Mineralium Deposita (1998) 33: 111±136
ARTICLE
G. R. AlmodoÂvar á R. SaÂez á J. M. Pons á A. Maestre
M. Toscano á E. Pascual
Geology and genesis of the AznalcoÂllar massive sulphide deposits,
Iberian Pyrite Belt, Spain
Received: 3 March 1996 / Accepted: 10 April 1997
Abstract The AznalcoÂllar mining district is located on
the eastern edge of the Iberian Pyrite Belt (IPB) con-
taining complex geologic features that may help to un-
derstand the geology and metallogeny of the whole IPB.
The district includes several ore deposits with total re-
serves of up to 130 Mt of massive sulphides. Average
grades are approximately 3.6% Zn, 2% Pb, 0.4% Cu
and 65 ppm Ag. Mined Cu-rich stockwork mineraliza-
tions consist of 30 Mt with an average grade of 0.6%
Cu. Outcropping lithologies in the AznalcoÂllar district
include detrital and volcanic rocks of the three main
stratigraphic units identi®ed in the IPB: Phyllite-Quart-
zite Group (PQ), Volcano-Sedimentary Complex (VSC)
and Culm Group. Two sequences can be distinguished
within the VSC. The Southern sequence (SS) is mainly
detritic and includes unusual features, such as basaltic
pillow-lavas and shallow-water limestone levels, the
latter located in its uppermost part. In contrast, the
AznalcoÂllar-Los Frailes sequence (AFS) contains
abundant volcanics, related to the two main felsic vol-
canic episodies in the IPB. These distinct stratigraphic
features each show a di€erent palaegeographic evolution
during Upper Devonian and Lower Carboniferous.
Massive sulphides occur in association with black shales
overlying the ®rst felsic volcanic package (VA1) Pal-
ynomorph data obtained from this black shale horizon
indicate a Strunian age for massive sulphides, and con-
sequently an Upper Devonian age for the VA1 cycle.
Field and textural relationships of volcanics suggest an
evolution from a subaerial pyroclastic environment
(VA1) to hydroclastic subvolcanic conditions for the
Editorial handling: E. Marcoux
G.R. AlmodoÂvar (&) á R. SaÂez á M. Toscano, á E. Pascual
Dpto. de GeologõÂ a, Universidad de Huelva,
21819 La RaÂbida (Huelva), Spain
E-mails: almodovar@uhu.es, saez@uhu.es,
mtoscano@uhu.es and pascual@uhu.es
J.M. Pons á A. Maestre
BOLIDEN - APIRSA, 41890 AznalcoÂllar (Sevilla), Spain
Ó Springer-Verlag 1998
VA2. This evolution can be related to compartmental-
izing and increasing depth of the sedimentary basin,
which may also be inferred from changes in the associ-
ated sediments, including black shales and massive sul-
phides. Despite changes in the character of volcanism,
the same dacitic to rhyolitic composition is found in
both pyroclastic and subvolcanic igneous series. The
main igneous process controlling chemical variation of
volcanics is fractional crystallization of plagioclase
(+accessories). This process took place in shallow, sub-
surface reservoirs giving rise to a compositional range of
rocks that covers the total variation range of felsic rocks
in the IPB. The Hercynian orogeny produced a complex
structural evolution with a major, ductile deformation
phase (F1), and development of folds that evolved to
thrusts by short ¯ank lamination. These thrusts caused
tectonic repetition of massive and stockwork orebodies.
In AznalcoÂllar, some of the stockwork mineralization
overthrusts massive sulphides. These structures are cut
by large brittle overthrusts and by late wrench faults.
The original geometric features of massive sulphide
deposits correspond to large blankets with very variable
thicknesses (10 to 100 m), systematically associated with
stockworks. Footwall rock alteration exhibits a zona-
tion, with an inner chloritic zone and a peripheral ser-
icitic zone. Silici®cation, sulphidization and carbon-
atization processes also occur. Hydrothermal alteration
is considered a multi-stage process, geochemically
characterized by Fe, Mg and Co enrichment and intense
leaching of alkalies and Ca. REE, Zr, Y and Hf are also
mobilized in the inner chloritic zones. Three ore types
occur, both in stockworks and massive sulphides, named
pyritic, polymetallic and Cu-pyritic. Of these, Cu-pyritic
is more common in stockworks, whereas polymetallic is
prevalent in massive sulphides. Zoning of sulphide
masses roughly sketches a typical VHMS pattern, but
many alternating polymetallic and barren pyritic zones
are probably related to tectonics. Although the para-
genesis is complex, several successive mineral associa-
tions can be distinguished, namely: framboidal pyritic,
high-temperature pyritic (300 °C), colloform pyritic,
112
polymetallic and a late, Cu-rich high-temperature asso-
ciation (350 °C). Fluid inclusion data suggest that hy-
drothermal ¯uids changed continuously in temperature
and salinity, both in time and space. Highest Th and
salinities correspond to inner stockworks zones and later
¯uids. Statistic population analysis of ¯uid inclusion
data points to three stages of hydrothermal activity, at
low (<200 °C), intermediate (200±300 °C) and high
temperatures (300±400 °C). 34S values in massive sul-
phides are lower than in stockwork mineralization sug-
gesting a moderate bacterial activity, favoured by the
euxinoid environment prevailing during black shale
deposition. The intimate relation between massive sul-
phides and black shales points to an origin of massive
sulphides by precipitation and replacement within black
shale sediments. These would have acted both as phys-
ical and chemical barriers during sulphide deposition.
Hydrothermal activity started during black shale depo-
sition, triggered by a rise in thermal gradient due to the
ascent of basic magmas. We suggest a three-stage genetic
model: (1) low temperature, di€use ¯uid ¯ow, producing
pyrite-bearing lenses and disseminations interbedded
with black shales; locally, channelized high-T ¯uid ¯ow
occurs; (2) hydrothermal cyclic activity at a low to in-
termediate temperature, producing most of the pyritic
and polymetallic ores, and (3) a late high-temperature
phase, yielding Cu-rich and Bi-bearing mineralization,
mainly in the stockwork zone.
Resumen (translated by E. Pascual) El distrito minero
de AznalcoÂllar esta situado en el extremo sureste de la
Faja PirõÂ tica IbeÂrica (IPB). Muestra rasgos geoloÂgicos
complejos que pueden ayudar a comprender la geologõÂ a
y la metalogenia de toda la IPB. El distrito abarca va-
rios depoÂsitos minerales con reservas totales de maÂs de
130 Mt de sulfuros masivos. Las leyes medias son de
alrededor de 3,6% de Zn, 2% de Pb, 0,4% de Cu y
65 ppm de Ag. TambieÂn se ha explotado una minera-
lizacioÂn de stockwork con una ley de 0,6% de Cu y
30 Mt. Entre los materiales que a¯oran en el distrito de
AznalcoÂllar aparecen rocas volcaÂnicas y detrõÂ ticas de las
tres unidades estratigra®cas principales descritas en la
IPB: grupo de ®litas y cuarcitas (PQ), complejo vul-
canosedimentario (VSC) y grupo Culm. En el VSC se
pueden distinguir dos secuencias. La Secuencia Sur (SS)
es principalmente detrõÂ tica, y como rasgo peculiar in-
cluye pillow-lavas basaÂlticas y niveles calizos de aguas
someras, estas uÂltimas hacia la parte superior de la
secuencia. En cambio, la secuencia de AznalcoÂllar-Los
Frailes (AFS) contiene gran cantidad de rocas volcaÂni-
cas, relacionadas con los dos principales episodios vol-
caÂnicos en la IPB. Estos diferentes rasgos estratigra®cos
indican una distinta evolucioÂn paleogeogra®ca durante
el DevoÂnico superior y el CarbonõÂ fero inferior. Los
sulfuros masivos aparecen asociados a pizarras negras
depositadas sobre el primer volcanismo feÂlsico (VA1)
Los datos de palinomorfos obtenidos de este horizonte
de pizarras negras indican una edad Estruniense para
los sulfuros masivos, y en consecuencia una edad de-
voÂnica superior para el primer ciclo volcaÂnico VA1. Los
datos de campo y texturales de las rocas volcaÂnicas
sugieren una evolucioÂn desde un ambiente de depoÂsito
subaeÂreo (VA1) hasta condiciones hidroclaÂsticas sub-
volcaÂnicas para el VA2. Esta evolucioÂn puede relacio-
narse con la compartimentacioÂn y profundizacioÂn cre-
ciente de la cuenca sedimentaria, tal como lo sugieren
tambieÂn los cambios en los sedimentos asociados, in-
cluidas las pizarras negras y los sulfuros masivos. Pese a
los cambios en el tipo de vulcanismo, eÂste corresponde a
una composicioÂn de dacõÂ tica a riolõÂ tica, tanto en las
series piroclaÂsticas como en las subvolcaÂnicas. El prin-
cipal proceso õÂ gneo que controla la variacioÂn quõÂ mica de
las rocas volcaÂnicas es la cristalizacioÂn fraccionada de
plagioclasa (+accesorios). Este proceso tuvo lugar en
reservorios subsuper®ciales a poca profundidad, y dio
lugar a un rango de composiciones que cubre el rango
total de variacioÂn de la IPB. La orogenia hercõÂ nica
produjo una evolucioÂn estructural compleja, con una
fase mayor de deformacioÂn duÂctil F1 en la que se pro-
dujeron pliegues que evolucionaron a cabalgamientos
por laminacioÂn del ¯anco corto. Estos cabalgamientos
produjeron repeticioÂn tectoÂnica de las mineralizaciones
masivas y de stockwork. En AznalcoÂllar, parte de la
mineralizacioÂn de stockwork cabalga los sulfuros masi-
vos. Las estructuras anteriores son cortadas por grandes
cabalgamientos en reÂgimen fraÂgil y por fallas tardõÂ as de
desgarre. Los rasgos originales de los depoÂsitos de sul-
furos masivos corresponden a mantos extensos con
espesores variables (10 a 100 m), asociados sistemaÂti-
camente con stockworks. La alteracioÂn del muro de los
depoÂsitos muestra una zona clorõÂ tica interna y otra
sericõÂ tica perifeÂrica. TambieÂn tienen lugar procesos de
silici®cacioÂn, carbonatizacioÂn y piritizacioÂn. La altera-
cioÂn hidrotermal debe considerarse como un proceso
multiestadio, que se caracteriza geoquõÂ micamente por
enriquecimiento en Fe, Mg y Co e intenso lixiviado de
alcalinos y Ca. REE, Zr, Y y Hf tambieÂn se movilizan
en las aureolas clorõÂ ticas internas. Tanto en stockworks
como en sulfuros masivos se distinguen tres tipos de
mineralizacioÂn, denominadas pirõÂ tica, polimetaÂlica y
pirõÂ tica rica en Cu. Esta uÂltima es maÂs comuÂn en
stockworks, en tanto que la polimetaÂlica predomina en
los sulfuros masivos. La zonacioÂn de las masas de sul-
furos corresponde aproximadamente a un VHMS tõÂ pi-
co, pero muchas de las zonas alternantes pirõÂ ticas y
polimetaÂlicas estaÂn probablemente relacionadas con la
tectoÂnica. Aunque la secuencia de cristalizacioÂn es
compleja, se pueden distinguir varias asociaciones mi-
nerales, a saber: pirõÂ tica framboidal, pirõÂ tica de alta
temperatura (300 °C), pirõÂ tica coloforme, polimetaÂlica
y una asociacioÂn tardõÂ a rica en cobre de alta tempe-
ratura (350 °C). Los datos de inclusiones ¯uidas sugieren
que los ¯uidos hidrotermales cambiaron continuamente
de temperatura y salinidad, tanto en el tiempo como en
el espacio. Las temperaturas y salinidades maÂs altas
corresponden a las zonas de stockwork maÂs internas y a
los ¯uidos maÂs tardõÂ os. Un anaÂlisis estadõÂ stico de po-
blaciones de las inclusiones ¯uidas senÄala tres estadios

de actividad hidrotermal, a temperaturas bajas
(<200 °C), intermedias (200±300 °C) y altas (300±
400 °C). Los valores de 34S en los sulfuros masivos son
inferiores a los de las mineralizaciones de stockwork, lo
cual sugiere una actividad bacteriana moderada, favo-
recida por un ambiente euxõÂ nico durante el depoÂsito de
las pizarras negras. La õÂ ntima relacioÂn entre eÂstas y los
sulfuros masivos apunta a un origen de estos uÂltimos
por precipitacioÂn y reemplazamiento de las pizarras
negras, que habrõÂ an actuado como barreras, tanto
fõÂ sicas como quõÂ micas, durante el depoÂsito de los
sulfuros. La actividad hidrotermal comenzo durante el
depoÂsito de las pizarras negras, iniciada por un ascenso
del gradiente teÂrmico debido al ascenso de magmas
baÂsicos. Sugerimos un modelo geneÂtico en tres etapas: 1)
CirculacioÂn difusa de ¯uidos a baja temperatura, que
habrõÂ a producido lentejones y diseminaciones de
pirita interestrati®cadas con las pizarras negras.
Localmente, tambieÂn se produjo ¯ujo canalizado a
mayor temperatura; 2) actividad hidrotermal cõÂ clica, a
baja o media temperatura, que produjo la mayor parte
de las mineralizaciones pirõÂ ticas y polimetaÂlicas, y 3)
etapa de alta temperatura, que produjo mineralizaciones
ricas en cobre con bismuto, sobre todo en la zona de
stockwork.
Introduction
The Iberian Pyrite Belt (IPB) is one of the largest mas-
sive sulphide provinces on Earth. At the same time, it
has some peculiarities that make it di€erent from clas-
sical volcanic hosted massive sulphide (VHMS) prov-
inces (SaÂez et al. 1996).
113
Previous works on AznalcoÂllar, by Coullaut et al.
(1975), Canicio et al. (1980), Hofstetter (1980), Her-
naÂndez Enrile (1981), Sierra (1984a and 1984b), Sierra
et al. (1985), show important discrepancies in the inter-
pretation of local geology, either due to the tectonic
complexity, the lack or discontinuity of reference hori-
zons or the misinterpretations of the signi®cance of Vi-
sean carbonate rocks. The AznalcoÂllar mining area is
located near the SE limit of the IPB, about 25 km from
Sevilla (Fig. 1). As in other areas in the IPB, ®rst mining
activities began prior to the Roman period, and con-
tinued until the present with some breaks. The original
AznalcoÂllar and the new Los Frailes open pits are cur-
rently managed by BOLIDEN-APIRSA. A number of
old smaller underground mines are known in the area,
including Caridad, CuchichoÂn and Zarcita (Fig. 2). In
total, a reserve of about 43 Mt of massive sulphides has
been estimated at AznalcoÂllar, with average ore grades
of 0.44% Cu, 1.77% Pb, 3.33% Zn and 67 ppm Ag. A
single sulphide body, which has not been completely
explored at depth, has been found at Los Frailes. The
available data indicate it comprises more than 70 Mt,
with average grades of 0.35% Cu, 2.21% Pb, 3.87% Zn
and 63 ppm Ag. Data from Caridad, Zarcita and Cu-
chichoÂn indicate similar grades. Stockwork mineraliza-
tions occur in all of these deposits, although they are
economic only in AznalcoÂllar, where it makes a total
reserve of 30 Mt with an average content of 0.58% Cu,
0.40% Zn and 10 ppm Ag.
Fig. 1 Geological map of the Iberian Pyrite Belt (modi®ed from
Carvalho et al. 1976), indicating location of the AznalcoÂllar district
114
Geological setting
The stratigraphic succession of the AznalcoÂllar district includes the
main lithostratigraphic units recognized in the IPB: the Phyllite-
Quartzite Group (PQ), the Volcano-Sedimentary Complex (VSC)
and the Culm Group (van den Boogaard 1967; Strauss 1970;
Schermerhorn 1971; LeÂcolle 1977; Routhier et al. 1978). Regional
rocks were folded during the Variscan Orogeny, showing features
of thin-skinned deformation (Silva et al. 1990), and were subjected
to very low- to low-degree regional metamorphism (MunhaÁ 1990).
Rocks of the PQ group and the VSC were a€ected by pre-Variscan
regional hydrothermal alteration (MunhaÁ 1990; Barriga 1990).
Papers by Schermerhorn (1971), LeÂcolle (1977), Routhier et al.
(1978), Barriga (1990), SaÂez and AlmodoÂvar (1993), SaÂez et al.
(1996) and Leistel et al. (this volume) contain additional informa-
tion on the IPB regional geology.
Lithostratigraphic sequence
The Phyllite-Quartzite Group mainly crops out north of
the AznalcoÂllar mines. It generally has tectonized con-
tacts with the overlying VSC, but a gradual stratigraphic
transition between PQ and VSC is observed in some
locations in the area. Characteristic lithofacies include
alternating layers of Devonian shales and sandstones.
Near-shore sedimentary structures suggest a shallow
marine environment, although slightly deeper than in
other regions in the IPB (Moreno and SaÂez 1990;
Moreno et al. 1996). On the other hand, only some
outcrops and drill cores in the area of Los Frailes have
been identi®ed as the Culm Group. At a regional scale,
this corresponds in the IPB to the postvolcanic, detrital
¯ysch formation, including the pelitic levels that sepa-
rate this from the VSC (Moreno 1993).
Fig. 2 Geological map of the AznalcoÂllar district
The Volcanic Sedimentary Complex is represented in
the AznalcoÂllar area by two di€erent volcano-sedimen-
tary successions: the Southern sequence (SS) and the
AznalcoÂllar-Los Frailes sequence (AFS). The former,
located outside the mineralized areas (Fig. 2), is essen-
tially pelitic, containing some carbonate rocks and basic
volcanites. The dominant pelitic rocks are sericitic slates,
composed by ®ne-grained phyllosilicates, quartz and
rare feldspar grains.Volcanic rocks are ma®c pillow la-
vas and ®ne-grained felsic tu€s, all interbedded within
the pelitic sequence. Carbonate rocks have detrital tex-
tures with fragments of crinoids, corals and felsic vol-
canic rocks, which are very similar in texture to
porphyritic dacites of the AFS. The AznalcoÂllar-Los
Frailes sequence comprises the VSC cropping out in
most of the studied area and contains the massive sul-
phide mineralizations (Fig. 2). The AznalcoÂllar-Los
Frailes sequence is subdivided in two felsic sub-units,
known as the Lower and Upper sequences. These may
be correlated with the two main volcanic episodes V1
and V2 that can be distinguished in the VSC at a regional
scale. From bottom to top, the following terms have
been distinguished in the Lower sequence: crystalline
tu€s, vitric tu€s and black shales with the massive sul-
phides.
Crystalline tu€s are the oldest volcanic deposits in the
VSC. They are characterized by abundant fragments of
coarse, embayed quartz phenocrysts, together with mi-
nor plagioclase. Biotite phenocrysts are rare and more
often indistinguishable. Altered sericitic fragments are
interpreted as minor glass shards. The matrix is com-

posed of variable amounts of sericite, chlorite and very
®ne-grained detritic fragments. No internal depositional
ordering, in either composition or grain size, has been
observed.
Vitric tu€s occur either intercalated with, or over-
lying crystalline tu€s, with a maximum thickness of
about 25 m. They comprise heterogeneous pyroclastics
containing vitric fragments with delicate cuspate bor-
ders (indicating no post-volcanic reworking), quartz
and plagioclase crystals, as well as lithic fragments up
to 10 cm in diameter, within a ®ne±grained matrix.
The unit shows no internal structure, but the grain size
of vitric (pumice) fragments increases towards the top
of the sequence, suggesting formation during a single
volcanic event, which increased in energy through
time. Vitric fragments are of two types: chlorite- and
sericite-rich. The former must be related to a more
``ma®c'' original composition, whereas the latter were
probably more feldspathic in origin. The lithic frag-
ments are dacitic with dominantly plagioclase (An60),
quartz and biotite phenocrysts embedded in a very
®ne-grained groundmass, very often showing perlitic
cracks. Despite the actual microgranular texture, these
fragments were glass-rich in origin. Transition to
overlying black shales is marked by epiclastic and
tutic rocks.
Black shales, very similar to those outcropping in
other areas of the IPB, are the host rocks of massive
sulphides. They are dark grey to black, related to a high
content in organic matter. In AznalcoÂllar, black shales
have been dated as late Devonian (Strunian) by pal-
ynomorph study (Pereira et al. 1996), which permits a
Devonian age to be assigned to all of the underlying
volcanic deposits in the area. Black shales show strong
variations in thickness, which is at its minimum in the
immediate vicinity of sulphide masses.
Regarding the Upper sequence, the following litholo-
gies can be distinguished: dacite porphyries, purple
tutes and felsic epiclastites.
Dacite porphyries are massive rocks composed of
albite, quartz and biotite ‹ amphibole (‹pyroxene)
phenocrysts in a massive or microlitic groundmass.
Hydroclastic structures are conspicuous towards the top
of the package where dacite porphyries intrude the
overlying purple tutes. Therefore, the age of dacites
must be slightly younger.
Purple tutes correspond to a reference stratigraphic
level, cropping out in many other areas in the IPB and
commonly known as purple slates. These separates the
second and third volcanic felsic episodes (V2 and V3). In
the AznalcoÂllar area, they are ®ne-grained tu€s and
tutes including hematitic jasper lenses.
Felsic epiclastites make the top of the VSC sequence.
They mostly consist of volcanoclastic rocks, containing
fragments of most of the rock types described. Dacitic
porphyry fragments predominate, and jaspers and
other sedimentary fragments (including massive sul-
phides) are common. Some rocks exhibit textures sim-
ilar to true pyroclastic rocks, suggesting that some
115
volcanic activity persisted at the end of the sequence.
The uppermost part of the epiclastic sequence grades
into pelitic rocks.
Rhyolitic lavas are common as dykes and domes, in-
truding into several di€erent parts of the stratigraphic
column. They are the youngest acid rocks in the Az-
nalcoÂllar area and cut the upper epiclastic sequence, in
addition showing hydroclastic interaction with these
volcanoclastic rocks.
Subvolcanic basic rocks occur only in one point in this
area, although they are described with some detail in
previous works in areas presently covered by mine dumps
(Coullaut et al. 1975; Hofstetter 1980). They are massive
and foliated diabases that cut PQ rocks and are highly
altered, with relics of augitic clinopyroxene, secondary
albite, chlorite, titanite, epidote and carbonates. Clino-
pyroxene, studied in thin sections obtained from pre-
vious studies (Simancas 1983), exhibits features
suggesting signi®cant Ti content. This, along with some
geochemical indications in basaltic lavas, suggests that
basalts are mildly alkaline, as has been recognized in
other areas of the IPB (MunhaÁ 1983; FernaÂndez-MartõÂ n
et al. 1996). They produce contact metamorphism in their
host rocks. Although their age is doubtful in the studied
area, basic rocks showing a similar position have been
assigned to the ®rst VB1 volcanic basic episode at a re-
gional scale (SaÂez and AlmodoÂvar 1993; SaÂez et al. 1996).
Relationships and signi®cance
of the two VSC sequences
The relationship between SS and AFS is a major prob-
lem, that cannot be solved directly as no normal contact
occurs between them.This contact is either tectonic or
covered by Tertiary sedimentary rocks. Some relations,
however, can be deduced from geological data, espe-
cially from carbonate horizons and volcanogenic rocks
found in the SS. Carbonate rocks contain dacitic frag-
ments similar to the porphyritic dacites in the AFS. It
can be inferred, therefore, that these carbonate lenses are
younger than the purple tutes. This is supported by
palaeontological dating by Hofstetter et al. (1979), that
assign them to the upper part of lower Carboniferous.
On the other hand, the acid vulcanites found in the SS
correspond to some tutic horizons, interpreted as
televolcanic products related to the volcanic activity in
the AFS.
Both sequences could result from synchronous pro-
cesses in a di€erent geological environment: the SS
would have been located far from the volcanic centres,
evolving over some time on a carbonate platform. In
contrast, the AFS would correspond to a strongly sub-
siding area that rapidly evolved from shallow or sub-
aerial volcanism to a much deeper environment in which
massive sulphide deposition and hydroclastic phenome-
na occurred. The sedimentological information suggests
that the development of two sub-basins should have
been separated by a major tectonic limit, probably a
116
fracture, at the end of the Devonian, coinciding with the
®rst AFS volcanic episode.
Structure of the AznalcoÂllar area
Deformation and structure are similar to those in other
areas in the IPB (GonzaÂlez Clavijo et al. 1994; Silva et al.
1990). Three phases of deformation are noted here, with
the initial phase responsible for all the main structures.
The general tectonic style is thin-skinned, with asym-
metric folds verging southwards and thrusts and pene-
trative foliation usually parallel to the axial plane of
major folds. The following structural interpretation
draws from the works of Coullaut et al. (1975), IGME
(1978), Hofstetter (1980), HernaÂndez Enrile (1981) and
Simancas (1976, 1983), as well as new information ob-
tained from mine works and drill cores. Large thrust
faults are prominent in the area, and divide several
major structural blocks, which contain minor structures
such as folds and faults (Figs. 3±5).
The ®rst Hercynian phase (F1)
This produced the main structures in the AznalcoÂllar
region. It can be subdivided into two subphases, repre-
senting an evolution from folding and S1 genesis to
thrust generation due to lamination of short ¯anks.
Deformation is essentially ductile, producing asymmet-
ric folds. These tend to be isoclinal, with limb thickening
and common lamination of short ¯anks. They verge
south with horizontal or slightly plunging axes (up to
30), and can be ascribed to the Ic category according to
Ramsay (1967). F1 folds occur at all scales, but later
phases have largely obliterated large-scale folds.
Most rocks show a planar fabric (S1). In slaty mate-
rials, foliation is marked by phyllosilicate preferred
orientation, corresponding to a ``slaty cleavage'' or a
``®ne continuous cleavage'', according to Twiss and
Moores (1992). In more competent rocks, foliation
corresponds to a ``rough foliation'' (Twiss and Moores
1992). The general cleavage orientation is 100±110°E/
50±70°N, with minor variations attributable to later
deformation phases. Intersection lineations S0/S1 and
fold axes are found to be related to F1. Stretching
lineations are also marked locally by tiny, deformed
phyllosilicate crystals.
Inverse faults and thrusts represent the evolution of
®rst phase folds from a ductile to a brittle regime. Earlier
faults are produced by the collapse of short limbs of the
folds. They are parallel to the foliation, and locally
contain an extensional crenulation foliation. This ex-
tensional foliation has S/C fabrics locally, with kine-
matic markers that indicate ductile deformation. These
inverse faults were responsible for overthrusting of
stockwork-type mineralizations onto massive sulphide
deposits. These structures are cut by large overthrusts
(out of phase), that generate cataclastic rocks. Semi-
ductile behaviour is rarely observed, and then only in
Fig. 3 Detailed map of the AznalcoÂllar open pit

shaly rocks. These overthrusts have a WNW-ESE trend
and dip 30°±45°N.
The second Hercynian deformation phase (F2)
This is limited in the AznalcoÂllar district. It produced
gentle folds of the main F1 foliation, with vertical, NS
Fig. 5 Cross section (as deduced from drill hole observations)
showing the structure of the Los Frailes orebody
117
Fig. 4 Cross section showing the structural interpretation of the
AznalcoÂllar area
axial planes. Two sets of faults, corresponding to late-
Hercynian fracturing phases, are observed. Some have
o€sets of hundreds of metres, although displacements
are usually much smaller. An E-W set and a conjugate
NNW/SSE and NE/SW system have been distinguished,
from which the NNW/SSE faults are more common.
Structure of the AznalcoÂllar open pit mine
The structural complexity of the eastern limit of the IPB
is evident in the AznalcoÂllar open pit (see Fig. 4), where
the multiplicity of thrust structures produces several
repetitions of the massive sulphide horizon, as well as
overthrusting of stockwork mineralization on massive
sulphides. This geometric relation between massive sul-
phides and the feeding stockwork, that has previously
led to di€erent interpretations (Hofstetter et al. 1979;
Simancas and RodrõÂ guez-Gordillo 1981; Sierra 1984a;
Sierra et al. 1985), is explained in terms of thrusting of
true stockwork mineralization over the massive sul-
phides (Pons et al. 1993).
Three structural units, named Crispinejo, Central and
Southern, are distinguishable in the AznalcoÂllar open
118
pit. The Crispinejo Unit occupies the northern part of the
open pit, and is limited by a late thrust obliquely cutting
the F1 structures (the Crispinejo thrust). It comprises
dacitic porphyries and epiclastic rocks related to the
upper felsic sequence. Only minor black shales and as-
sociated pyrite disseminations occur in the NW part of
the unit. Fault rocks related to the limiting thrust show
brittle deformation. The Central Unit is bounded by two
major thrusts, and has a highly complex internal struc-
ture. It contains all the sulphide and stockwork masses
exploited in AznalcoÂllar. Several minor tectonic blocks,
related to F1 inverse faults, can be distinguished within
this unit, in which massive sulphide deposits are tec-
tonically repeated. The Southern Unit is mostly covered
by Neogene material, and it comprises rocks belonging
to the Southern stratigraphic sequence described al-
ready. Most rocks are ®ne-grained and show a pene-
trative foliation, locally a€ected by extensional
crenulation related to shear zones. These could be linked
to the second phase (or out of phase) thrusts.
Felsic volcanism
Alteration in the AznalcoÂllar area is a major problem in
the study of volcanic rocks, because it is produced by
di€erent events and at di€erent stages during the rock
history. Apart from possible changes in the original rock
composition that could have been caused by magma-
sediment interaction and mixing of detritic rocks and
®ne-grained volcanic fragments, two major alteration
processes can be distinguished in the area, namely re-
gional and focused hydrothermal alteration. The latter
process is clearly restricted to the footwall mineraliza-
tions, whereas regional alteration, which is not related to
massive sulphides, a€ects all of the igneous rocks in the
area, and the IPB. Regional hydrothermal alteration
(MunhaÁ 1980; MunhaÁ et al. 1986; Barriga 1990) includes
albitization, uralitization/chloritization of ferromagne-
sian phenocrysts, carbonatization, silici®cation, ad-
ularization and sericitization. It is a pervasive process
with the result that none of the studied rocks has com-
pletely retained its original mineral or chemical com-
position. As regional hydrothermal alteration is older
than focused hydrothermal haloes, it cannot be related
to regional metamorphism. Some suggestions about the
origin of regional alteration have been proposed by SaÂez
et al. (1996).
In these circumstances, textures and modal pheno-
cryst composition are the main criteria in petrologic
classi®cation, as they indicate the nature of the mineral
phases with which magmas were saturated, but not their
primitive chemical composition. Whole-rock chemical
data have been used in addition, but due to the com-
plexities of all of these processes, chemical criteria must
be considered with caution, especially if based on highly
mobile elements.
Felsic volcanism is represented by two successive se-
quences with contrasting genesis, separated by the sed-
imentary horizons with which massive sulphides are
associated. The ®rst one consists mainly of pyroclastic
rocks, whereas the second is hydroclastic subvolcanic.
Pyroclastic volcanism is widely represented by crys-
talline tu€s, vitric tu€s and associated tutes, although
most of the signi®cant petrologic information has been
yielded by vitric tu€s. The lack of sedimentary struc-
tures, the extremely poor degree of sorting in the whole
deposit, and the coexistence of vitric clasts of contrasting
composition, suggest that vitric tu€s were erupted dur-
ing a single volcanic episode, possibly as an ignimbrite
(sensu Sparks et al. 1973). Similar cases have been re-
ported in recent volcanic deposits (Whitney et al. 1988),
as being related to the zoning of a felsic magma cham-
ber, produced by the input of ma®c magma in its lower
part. From the chemical data, a genetic link between the
di€erent types of fragments in the vitric tu€ may be
deduced, but the more ma®c, chlorite-rich juvenile
fragments show no chemical similarity with basaltic
rocks in the AznalcoÂllar area (Figs. 6A, 7) (Pascual et al.
1994). Therefore, we tentatively suggest that the more
probable mechanisms to have produced zoning in the
magma chamber could have been either fractional
crystallization or di€usion (sensu Hildreth 1981). The
volcanic episode itself is interpreted to have been very
shallow marine or most probably subaerial, possibly an
ignimbritic episode following a volcanic collapse.
Local interbedding of vitric and crystalline tu€s
suggests that both pyroclastic rock types are coeval.
However, crystalline tu€s are commonly overlain by
vitric ones. Chemical data indicate an equivalent, dacitic
composition for crystalline and vitric tu€s, with minor
compositional variations. Consequently, we suggest that
both may represent successive volcanic episodes, very
close in time and space. Crystalline tu€s as described are
by far the most common rocks in the ®rst acid volcanic
episode (VA1) at a regional scale. Therefore, these con-
clusions on type of eruption and subaerial character of
vulcanism are probably of general application for large
areas in the IPB.
Hydroclastic subvolcanism in the Upper felsic se-
quence is represented by dacitic porphyries. These are
subvolcanic, massive or brecciated lavas, the latter
formed by interaction with sediments. Hydroclastic
structures are only conspicuous towards the top of the
dacitic bodies, where they interact with purple tutes.
Individual bodies form continuous outcrops with
thicknesses up to 30 m. Given their lateral extent, an
original sill geometry is deduced for subvolcanics.
Dacitic porphyries consist of plagioclase, quartz,
biotite, amphibole and rare pyroxene phenocrysts, em-
bedded in a ®ne-grained, devitri®ed groundmass, in
which feldspar (albite) microliths are apparent. Primary
fabrics are commonly massive or brecciated, in places
giving the appearance of an agglomerate. Very often,
however, these rocks have fragments and ``matrices''
with similar textures and mineral composition. These
``pseudoagglomerates'' probably formed by di€erential
alteration of a fractured, massive porphyritic dacite,
 119

1.4 10
Crystalline and vitric tuffs

Mean rock values/"mean dacite"(Schütz, 1985)

1.2 Dacite porphyries
Rhyolitic lavas
1.0 Chloritic-altered volcanics
Basaltic rocks
0.8
TiO2 %

0.6 1

0.4

0.2
A
0
0 5 10 15 20 25
Al2O3 %
0.1
1.2
Ba Th Nb Ce P Zr Hf Sm Ti Y Yb

1.0 Vitric tuffs Lithic fragments

Mafic juvenile clasts Basaltic rocks

0.8
Felsic juvenile clasts
Eu/Eu*

0.6 Fig. 7 Spider diagram (normalized to the mean value of dacitic

samples reported by SchuÈtz 1985), showing the complementary trace
element spectra for juvenile fragments of contrasted composition and
pyroclastic rocks. The spectrum of a basaltic rock, exhibiting no
0.4 similarity with chloritic fragments, is also shown

B followed by intense deformation, mostly during the ®rst

0.2 F1 Hercynian phase.
0 0.04 0.08 0.12 0.16 0.20 0.24
Dacitic porphyries have a chemical composition very
P2O5
1.2
close to the mean dacite by SchuÈtz (1985) in terms of
major and trace elements. They are also similar to the
VA1 pyroclastic rocks, but they show a more restricted
1.0 compositional range, suggesting that magmatic di€er-
entiation is less ecient in this rock group.
The other subvolcanic acid rocks in the AznalcoÂllar
0.8 area are rhyolites, intruding either the lower sequence or
the epiclastic upper sequence. These rhyolites are glassy,
Eu/Eu*

devitri®ed rocks with rare quartz phenocrysts. Vesicles

0.6 ®lled by chlorite, epidote or quartz are common, in
places aligned with magmatic ¯ow. Groundmass is
composed of ®ne-grained albite and quartz. Intrusive
0.4 rhyolitic sills also interact in places with the surrounding
sediments, producing vesiculation and ¯ow structures.
C Considering their petrographic and geochemical ho-
0.2 mogeneity, all of the rhyolitic rocks seem to be coeval
0 0.20 0.40
TiO2
0.60 0.80 1.00 and younger than igneous rocks described already.
However, a more complex temporal sequence cannot be
Fig. 6A±C Chemical features of volcanics in the AznalcoÂllar area excluded. For instance, it is possible that a pyroclastic
related to fractional crystallization. A Al2O3 vs TiO2 diagram, note sequence could have been followed by intrusive rhyolite
that chloritized rocks de®ne an Al-poorer parallel trend. Also note domes, prior to the deposition of the massive sulphide
that basic rocks are not related to the trend, discarding mixing as a
major petrogenetic process. B and C: Eu/Eu* versus TiO2 and P2O5, mineralization. A later dacite porphyry sequence could
indicating that Eu anomaly development is related to the di€erenti- have been followed in turn by later rhyolite dykes. This
ation process alternative is interesting in view of the very di€erent
Table 1 Selected chemical analysis of rocks from the AznalcoÂllar district
Chloritized felsic volcanic Basic volcanics Felsic VA1 pyroclastics Felsic VA2 dacitic rocks Rhyolitic rocks
rocks

A34±400 A34±413 A34±416 A58±576 BRT-39 BAS-1 CD-6 BRT-204 BRT-99 BRT-100 BRT-6 A58-361B DAC DAC-1 A34±304 A58±446 A75±207 BRT-1 A58±274 A34±55

%
SiO2 60.70 39.10 35.30 36.90 51.80 56.70 49.70 76.50 64.10 67.70 69.00 74.50 67.70 71.50 61.90 71.20 71.90 74.90 80.70 75.70
Al2O3 6.22 11.80 14.30 12.00 12.70 17.80 15.50 13.70 18.50 16.30 15.30 12.30 13.70 12.90 17.50 13.90 14.80 11.90 10.10 11.90
CaO 0.01 0.12 0.18 0.23 0.10 4.70 7.27 0.13 0.53 0.16 0.54 1.72 3.03 0.84 2.36 1.94 0.69 0.06 0.72 0.82
MgO 2.14 3.81 6.37 6.47 7.31 4.39 2.23 0.69 3.52 2.46 0.86 0.81 0.45 0.50 2.39 0.87 0.70 0.24 0.24 1.68
FeO 20.79 28.79 30.14 28.97 19.44 5.25 7.86 0.79 2.92 4.73 3.52 2.34 3.10 2.74 3.46 2.31 0.49 1.13 1.20 2.58
MnO 0.09 0.22 0.34 0.24 0.22 0.10 0.25 0.01 0.04 0.04 0.10 0.02 0.06 0.06 0.06 0.01 0.02 0.03 0.02 0.06
Na2O 0.18 0.19 0.17 0.02 0.23 6.24 7.37 3.31 1.27 1.28 8.30 4.99 2.90 2.32 4.65 3.73 7.79 1.01 3.24 0.19
K2O 0.02 0.90 0.02 0.24 0.01 0.06 0.03 2.78 3.11 2.65 0.04 0.46 6.25 6.23 2.37 2.96 0.04 8.15 2.28 2.69
TiO2 0.22 0.49 0.65 0.44 0.53 1.23 1.40 0.21 0.33 0.48 0.44 0.34 0.37 0.21 0.50 0.33 0.16 0.12 0.10 0.35
P2O2 0.02 0.11 0.13 0.09 0.09 0.15 0.39 0.03 0.04 0.08 0.09 0.10 0.11 0.05 0.12 0.12 0.02 0.04 0.02 0.07
LOI 7.55 11.3 9.45 11.5 5.55 2.7 5.65 1.65 4 3.7 1 0.65 1.25 1.4 2.85 2.15 0.75 0.65 1.05 3.45
SUM 97.93 96.83 97.05 97.10 97.97 99.32 97.65 99.80 98.36 99.58 99.19 98.23 98.92 98.75 98.16 99.53 98.36 98.24 99.67 99.49
ppm
Ni 4 8 5 7 13 39 36 2 9 18 6 5 9 5 11 3 2 2 3 4
Co 78 95 45 17 55 16 16 3 3 3 2 4 1 10 2 6
V 49 103 139 56 110 176 252 5 27 58 43 16 53 7 61 41 3 39
Cr 24 59 46 110 69 210 89 47 85 89 26 200 190 260 16 63 120 77 190 24
Sc 6 11 14 8 11 23 20 9 8 12 8 6 7 9 9 6 4 4 3 10
Zn 375 135 234 276 477 58 69 14 50 138 831 34 37 36 41 46 40 135 17 38
Cu 1020 5770 649 18.5 1070 20.2 41.7 6.9 12.9 23.6 1.3 24.9 15.7 8.5 6.8 2 1.8 3.5 9.5 9.5
Rb 7 47 14 5 113 160 125 9 19 104 140 65 89 5 170 100 88
Sr 5 6 2 3 62 172 317 72 164 173 111 246 378 17 424 151 218 58 76 17
Y 4 9 13 23 21 26 13 50 47 49 83 25 37 64 12 24 85 62 49 37
Zr 56 99 100 117 120 127 153 213 323 252 159 133 156 203 181 129 261 188 168 142
Hf 1.7 2.8 3.3 3.9 3.7 3.1 2.2 6.5 12 7.6 4.7 2.9 4.6 6.8 4.9 3.5 8.8 6.8 6 4.5
Nb 3 8 7 4 13 9 14 13 7 9 12 11 14 8 10 8 9 10
Sn 17 27 19 33 14 12 17 11 17 7 9 10 13 15 12 18 14 9 14
Ba 99 240 99 64 111 120 162 437 1110 512 100 145 968 538 539 407 41 845 486 671
La 8.2 13.6 19.7 24.7 8.1 8.4 11.4 28.7 40 45.2 25.6 41.4 23.6 27.6 25.3 21 47.4 55.3 43.3 25.4
Ce 16.1 27.7 40.1 52.7 18.9 19.9 26.3 63.2 91.3 101 45.9 80 50.9 60.9 54.8 42.5 103 107 88.9 57.4
Pr 1.8 3.2 4.6 5.8 2.3 2.5 3.5 7.9 10.3 10.8 5 9.5 5.8 7.1 6.2 4.9 12.1 12.3 10.5 6.6
Nd 7 12.5 18.1 22.2 9.8 11.4 15.7 31.8 38.2 42.2 19.8 36 21.5 28.5 23.2 18.3 47.3 49 40.5 26.8
Sm 1.5 2.7 3.9 5 2.4 3.3 4.1 8.2 9.1 9.6 4.7 7.9 4.5 7.1 5 4.1 12 10.6 9.9 6.6
Eu 0.73 0.78 0.8 0.81 0.39 1.14 1.64 1.3 1.23 1.84 0.98 1.22 1.31 1.18 1.38 1.02 1.07 1.34 0.9 1.26
Gd 1.4 2.7 3.8 4.7 3 3.1 4 8.4 8.6 91 6.4 6.4 4.2 6.9 4.5 4 11.3 9.9 9 6.2
Tb 0.2 0.4 0.6 0.5 0.8 0.6 0.7 1.5 1.6 1.5 1.1 1 0.7 1.3 0.7 0.7 2.1 1.6 1.4 1.1
Dy 1.1 2.4 3.3 4.3 5.3 3.5 3.9 9.8 9.8 8.3 6.8 6.2 3.8 8.2 3.8 4.4 14.1 8.7 8.9 6.5
Ho 0.2 0.43 0.6 0.73 1.2 0.72 0.8 1.97 1.95 164 1.54 1.17 0.74 1.73 0.65 0.92 2.94 1.49 1.83 1.26
Er 0.6 1.2 1.8 2.5 3.4 2 2.2 5.8 5.5 4.7 3.9 3.5 2.2 5 2 2.9 8.4 4.3 5.1 3.6
Tm 0.1 0.2 0.2 0.2 0.5 0.3 0.3 0.9 0.8 0.7 0.5 0.5 0.3 0.8 0.3 0.5 1.3 0.6 0.8 0.5
Yb 0.5 1.2 1.6 2.2 3 1.7 1.9 5.8 4.8 4.2 2.3 3.5 2.1 4.9 2 3.1 8 3.7 5.2 3.4
Lu 0.08 0.18 0.26 0.18 0.47 0.26 0.3 0.87 0.68 0.65 0.36 0.55 0.32 0.76 0.31 0.55 1.17 0.52 0.72 0.51
Th 2.5 5.6 2.1 7.2 6.4 1.7 0.8 10 38 15 8.8 6.4 11 12 9.5 8 27 22 19 12
U 1.2 2.7 2.6 4.5 4.9 2.5 1 2.9 12.3 3.5 2.5 2.1 4.3 4.5 7.7 2.5 10.9 7.4 6.3 5.4
 121

shape of rhyolitic domes (cutting the lower sequence)
and rhyolitic sills (all cutting the upper sequence), and
the spatial relation of domes with the coarser-grained
vitric tu€s suggest formation from a same volcanic
center.
LREE patterns are quite steep, HREE patterns change
towards a completely ¯at shape with di€erentiation.
Also, a marked Eu anomaly is characteristic of pro-
gressive di€erentiation. Minimum Eu/Eu* values are
systematically found in rhyolites (Fig. 6B, C), but a

Geochemistry

Due to the regional alteration many of the chemical el-

ements analyzed Table 1 cannot be used to evaluate
petrogenetic processes, even in rocks sampled far away
from the hydrothermal VHMS feeder zones, where later,
focused alteration haloes developed. As discussed later,
rocks sampled in these latter areas have no immobile
elements. However, no evidence suggests such a high
mobility degree during regional alteration. Therefore, it
is assumed here that regionally altered rocks, sampled
away from footwall alteration zones, have partly re-
tained their original igneous rock composition (at least
for the less mobile elements). If so, some of their
chemical variation trends partly re¯ect magmatic dif-
ferentiation processes. For instance, strong linear vari-
ations are obtained on Harker diagrams for relatively
immobile elements (e.g., TiO2 versus Al2O3, Fig. 6A). It
is to be emphasized that, in this diagram, chloritized
rocks that are the most strongly altered during focused
hydrothermal processes related to VHMS deposition,
mark a variation trend that is essentially parallel to the
general one. This fact supports the conclusion that the
two observed trends are related to igneous processes,
and that the only e€ect of chloritization has been a loss
of alumina.
Assuming that most of the Al2O3±TiO2 variation is
related to igneous processes, it appears that the chemical
variation of a single rock (the vitric tu€), plus the ig-
neous fragments it contains, covers almost the whole of
the variation found, including all of the analysed dacitic
porphyries. Therefore, this suggests a close chemical
similarity between dacitic rocks of the Lower and Upper
felsic sequences. On the other hand, rhyolitic lavas are
extreme products of fractionation, whereas basic rocks
are unrelated to the general variation trend for felsic
volcanics.
The variation trend on the Al2O3±TiO2 diagram can
be interpreted in terms of magmatic di€erentiation, as
supported by trace-element geochemistry, that shows a
chemical relation between vitric tu€s and their lithic and
vitric fragments in terms of incompatible elements
(Fig. 7, Pascual et al. 1994). As mean values for dacitic Fig. 8A, B Chondrite-normalized REE spectra of volcanic rocks in
porphyries are equivalent to those in the tu€s, it is de- the AznalcoÂllar area. A: regional altered volcanics outside the footwall
duced that parental magma compositions should have zones. Triangles: dacite rock with no Eu anomaly. Circles with crosses:
dacitic rock with positive Eu anomaly. Stars: dacitic rocks with
been the same. Di€erentiation processes should have variable degree of HREE ¯attening slope and negative Eu anomaly.
occurred at a level shallow enough to allow the explosive Diamonds: di€erentiated rhyolitic rock. Shaded area: total variation
mixing of fragments of contrasting composition. range for upper and lower sequence volcanics. B: altered volcanics
In addition, REE show two features of the di€eren- from the footwall chlorite zone. Shaded area: total variation range.
Note the depletion with regard to regional rocks. Three individual
tiation process(es). First, a marked HREE enrichment spectra are also shown to make clear that intensely altered volcanics
characterizes the more evolved rocks in the igneous se- can exhibit positive, negative or no Eu anomaly, as well as di€erent
ries, i.e., rhyolites and more evolved dacites. Whereas HREE slopes
122

100 100

10 10
Co/Ni

Co/Ni
1 1

A B
0 0
10 100 1 10
Ce (ppm) Sm (ppm)
100 100

10 10
Co/Ni

Co/Ni

1 1

C D
0 0
0 1 10 0 1 10
Eu (ppm) Tb (ppm)
100

10
Co/Ni

Fig. 9A±E Selected variation diagrams of REE versus the Co/Ni

ratio. Note the depletion for any of the elements shown with Co/Ni
increase. Asterisks: footwall chlorite zone rocks. Stars: footwall
E sericite zone rocks. Triangles: regional subvolcanics felsic rocks.
0 Diamonds: regional pyroclastic felsic rocks
0 1 10
Yb (ppm)

negative anomaly is found in evolved dacites as well.
Conversely, a positive Eu anomaly has been found in a
plagioclase rich dacite porphyry.
Both the HREE enrichment and the Eu anomaly
correlate between each other and with the Ti or P vari-
ation (Fig. 6B, C). This is consistent with a di€erentia-
tion pattern that can be distinguished from alteration-
related chemical variations. We suggest that fractional
crystallization, with separation of plagioclase + bioti-
te + apatite, can account for the chemical variations
found.
Figure 8 shows REE pro®les for di€erent regionally
altered volcanic types, compared with those from vol-
canics from the chlorite footwall zone in the AznalcoÂllar
VHMS. First, Eu anomalies are related to di€erentia-
tion, not to the intensity of the VHMS-related alteration
processes. Both the ¯attening of the HREE pro®les and
the Eu-anomaly are progressively more marked in the
rhyolithic rocks, whereas these e€ects are not charac-
teristic of intensely chloritized rocks. In fact, the e€ect of
intense footwall alteration is a general REE depletion.
Even chloritized rocks have REE patterns parallel to
those in the regional rocks, indicating that hydrothermal
circulation had no e€ect on the La/Yb or Eu/Eu* ratios.
This is also supported by the depletion in any REE el-
ements with respect to the Co/Ni ratio (Fig. 9), which is
a good chemical indicator of the alteration intensity, as
shown later.
REE patterns are very similar for the Lower sequence
tu€s and the Upper sequence dacite porphyries, which
supports their mutual chemical anity, also shown by
their (immobile) major element and P contents. There-
fore, the chemical composition of felsic volcanics does
not vary with time, in spite of the major variation in the
character of volcanism occurring between the two epi-
sodes. We conclude that no particular composition of
felsic volcanics is speci®cally related to VHMS deposi-
tion in the AznalcoÂllar area.
Massive sulphide deposits
The study of the ore bodies and associated hydrothermal
alteration zones has been performed on drill cores from
the Los Frailes hidden orebody and Caridad mine, as
well as on surface observations from the AznalcoÂllar
open pit.
Massive sulphide deposits appear to be closely related
to black shales. However, the relative thicknesses of
both materials show a rough inverse relationship, so that
in areas where massive sulphides reach thicknesses up to
90 m black shales are scarce or lacking, and vice versa.
Also, massive sulphides include some lensoid bodies of
black shales which are commonly silici®ed and chloriti-
zed. These facts suggest that massive sulphides were
formed by replacement of organic rich sediments. Sim-
ilar country rock replacement has been shown to occur
in many present-day oceanic hydrothermal systems
(Herzig and Hannington 1995).
123
The original geometry of massive sulphide bodies is
dicult to reconstruct, as their present geometric fea-
tures are largely a consequence of overthrusting and
faulting (Figs. 3, 4 and 5). The original geometric fea-
tures apparently relate to large blankets with variable
thickness, covering at least a 8 to 10 km2 zone corre-
sponding to the massive sulphide bodies of AznalcoÂllar,
CuchichoÂn, Caridad and Los Frailes. These blankets
would have overlain stratigraphically controlled stock-
works or stringer mineralizations, with little vertical
extent, where ore minerals occurred mostly following a
network of fractures and previous S0 surfaces. These
cross-cutting mineralizations, which may look somewhat
stratabound, developed mainly on vitric and crystalline
tu€s, and to a lesser extent on black shales.
Hydrothermal alteration
Footwall rock alteration in the AznalcoÂllar district ex-
hibits a roughly concentric zonation, with an inner
chloritic zone and a peripheral sericitic zone, as in many
other deposits in the IPB (Carvalho 1976; Plimer and
Carvalho 1982; Barriga 1983, Toscano et al. 1993; SaÂez
et al. 1996). The chloritic zone is characterized by ex-
treme leaching of Ca, Na and K and enrichment in Al,
Fe and Mg, whereas in the outer, sericitic zone leaching
of Na and Ca is accompanied by a signi®cant enrich-
ment in K and Al. Silici®cation, sulphidization and
carbonatization are common in both alteration zones.
6
Regional chlorite
Stockwork chlorite
0.8
4
Fe(tot.)
Fe/(Fe+Mg)
2
0.4
0 0
2.0 2.5 3.0 3.5 4.0
Si
Fig. 10 Chlorite compositions on the Hey's diagram, showing the
clear di€erence between regional and stockwork chlorites
124
Paragonite
Regional sericite
Stockwork sericite
Celadonite Moscovite
Fig. 11 Ternary diagram showing regional and hydrothermal sericite
compositions in the AznalcoÂllar area
Alteration is considered a multi-stage process, in
which silici®cation broadly preceeded both sericitization
and chloritization. This complex process produced re-
placement of amphiboles, feldspars, biotite and rock
fragments, as well as rutile precipitation and in®lling of
fractures and other open spaces. Chloritization obliter-
ated most of previous structures, whereas sericitization
mostly a€ected rock matrices and some feldspars.
Regional hydrothermal alteration is marked in the
AznalcoÂllar area by albitization and sericitization. Ad-
ularization is observed in an altered rhyolitic dome un-
derlying massive sulphides in the AznalcoÂllar open pit,
although relationships to other alteration types is un-
5 the inner high-alteration zones, whereas Si/Al decreases
4 Dacites
Vitric tuffs
Vitric + lithic fragments in tuffs
Sericitic alteration
3 Chloritic alteration
Ni (ppm)
2 c
1 interstitial sphalerite; C early marcasite growing in silici®ed black
0 (cs) inclusions, and galena are late interstitial phases; E subidiomor-
0 20 40 60 80
Co (ppm)
Fig. 12 Ni versus Co diagram, showing the contrasted magmatic and
hydrothermal Ni-Co evolution. Chloritic rocks show a marked Co
enrichment with little or no Ni increase, whereas regional and sericitic
rocks, especially considering di€erentiated clast, show the opposite.
Note that equivalent volcanic compositions have been choosen for
comparison (modi®ed from AlmodoÂvar et al. 1995)
500
Vitric tuffs
Dacitic porphyries
400 Sericitic alteration
Chloritic alteration
Massive sulphides
300
Zr ppm
200
100
0
10 100 1000 10000 100000 1000000
Pb + Zn ppm
Fig. 13 Zr versus Pb + Zn diagram, showing both the Zr leaching
during hydrothermal alteration and the Zr concentration in massive
sulphides (modi®ed from AlmodoÂvar et al. 1995)
certain. Regional chloritization only a€ects to Fe-Mg-
rich materials, such as ma®c minerals and clasts.
Hangingwall sericitization has also been observed in the
Los Frailes massive sulphide.
Chlorites from hydrothermal alteration haloes are
Fe-rich, the Fe/Fe + Mg relation varying from 0.7 in
the inner chloritic zone to 0.35±0.20 in regional chlorites
(Fig. 10). Iron content increases progressively towards
in the same direction. These tendencies have been de-
scribed in other VHMS deposits (McLeod and Stanton
1984; Large 1992; Toscano et al. 1993). According to the
chlorite geothermometer of Walshe (1986), chlorite
temperatures range from 240 to 272 °C (Ruiz de Al-
modoÂvar et al. 1994). Sericite compositions correspond
to celadonitic muscovite, similar to those related to re-
Fig. 14 A Framboidal pyrite with intergranular and ®ne rims of
galena; B colloform texture composed by a nucleous of framboidal
pyrite rolled by an interbanding of pyrite, galena and tetrahedrite with
shales included in massive sulphides from Los Frailes orebody; D
early arsenopyrite (asp) crystal, partially replaced by pyrite and
overgrown by colloform pyrite (py), sphalerite (sph), with cassiterite
phic corroded pyrite included in alternating bands of galena and
100
sphalerite; F late idiomorphic arsenopyrite (asp) together with
sphalerite, galena and tetrahedrite ®lling voids in banded pyrite ore;
G electrum (el ) grain associated with tetrahedrite, galena, chalcopyrite
and sphalerite interstitial in a groundmass made of idiomorphic pyrite
crystals; H crushed massive sulphide showing ductil deformation of
sphalerite grains including colloform pyrite fragment and S/C
orientated galena blebs. The long side of the photograph represents
0.7 mm for B and F; 0.35 mm for E and H; 0.175 for A, C and D; and
0.014 mm for G
125
126
gional hydrothermal alteration (Fig. 11), and suggest
reequilibration during regional metamorphism.
The chloritic stockwork rocks are signi®cantly en-
riched in Co with respect to Ni (Fig. 12). Taking the Co/
Ni ratio as an alteration indicator, most of chemical
elements, including REE, Zr, Y and Hf, are mobilized
following characteristic alteration trends (AlmodoÂvar
et al. 1995). Hydrothermal mobility of zirconium is
strongly supported by textural evidence suggesting that
zircon crystals both dissolved and crystallized during
this process. Inclusions of pyrite, rutile, sericite and
apatite, among other mineral phases, are observed
within zircon crystals.
On the other hand, it is apparent that the Zr leached
during hydrothermal alteration precipitated with massive
polymetallic sulphides (Fig. 13). The hydrothermal al-
teration occurred in an environment in which both Zr and
REE dissolved, and eventually precipitated. Dissolution
processes are re¯ected as corroded borders in zircons,
often showing a cut zoning. In turn, zirconium precipi-
tation processes are marked by overgrown processes and
neoformation of zircon crystals (Fig. 15A). Zirconium
mobility has been described previously in F-rich
hydrothermal systems (Rubin et al. 1993), or related to
gold-bearing tourmaline veins (ClaoueÂ-Long et al. 1990;
Kerrick and King 1993).
Mineralogy and zoning
As in other deposits in the IPB, massive sulphide
deposits are characterized by a limited number of major
minerals (pyrite, sphalerite, galena and chalcopyrite),
together with a wide variety of minor species (Strauss
1970; Routhier et al. 1978; GarcõÂ a de Miguel 1990;
Marcoux et al. 1996). Previous data on ore minerals in
AznalcoÂllar can be found in Hofstetter (1980), Sierra
(1984b) and Marcoux et al. (1996).
According to their mineral composition, three ore
types can be distinguished in the area, both in massive
sulphide and stockwork mineralizations: polymetallic,
pyritic and Cu-pyritic (Figs. 14 and 15). Pyrite is the
commonest mineral in all types, showing a wide range of
textures, including framboidal, colloform, replacement,
banded, idiomorphic and recrystallization. The poly-
metallic type (Fig. 14E, G and H, Fig. 15E) is charac-
terized by sphalerite and galena, with minor tetrahedrite,
arsenopyrite, chalcopyrite and other less frequent min-
erals, such as bournonite, boulangerite, stannite and
cassiterite. In turn, Cu-rich associations (Fig. 15E±H)
are characterized by chalcopyrite and Bi-minerals (na-
tive bismuth, bismuthinite, nueldite, Bi-meneghinite,
jaskolskiite). This association is common in the stock-
work zones, but rare in the massive sulphides. Gold has
been found as electrum in polymetallic massive miner-
alizations, associated with tetrahedrite (Fig. 14G), as
well as in Cu-rich stockworks, related to chalcopyrite.
Two mineral assemblages can be distinguished in py-
ritic ores. The low-temperature pyritic association con-
sists of framboidal pyrite (Fig. 14A) with minor
marcasite, commonly replaced by pyrite (Fig. 14C). In
this type, framboidal pyrite exhibits rings with ®ne galena
intergrowths (Fig. 14A). Conversely, high-temperature
ones contain pyrite and pyrrhotite ‹ arsenopyrite
‹ cobaltite, the latter mineral occurring only in stock-
works zones (Fig. 15C and E). The application of ar-
senopyrite geothermometer (Sharp et al. 1985) indicates
temperatures of about 300 °C with log f(s2) of ) 8. Both
pyrrhotite and arsenopyrite are partially replaced by py-
rite (Figs. 14D and 15C). The two types of pyritic asso-
ciations show late in®lling or overgrowth by colloform
pyrite (Fig. 14B), which is the most common textural
feature in massive ores. Sphalerite, galena, tetrahedrite
and idiomorphic arsenopyrite ®ll voids (Fig. 14F) and
replace selective layers of colloform pyrite.
Polymetallic assemblages typically show banding
(Fig. 14E), interlayered with colloform, granular or
framboidal pyrite. The application of the stannite-
sphalerite geothermometer (Nakamura and Shima 1982;
Shimizu and Shikazono 1985) has yielded a temperature
of 279 °C and a f(s2) of )8.5. Chalcopyrite and Bi-
minerals are late phases, indicating a very high temper-
ature close to 400 °C (Marcoux et al. 1996). In these, the
very uncommon mineral nueldite has been found,
having the approximate composition Cu0.8Pb2.0
Bi2.1Sb0.8S6.9. The more abundant Bi-mineral is jas-
kolskiite, which exhibits a tetrahedrite and galena reac-
tion rim, possibly related to a reaction between Bi-
meneghinite and chalcopyrite.
From this description, it is apparent that temporal
sequences of mineral precipitation and recrystallization
or replacement are very complex. Nevertheless, some
cyclic episodes have been identi®ed that may be related
to recurrences in the hydrothermal system. The follow-
ing primary depositional sequence is proposed: (1) py-
ritic framboid association; (2) high-temperature pyrite
association; (3) colloform pyrite and polymetallic sul-
phide associations; and (4) chalcopyrite with minor Bi
minerals. In addition, it must be stressed that many of
the actual fabric patterns were generated after sulphide
c
Fig. 15 A Pyritic stockwork developed on a silici®ed and chloritized
black shale; B petrographic features of a chloritized felsic tu€ in the
AznalcoÂllar stockwork. Small zircon crystals showing pleochroic
haloes as neoformed phases. Silici®cation is manifested by quartz
pseudomorph of a feldspar phenocryst. C Quartz-pyrite vein from the
Los Frailes stockwork. Some of the pyrite grains exhibit pyrrothite
habit; D polymetallic vein with quartz, chlorite, pyrite, sphalerite,
galena and tetrahedrite in silici®ed black shale. AznalcoÂllar stock-
work; E Cu-rich stockwork in AznalcoÂllar, composed of pyrite,
chalcopyrite and sphalerite. Skeletal cobaltite grains (not visible) occur
as inclusions in pyrite; F Cu-rich stockwork with Bi minerals.
Tetrahedrite + galena reactions rims are conspicuous around
jaskolskiite ( j) crystals; Los Frailes stockwork. G Cu-rich stockwork
showing late recrystallization of chalcopyrite, tetrahedrite (t) and
sphalerite; H highly deformed mylonitic bands of chalcopyrite and
®ne-crushed pyrite surround coarse pyrite phenoclast. Graphic scale
on A is in centimetres. The long side of the photograph represents
0.7 mm for D and H; 0.175 for B, C, E, and G and 0.014 mm for F
127
128

> 0.5% Cu > 5% Zn

0.3-0.5% Cu 1.5-5% Zn
< 0.3% Cu < 1.5% Zn

> 3% Pb > 80 ppm Ag

1-3 % Pb 50-80 ppm Ag
< 1% Pb < 50 ppm Ag

> 900 ppm Sb > 0.5% As

500-900 ppm Sb 0.25-0.5% As
< 500 ppm Sb < 0.25% As

0 200 m

deposition, by recrystallization, replacement and void Fig. 16 Cross sections of the Los Frailes orebody, showing metal
®lling. Cataclastic and recrystallization textures related zoning as deduced from drill core data. Note the di€erent distribution
to deformation and metamorphism are also found lo- of Cu-rich and polymetallic sulphides
cally (Figs. 14H and 15H).
Massive sulphide bodies show a banded structure,
with alternating polymetallic and barren pyritic zones.
 129

100 1000

10
100

Sn/Bi
Cu %

10

0.1

ORE TYPES 1
0.01 MS Stock
Polymetallic
Piritic
A Cu-Piritic B
0 0
0.01 0.1 1 10 100 0.01 0.1 1 10 100 1000
Zn+Pb % Zn+Pb/Cu

10000
1000

100

1000
10
Au (ppb)
Sn/Bi

1
100

0.1

C D
0.01 10
0.01 0.1 1 10 100 1000 0.01 0.1 1 10 100 1000
Zn+Pb/Cu Zn+Pb/Cu

In some sections of the Los Frailes deposit, zoning is
roughly similar to that commonly proposed for other
VHMS deposits (see, for instance, Stanton 1955, 1972;
Sangster 1972; Sato 1972; Large 1977; Routhier et al.
1978; Franklin et al. 1981), with the highest copper
content towards the central and lower parts of the
masses and high Zn + Pb concentrations towards the
upper and lateral zones of the bodies (Fig. 16).
Chemical data show di€erential concentrations of
major (Fig. 17A) and some minor elements between the
various ore types of mineralization. Ag, Au, Cd, Sn, Hg,
and Tl are clearly more abundant in polymetallic sam-
ples, whereas Co and Bi are concentrated in Cu-pyritic
and in some pyritic ores (Fig. 17B, C). Strong linear
correlations are obtained for several elements in the
former group, both between each other and with Zn, Pb,
and Sb. A similar distribution is found for Zn, Pb, As,
Sb and Ag in the orebodies (Fig. 16). Tetrahedrite is the
only sulphide phase in which a marked compositional
Fig. 17A±D Selected diagrams showing the contrasted composition
of the distinguished mineralization types: A Cu versus Pb + Zn; B
Sn/Bi versus Zn + Pb/Cu; C Sn/Co versus Zn + Pb/Cu; and D Au
versus Zn + Pb/Cu
variation has been found that can be correlated with
zoning, with higher Ag contents (up to 14 wt.%) asso-
ciated with massive polymetallic ores and lower contents
in stockwork zones.
Au is chie¯y concentrated in the polymetallic ores, but
it is also present in Cu-pyritic ores. Regarding correlation
of the gold content to the Pb + Zn/Cu ratio, Fig. 17D
shows two trends. In massive sulphide hydrothermal
systems, gold is mainly transported as bisulphide com-
plex (Hayashi and Ohmoto 1991; Ohmoto 1996), two
mechanisms of gold precipitation are suggested. In Cu-
pyritic ores, precipitation of gold from bisulphide com-
plexes may occur by destabilization due to oxidation
related to partial boiling or seawater mixing. In poly-
130

metallic ores the destabilization of bisulphide complexes 120

is promoted by a dramatic decrease in the activity of gold Type I A
bisulphide complexes across sulphide-sulphate boun-
dary, near the seawater-massive sulphide interface (Large
et al. 1988; Hannington and Scott 1988).
80

Fluid inclusions

N
Type II
Fluid inclusions occurring within quartz crystals in veins
of the stockwork of the AznalcoÂllar and Los Frailes 40
Type III
have been studied. Primary inclusions, isolated in
growth zones of the quartz crystals, are clearly di€er-
entiated from secondary inclusions, related to fractures
and irregular in shape.
Microthermometric study has been performed with a 0
heating/freezing LINKAMÒ stage, covering a total
100 150 200 250 300 350 400
number of 775 measurements of primary inclusions.
T (°C)
These correspond to eight samples from three di€erent
sectors of the stockwork: deep, intermediate to shallow 200
B
and peripheral zones. In most of samples, various types
of superimposed mineralizations occur. Fluid inclusions
have all very similar textural features, most of them 160
being ellipsoidal and small-sized (5±20 lm). They are
two-phase (L + V), although some three-phase inclu-
sions with halite crystals have also been found. These 120
latter are not considered in the further discussion, as
N

they show evidence for post-formation changes.

Fluid inclusions can be classi®ed into three types,
according to their position in the quartz veins and their
microthermometric data (Fig. 18A and B). Type-I in-
clusions are mostly found close to the selvages in the
quartz veins. They show a temperature homogenization
(Th) from 139 to 214 °C, and salinities from 0.4 to 7.2
wt.% NaCl. Mean salinity values (about 3.8 wt.%
NaCl) are close to those in unmodi®ed seawater (3.2%
wt. NaCl). Type-II inclusions have Th between 203 and
299 °C, with mean values of about 245 °C, and mean
salinities of about 5 wt.% NaCl (1.2 to 8.3 wt.% NaCl).
Some of these inclusions could contain CO2, as shown
by the formation of clathrate during freezing. Finally,
Type-III inclusions are more common in the inner zones
of veins, in most cases as isolated inclusions. They
generally homogenize to a liquid phase with Th ranging
from 306 to 384 °C and salinities between 4.3 and 12.4
wt.% NaCl , with mean values close to 6 wt.% NaCl.
Both the salinities and Th obtained are similar to
those in actual and ancient VHMS (Heaton and Shep-
pard 1977; Spooner 1981; Rona 1984; Von Damm 1990;
Pisutha-Arnond and Ohmoto 1983). In fact, actual
systems have also a large variation range and, in most
cases, two ore mineral assemblages can be distinguished,
one of them at a temperature lower than 300 °C and
other at temperatures between 300 to 400 °C (Herzig
and Hannington 1995). Hydrothermal ¯uid consists es-
sentially of marine water, although in some cases me-
teoric and magmatic ¯uids may be also involved
(Roedder 1984; Rona 1984).
80
40
0
0 3 6 9 12 15
Salinity (wt % NaCl)
Fig. 18A, B Statistical distribution of ¯uid inclusions from the
AznalcoÂllar and Los Frailes stockworks. A temperatures B salinities
From salinity values, the hydrothermal ¯uids can be
interpreted as related to modi®ed marine water, due to a
greater degree of interaction with rocks and also to
water loss by hydration/hydrolysis reactions. In turn, the
lowest salinities can be explained in terms of dilution of
marine water by meteoric (Roedder 1984) or condensa-
tion vapour-rich ¯uids originated by boiling processes
(Rona 1988; Cathles 1993; Humphris et al. 1995). This is
consistent with the interpretation by MunhaÁ et al. (1986)
of deuterium and oxygen isotopic data for ore ¯uids in
the IPB, indicating that they mainly consisted of modi-
®ed seawater.
On the salinity versus Th plot (Fig. 19), it is shown
that salinity and Th increase with depth (i.e., distance
relative to the massive sulphide bottom). Also, temper-
ature and salinity increase from the periphery to the
central parts of the stockwork. The succession of type-I
 131

ships between massive sulphides and hydrothermal

feeder vents. In fact, all of the deposits mentioned have
12 stockwork zones (SaÂez et al. 1996), and should be con-
sidered proximal (sensu Large 1977). The most obvious
3
1 di€erence between the groups described is found in the
2 nature of their respective underlying rocks, as well as in
the redox conditions in which the massive sulphides
Salinity wt. % NaCl

8 formed. In the case of San Dionisio, San Telmo and

other mineralizations classi®ed by Yamamoto et al.
(1993) as proximal, the most signi®cant feature is the
occurrence of oxidized phases (sulphates and oxides)
4 within the massive ores, as well as a dominantly volcanic
substratum. In contrast, a reducing environment is
1 shown by thick black shale horizons. In these reducing
2 conditions, pH and/or fO2 do not signi®cantly a€ect
3 isotopic sulphur fractionation. Recent studies (Velasco
0 et al. 1997) show a good correlation between textural
100 200 300 400 features and sulphur isotope signature on AznalcoÂllar
T (°C) and others massive sulphide deposits from the IPB.
Regarding the origin of sulphur in the AznalcoÂllar
Fig. 19 Th versus salinity diagram of ¯uid inclusions. Note that each district, 34S values of the stockwork zone are consistent
of the ¯uid inclusion populations corresponds to a roughly de®nite with an origin from seawater modi®ed by interaction
position with regard to the deduced original geometry of stockwork
zones and sulphide masses with the underlying volcano-detritic rock pile. However,
the participation of some sulphur derived from disso-
lution of volcanics cannot be discarded. The slight
to type-III inclusions also shows a signi®cant increase of negative 34S increment of massive sulphide samples, with
Th and salinity with time. Variations in these parameters regard to their respective stockworks, may admit very
are consistent with ¯uid mixing processes, suggesting a diverse interpretations. By analogy to other IPB depos-
hydrothermal activity in three stages, at low (<200 °C), its, and according to Hofstetter (1980) and Mitsuno et al.
intermediate (200±300 °C) and high temperatures (1988), we suggest this variation to have been caused by
(300±400 °C). Isothermal increase of salinity values moderate bacterial activity, partly favoured by the eu-
(Fig. 19) in Type III inclusions suggest partial boiling. xinic environment indicated by black shale deposition.

Sulphur isotopes Discussion

New 34S analyses have been performed on separated
mineral phases of massive sulphides and stockworks
from AznalcoÂllar and Los Frailes. The results range
within a )6 to +4.4& interval, with mean values close
to zero. This is consistent with previous data (Mitsuno
et al. 1986, 1988; Hofstetter 1980). Values corresponding
to massive sulphides range from )6.0 to +1.3 &, and
those in Cu-pyritic stockwork fall within the )0.5 to
+4.4 & range. As in other areas in the IPB, heavy
sulphur is preferentially concentrated in stockwork,
whereas massive sulphides tend to concentrate lighter
sulphur. Similar sulphur isotope distributions have been
interpreted elsewhere as indicating sulphur reduced by
bacterial activity during massive sulphide deposition
(Routhier et al. 1978; Kase et al. 1990; Tornos et al. this
volume).
Using the sulphur isotope data, Yamamoto et al.
(1993) included the AznalcoÂllar deposits in the ``inter-
mediate'' group between proximal deposits (e.g., San
Dionisio at Riotinto, San Telmo, La Zarza and Con-
cepcioÂn) and distal deposits (Tharsis and Lousal). This
classi®cation, however, is not consistent if the proximal/
distal criterion is considered as relying on the relation-
Using these data, we propose a geological scenario
during Late Devonian-Carboniferous for AznalcoÂllar.
PQ clastic rocks were formed in a siliciclastic, wave-
dominated platform, its upper part having been dated as
Zone-VI Fammenian (Hofstetter 1980). On the other
hand, Late Devonian times in the IPB are characterized
by tectonic fragmentation and compartmenting of the
platform (Moreno et al. 1996). In the AznalcoÂllar area,
this tectonic unstability may have simultaneously
favoured the initiation of the volcanic activity. The ex-
plosive VA1 volcanism, which is essentially subaerial or
deposited at a very shallow depth (Pascual et al. 1994),
would represent this ®rst volcanism, deposited on the
early PQ platform, to which it grades transitionally.
This volcanic episode was followed by a period of
black shale deposition, including Strunian horizons with
palynomorphs (Pereira et al. 1996). The environments
more favourable to the deposition of these types of
sediments are related to transgression/regression epi-
sodes and tectonic movements (Bitterli 1963; Hallam
and Bradshaw 1979), indicating, in general, an increase
in depth (Vogt 1989). Therefore, and comparing these
conditions with those in which volcanics were deposited,
132
it is deduced that black shales, and hence the spatially
associated massive sulphide deposits, were generated in
euxinic conditions, following a collapse stage in the
basin. This collapse could also account for the genera-
tion of massive sulphides, which need an estimated
minimum depth of about 1500 m to be deposited (Her-
zig and Hannington 1995).
Considering these chronostratigraphic constraints,
the whole of the VA1 felsic episode, the black shales and
the overlying tute horizons would represent a short
time span of about 5 Ma. In spite of this, and consid-
ering the low sedimentation rate estimated for black
shales (Einsele 1992), the time interval that the latter
represent was long enough to discard a direct genetic
relation between the VA1 volcanism and the massive
sulphide deposition.
This compartmentizing of the basin is shown by the
di€erent features of the two stratigraphic sequences
outcropping in the AznalcoÂllar area. The mineralized
sequence evolved in a relatively deep water environment,
in which the volcanic stages subsequent to mineraliza-
tions and to black shales were emplaced as sills, mostly
intruding unconsolidated sediments. Similar relation-
ships have been described in the Riotinto area (Boulter
1993). These volcanic episodes are, at least in part,
younger than the purple slate horizons used in the IPB
as regional marker beds, as they intrude them. It is also
worth noting that, in spite of the sharp variation in the
character of volcanism, the composition of the felsic
Fig. 20A±E Sketch model of the geologic and palaeogeographic
evolution proposed for the AznalcoÂllar mining district. A early
volcanic stage, corresponding to VA1 volcanic activity, prior to the
collapse in the sedimentary basin; B erosion and reworking of volcanic
materials; C basin collapse and black shale deposition in the
AznalcoÂllar sector. Southern area remains in platform conditions.
Basaltic magmas rise and sulphide deposition starts in euxinoid
conditions. Pillow lavas can occur in the southern sector. D Volcanic
VA2 sills intrude the sequence overlying massive sulphides, including
purple slates; E ®nal collapse stage and deposition of the upper
volcano-detritic sequence. All scales are approximate. See also text for
explanation
volcanic rocks does not change with time, which indi-
cates that magma generation was produced by the same
major source.
In contrast, the SS continued to evolve in a much
shallower environment, with the development of a car-
bonate platform during lower Carboniferous, which
yielded conodonts indicating a lower Visean zone
(Hofstetter et al. 1979). Finally, the increasing unsta-
bility in the basin produced the thick, upper volcano-
detritic sequence. Some felsic volcanic activity still
occurred at this time, producing the small rhyolitic
stocks and sills intruding the upper sequence.
A sketch model of this evolution is shown in Fig. 20,
in which massive sulphide generation is linked to the
ascent of basaltic magmas, as is evident in other areas in
the IPB (SaÂez et al. 1996 and in press). Nevertheless, in
the case of AznalcoÂllar this is a tentative assumption, as
no de®nite stratigraphic relation can be observed be-
 133

tween basic rocks and mineralizations. In any case,

massive sulphides can be related neither to the shallow/
subaerial VA1, nor to the VA2 subvolcanic sequence,
which clearly postdates mineralizations.
These latter points are of regional interest, not only in
the AznalcoÂllar area. In fact, the scenario described can
account for a major problem that still remains in the
IPB, that is the number of giant or supergiant deposits,
of which the AznalcoÂllar district is but one example. In
general, it is accepted that direct sulphide precipitation
on the sea¯oor from hydrothermal vents is not a
mechanism ecient enough in the formation of very
large sulphide bodies (Rona 1984; Finlow-Bates 1980;
Lydon 1988), except in systems involving very saline
¯uids, such as in the Red Sea (Mustafa et al. 1984).
However, the ¯uid inclusion data shown do not support
this latter possibility in AznalcoÂllar. Therefore, the only
way to make the process more ecient must be to en-
gage some type of barrier model, as previously suggested
by Barriga (1983) and Barriga and Fyfe (1988), which
suggests that some IPB deposits formed below a colloi-
dal siliceous cap, preventing sulphide dispersion. This
idea has support in the existence of similar barriers in
actual sulphide mounds (Peter and Scott 1988). How-
ever, silica-rich horizons directly overlying massive sul-
phides are rare in the IPB, and have been not observed
in the AznalcoÂllar area.
We suggest that the relationship found in AznalcoÂllar
between massive sulphides and black shales could infer
that the latter acted as both physical and chemical bar-
riers, due to the highly reducing conditions they imply.
Massive sulphides would then form, at least in part, by
precipitation and replacement within black shale sedi-
ments. Regarding this suggestion, it should be consid-
ered that the largest deposits found in actual systems are
related to heavily sedimented ridge environments (Davis
et al. 1992; Herzig and Hannington 1995). In these,
sediments retain crustal heat longer than other non-se- Fig. 21A±C Sketch model for sulphide deposition. A Faulting related
dimented systems and allow sulphide precipitation to basin collapse. Starting of di€use ¯ow and low-T pyritic deposition.
within the sediments that cover the ¯uid surges (Koski B Main stage of pyritic and polymetallic massive sulphide and
1987; Davis et al. 1992). stockworks. C Late high-T stage, related to a closer ascent of basic
magmas, producing Cu-Bi stockworks. All scales are approximate.
In this model, massive sulphides would form mainly See also text for explanation
by precipitation and replacement within black shales,
although some true vents would also exist, especially
near the zones of maximum hydrothermal ¯ow, related rhyolitic compositions, all the compositional varieties
either to partial removing of black shales or to upwelling having been produced from dacitic parental magmas
in®ltration. Accordingly, we suggest the model to have through fractional crystallization processes, and (b) all
evolved in several steps as described later (Fig. 21). of the felsic rocks were produced in two major volcanic
stages without signi®cant changes in chemical compo-
sition, so that no magma source migration occurred with
Conclusions time. Therefore, no particular magma composition of
felsic magmas can be speci®cally considered as ``fertile''
The AznalcoÂllar has several analogies with other regarding massive sulphide mineralizations, or in terms
deposits of the IPB, such as a same general stratigraphic of trace element geochemistry.
sequence, volcanic mineralogy and geochemistry, tec- The new tectonic interpretation has led to the char-
tonic style, alterations and ore mineralogy. Considering acterization of an overthrusted stockwork. This is an
magmatism, and apart from its volcanological/strati- important point, in particular because if this structure is
graphic signi®cance, two points are to be noted in the not recognized, massive sulphide deposits may be mis-
studied area: (a) felsic magmatism ranges from dacitic to interpreted, even denying the existence of a true stock-
134
work zone. It has been shown that in hydrothermal al-
teration, this involves mobility of almost any of the
chemical elements in the system, including REE and Zr.
On the other hand, previous data indicating a higher
temperature during late stages in the hydrothermal
process have been con®rmed by ¯uid inclusion studies,
which in addition may trace the spatial evolution of the
hydrothermal system. The mineralogical sequence now
suggested also di€ers in detail from that previously
proposed. Hydrothermal activity started (Fig. 21A) well
after the end of volcanic VA1 activity and black shale
deposition, triggered by a rise in thermal gradient due to
the ascent of basic magmas. This ®rst phase would have
been dominated by di€use ¯uid ¯ow at a low tempera-
ture, and would have produced pyrite-bearing lenses and
disseminations interbedded with black shales. At some
points, channellized, high-T zones would exist. The
second phase (Fig. 21B) would have been more complex.
During this stage, the hydrothermal system had a cyclic,
episodic activity at a low to intermediate T. This would
be the moment at which most of the sulphide masses and
stringer zones of pyritic and polymetallic composition
formed, mainly by replacement of black shales and
earlier pyritic associations. A third phase (Fig. 21C),
roughly coinciding with a closer ascent of basic magmas,
would have produced the late-stage, Cu-rich mineral-
izations containing Bi. This phase should correlate with
the last phase described by Marcoux et al. (1996) fol-
lowing the model by Large (1992). Accordingly, this
would have produced the migration of polymetallic
sulphides from the inner to the peripheral zones. In the
AznalcoÂllar area, however, there is no evidence to sug-
gest that this migration was signi®cant.
Acknowledgements This study was supported by the ECC contract
BRE2-CT92-0299 and the 4067 Research Group of the Regional
Andalusian Government. The authors thank BOLIDEN-APIRSA
for the ®eld assistance and sampling facilities. Fluid inclusion data
were obtained by M. Toscano in the Department of Geology
(University of Southampton), and we are indebted to R. W. Nesbitt
and S. Roberts for their assistance. We are also grateful for help
from BRGM (Orleans) and University of Oviedo in making EMP
analyses. The manuscript has been greatly improved by the com-
ments and suggestions of two anonymous reviewers and the En-
glish improved by the SGA English-Language Correction Service.
Editorial assistance by E. Marcoux and D. Rickard is also ac-
knowledged with thanks.
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