au.
In order to evaluate the Cu, Mo, and Au contents of
rocks from the open pit, three geochemical profiles
were sampled (+925, +1,000, +1,195 m) (Fig. 2B)
(Milu 1999). The results are summarized in Table 6.
Copper is positively correlated with gold (Fig. 9),
whereas there is no correlation between these elements
and molybdenum. Both copper and gold grades de-
crease towards the upper levels of the open pit. High-
Fig. 8 Three superimposed horizontal maps showing copper
contour values (in %) at the mine levels: A +925 m, B +770 m,
and C +550 m above see level. Outline of Fundoaia intrusion
(dark dashed line) at each level is also shown. The contour values
are from Borcos and Milu 1994 (unpublished data)
Cu content is invariably related to the potassic alter-
ation zone. Outside the potassic alteration limits, cop-
per content decreases to <1,000 ppm, except where
phyllic alteration is superimposed on potassic alter-
ation. Mo contents are usually low; the maximum
content (683 ppm) was found in a sample with
molybdenite collected from the open-pit at the
+1,000 m level. Gold values greater than 0.02 ppm Au
(lower limit of detection) are almost restricted to the
potassic (± phyllic) altered rocks. The upper part of
the Rosia Poieni structure with advanced argillic
alteration is barren (less than 200 ppm Cu, 10 ppm
Mo, and 0.05 ppm Au), a feature often observed in
association with porphyry copper deposits (Hedenquist
et al. 1996).
 185

Table 6 Average Cu, Mo and Au contents (all values in ppm) at 2KðMg; FeÞ3 AlSi3 O10 ðOHÞ2 þ4Hþ ! AlðMg; FeÞ5
three levels (+925 , +1,000, and +1,195 m) of the open-pit mine.
Minimum and maximum content values are indicated in brackets. AlSi3 O10 ðOHÞ8 þðMg; FeÞ2þ þ2Kþ þ3SiO2
For location of geochemistry profiles, see Fig. 2B. Fm Fundoaia
microdiorite, Pa Poieni andesite, AA advanced argillic alteration,
K potassic alteration, S phyllic alteration, n number of analyses
The release of potassium favors the formation of
sericite commonly found associated with this type of
Elevationa (m) +925 m +1,000 m +1,195 m chlorite. Titanium released by the breakdown of biotite
formed small rutile grains occurring mainly along
Rock type Fm Fm Pa cleavage planes of chlorite.
Alteration type K K±S AA
n 14 23 8 The amount of Al substitution for Si in tetrahedral
Cu 3,539 1,508 50 sites typically increases with increasing temperature
(433‚7938) (36‚4731) (10‚171) (McDowel and Elders 1980; Cathelineau and Nieva
Mo 50 61.41 4.13 1985). Cathelineau (1988) found that for chlorite from
(8‚175) (<5‚683) (<5‚7)
Au 0.062 0.022 0.015
the Los Azufres (Mexico) and Salton Sea (California)
(<0.02‚0.115) (<0.02‚0.065) (<0.02‚0.05) geothermal systems, the relation T(C)=)61.92+
321.98 (AlIV) was valid in the temperature range of 130
a
Meters above sea level to 300 C and suggested that this relation could be
extrapolated to lower and higher temperatures. Apply-
ing this chlorite geothermometer to chlorite from the
Mineral geothermometry Fundoaia intrusion, a calculated temperature of around
300 C is obtained for replacement chlorite, and tem-
Using mineral chemistry of some alteration minerals, peratures of 210 C (Table 4, analysis 5) and 260 C
their crystallization temperatures were estimated (Table 4, analyses 6 and 7) for veinlet chlorite (Table 4
applying different geothermometers. In the potassic and Fig. 10A).
zone, the mineral assemblage includes Mg-rich biotite, The K interlayer content and the interlayer occu-
alkali feldspar, quartz, and minor chlorite, anhydrite, pancy of illite were used to estimate crystallization
and sericite. Using the solubility curve of Ti4+ as a temperatures of illite from Rosia Poieni based on the
function of temperature established by Le Bel illite geothermometer (Cathelineau 1988). A temperature
(1979) for biotite from the Cerro Verde-Santa range from 215 to 255 C was obtained (Fig. 10B). For
Rosa porphyry copper system in southern Peru, biotite illite crystallized in veinlets, the temperature interval is
from Rosia Poieni would have crystallized between 550 smaller, between 235 and 255 C. This temperature
and 400 C. These temperatures are somewhat lower interval represents only part of the temperature range in
than fluid-inclusion temperatures of around 600 C which phyllic alteration took place. Illite crystallized at
obtained by Damman et al. (1996) for the potassic lower temperatures than phengite and at higher tem-
alteration. peratures than illite-smectite mixed-layer minerals and
The relationship between chlorite and the other smectite. In hydrothermal environments, smectite has
alteration minerals in potassically altered rocks shows been reported to form at temperatures up to 100 C
that chlorite crystallization started toward the end of (Velde 1985) or up to 150 C (Harvey and Browne 1991)
the potassic alteration stage and continued during the and illite-smectite mixed layer minerals form at tem-
phyllic alteration stage. This chlorite replaced ferro- peratures between 100 and 200 C.
magnesian minerals (mainly secondary biotite) and The abundant alunite in the advanced argillic alter-
precipitated in veinlets. The chlorite formation from ation indicates high aSO42-. Large crystals of alunite
biotite corresponds to a hydrogen metasomatism (alu1, Fig. 4F–H) suggest a hypogene origin. Such alu-
reaction (Hemley and Jones 1964) that can be written nite is believed to form at about 200–400C (Hemley
as: et al. 1969; Rose and Burt 1979; Rye et al. 1992). The

Fig. 9 Cu vs. Au plot for

samples from Rosia Poieni
open pit. Solid dot +925 m
level; open triangle +1,000 m
level; rhomb +1,195 m level.
The sampling profiles are
shown in Fig. 2B
186
Fig. 10 A Temperature-
dependent Si-Al substitution in
octahedral positions for chlorite
from Rosia Poieni (Cathelineau
and Nieva 1985); B Range of
crystallization temperatures of
illite from the Rosia Poieni
system obtained with the illite
geothermometer of Cathelineau
(1988): (a) using all analyzed
illites; (b) using only K values
of illites from veinlets. Illite
from the Los Azufres
geothermal system (Mexico) is
shown as solid dots
presence of the pyrophyllite-kaolinite assemblage con-
strains the temperature range for the process to
<300 C (Hemley et al. 1980).
Conclusions
Mineralization and associated alteration of the Rosia
Poieni porphyry system are controlled by the shallow-
level emplacement of the Middle Miocene Fundoaia
intrusion. On the basis of different mineral assemblages,
four alteration types have been distinguished: potassic,
propylitic, phyllic and advanced argillic. A zonation of
the alteration is recognized from deep and central parts
of the porphyritic intrusion towards shallower and outer
parts (Fig. 3). A close relationship between sulfide
mineral assemblage and silicate alteration style is ob-
served (Table 1). The porphyry copper mineralization is
generally within the Fundoaia intrusion, extending be-
yond it locally only, and is associated with the potassic
(± phyllic) alteration zone.
Based on the chemical composition of the alteration
minerals, and the application of mineral geothermometry,
the evolution of the system can be tentatively recon-
structed. The mineralogical and chemical composition of
both the porphyritic Fundoaia intrusion and its andesitic
host rock is very similar. Therefore, the observed alter-
ation styles cannot be related to initial differences of the
altered rocks and appear mainly controlled by the chem-
ical composition of the hydrothermal fluids and/or tem-
perature of the system, with a continuity from magmatic
to hydrothermal conditions as indicated by fluid inclusion
data (Pintea 1993, 1995; Daman et al. 1996). According to
these data, the potassic alteration formed in the core of the
system from high-salinity, high-temperature fluids ex-
solved during the final stage of crystallization of the
Fundoaia subvolcanic body.
The phyllic alteration is superimposed on the mar-
ginal part of the potassic alteration zone. Early alter-
ation minerals were replaced by abundant quartz,
phengite, variable amounts of chlorite, illite-smectite
mixed-layer minerals, and minor smectite and kaolinite.
The instability of K-feldspar and the crystallization of a
quartz-phengite or quartz-illite assemblage indicate ei-
ther changes in K+/H+ ratio towards slightly acid pH
(pH 4–6 for illite) (Hemley et al. 1969) and/or a tem-
perature decrease. The crystal-chemical variations pre-
sented by illite-smectite mixed-layer minerals can also be
influenced by variations of both fluid temperature and
chemical factors such as the K+/H+ ratio (Helgeson
et al. 1978). The formation of smectite reflects late-stage
adjustment of the phyllic assemblage to lower tempera-
tures and probably more neutral pH.
The advanced argillic alteration developed in the
upper levels of the Rosia Poieni structure and is partially
controlled by fractures that converge on the subvolcanic
cupola, suggesting a relation with the underlying mic-
rodiorite porphyry. It overprints the earlier potassic,
phyllic and propylitic alteration. The mineral assem-
blage consists of minerals stable in an acid, relatively
low-temperature and near-surface environment: alunite,
kaolinite, dickite, pyrophyllite, diaspore, zunyite, and
minamyite, pyrite, enargite and luzonite. The origin of
advanced argillic alteration is related to acid fluids
possibly generated by the condensation of HCl, SO2 and
HF-enriched vapors into meteoric waters channeled
along the fault system. The acidity of the fluids de-
creased progressively from the fracture outward to the
host rocks, giving rise to successive alteration assem-
blages characterized from the core outwards by (a)
quartz + alunite; (b) quartz + kaolinite + alunite or
quartz + pyrophyllite + diaspore (in the deeper part of
the argillic zone); (c) illite + illite-smectite mixed-layer
minerals (ISII, IS) ± kaolinite ± alunite, and (d)
chlorite + albite + epidote. Vuggy quartz is the product
of extreme acid leaching at pH<2 (Stoffregen 1987).
According to Stoffregen and Alpers (1987), an argilli-
zation process in which alunite + kaolinite are the main
alteration minerals takes place at pH 4 to 5. Acid con-
ditions and a high activity of PO43- are necessary for the
crystallization of minerals belonging to the svanbergite-
woodhouseite series (beudantite group). The alteration
zoning, the coarse alunite crystals, the large amounts of
pyrite and alunite, and a high sulfidation assemblage
with enargite, covellite and native sulfur indicate a
shallow environment.

The Rosia Poieni system consists of a porphyry
copper deposit with a nearly barren advanced argillic
overprint. The close spatial association between por-
phyry mineralization and advanced argillic alteration
suggests that they are part of the same magmatic-
hydrothermal system with a porphyry intrusion at depth
and an epithermal environment of the advanced argillic
type near the surface.
The spatial association between porphyry copper
deposits and high-sulfidation epithermal mineralization
is common (Sillitoe 1983; Arribas 1995; Hedenquist
et al. 1996, 1998). Hedenquist et al. (1994) propose a
four-stage model: (1) Metal fractionation from melt to
fluid during magma crystallization under lower pressure
conditions; (2) Separation of this exsolved fluid into a
gas-rich vapor and a metal-rich saline liquid; (3) The
gas-rich vapor phase ascends to the surface and con-
denses into meteoric water to form an acid fluid which
reacts with the host rock (advanced argillic alteration).
This leaching creates a permeable zone; (4) The dense,
metal-rich liquid then ascends into the permeable and
leached zone and precipitates Cu and Au.
However in some places, such as Ugusu in Japon
(Iwao 1962, 1963), the porphyry system is associated
with only leached, barren rocks. Hedenquist et al. (1994)
indicate that this situation may occur when the dense,
saline, metal-bearing liquid is not released from its
source adjacent to the magma, due to lack of fracturing
or when a high relief causes a hydraulic gradient which
prevent the saline liquid ascent.
Acknowledgements This study forms part of a Ph.D. research
program carried out by V.M. at Bucharest University, Romania.
Financial support for the research was provided by host institu-
tions of the authors and by the European Science Foundation (a
GEODE visiting grant to VM from Geological Institute of
Romania to Henri Poincaré University-Nancy 1). We thank Min-
vest S.A. Company and MINEXFOR S.A. (Deva) for providing
access to the deposit. Special thanks are extended to M. Borcos,
P. Piantone, and E. Marcoux for their helpful suggestions and to
J.W. Hedenquist, J.M. Guilbert, and B. Lehmann for their fruitful
comments on the manuscript.
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