561

Volume 41 June 2003 Part 3

The Canadian Mineralogist

Vol. 41, pp. 561-579 (2003)

V-RICH MINERALS IN CONTACT-METAMORPHOSED SILURIAN SEDEX

DEPOSITS IN THE POBLET AREA, SOUTHWESTERN CATALONIA, SPAIN

CARLES CANET§
Departamento de Recursos Naturales, Instituto de Geofísica.
Universidad Nacional Autónoma de México, 04510 México, D.F., México

PURA ALFONSO AND JOAN-CARLES MELGAREJO§

Departament de Cristal•lografia, Mineralogia i Dipòsits Minerals.
Universitat de Barcelona, E–08028 Barcelona, Catalonia, Spain

SUSANA JORGE
Departamento de Didácticas Específicas. Facultad de Humanidades y Educación (Educación),
C/ Villadiego s/n, E–09001 Burgos, Spain

ABSTRACT

The Lower Llandoverian metasedimentary rocks of the Prades Mountains, southwestern Catalonia, Spain, consist of
interstratified anorthite-rich beds, chert beds, phosphate beds, sulfide-rich black shale (with mainly pyrrhotite and minor
chalcopyrite), massive sulfide lenses and calc-silicate beds. These metasedimentary rocks are anomalously enriched in V and Cr,
and have disseminated minerals of precious metals: mainly sperrylite and palladian löllingite. The V- and Cr-rich associations are
the result of an isochemical metamorphism of V- and Cr-rich protoliths. The contact metamorphism of V-rich shale produced
metapelitic hornfels with V-rich aluminosilicates and V–Cr oxides. The occurrence of V oxides in apparent equilibrium with V-
rich silicates suggests a limit for the V and Cr contents in these aluminosilicates at the conditions of thermal metamorphism. On
the other hand, metamorphism of anorthite- and V-,Cr-rich sedimentary rocks produced V- and Cr-rich silicates, such as
goldmanite, V-rich amphiboles, V-rich titanite and V-rich allanite.

Keywords: vanadium oxides, vanadium silicates, chromium, sedex, black shale, Silurian, contact metamorphism, Catalonia, Spain.

SOMMAIRE

Les roches métasédimentaires du Silurien Inférieur des montagnes de Prades, dans le sud-ouest de la Catalogne, en Espagne,
contiennent des alternances de couches de roches à anorthite, des cherts, des niveaux à phosphates, des schistes noirs à sulfures
(pyrrhotite surtout, avec chalcopyrite), des sulfures massifs et des calc-silicates. Ces roches métasédimentaires sont très riches en
V et Cr, et elles contiennent des minéraux disséminés de métaux précieux: sperrylite et löllingite palladifère. Ces paragenèses à
V et Cr sont le produit d’un métamorphisme isochimique de protolithes riches en V et Cr. Le métamorphisme de contact d’ardoises

§
E-mail addresses: [email protected], [email protected]
562 THE CANADIAN MINERALOGIST

riches en vanadium a produit des cornéennes à aluminosilicates vanadifères, biotite vanadifère, et des oxydes de V–Cr. La présence
locale des associations d’oxydes et des silicates de V apparemment en équilibre témoignerait d’une limite pour les activités de V
et Cr dans ces silicates aux conditions du métamorphisme de contact. En plus, le métamorphisme de roches riches en anorthite,
V et Cr a mené au développement de silicates de V et Cr, par exemple la goldmanite, les amphiboles vanadifères, la titanite
vanadifère et l’allanite vanadifère.

Mots-clés: oxydes de vanadium, silicates de vanadium, chrome, gisement de type sedex, schistes noirs, Silurien, métamorphisme
de contact, Catalogne, Espagne.

INTRODUCTION (García-López et al. 1990), the occurrence of limestone

olistholiths of these ages within Carboniferous detrital
The Paleozoic series of the Catalonian Coastal series near the Prades Mountains seems to indicate that
Ranges, in northeastern Spain, contains several sedex- limestone sedimentation during the Upper Silurian and
type deposits (Ayora et al. 1990). Similar deposits oc- Early Devonian was also taking place in this area
cur in the Hercynian terranes of the Pyrenées, the Iberian (Melgarejo & Martí 1989).
Massif and the Montagne Noire district in southern The above limestones are followed by a 100-m-thick
France. Most of the reported occurrences occur in Car- sequence of marl interbedded with limestone, corre-
boniferous and Cambrian–Ordovician series, but the sponding to the Gedinnian–Siegenian, and those units
Silurian series also contain several deposits at its base. are overlapped by 80 m of alternating calcarenite and
In some of these Silurian deposits in the Prades Moun- slate of Emsian age, which grade upward into black
tains, near the monastery of Poblet, in the southern part shale with quartzite beds corresponding to Eifelian–
of the Catalonian Coastal Ranges (Fig. 1), Pd and Pt Famennian (up to 200 m thick) (Melgarejo 1992).
minerals related to a V–Cr anomaly have recently been The Carboniferous series unconformably lies above
found (Melgarejo 1992, Melgarejo et al. 1994). In addi- the Silurian and Devonian rocks. In the Prades Moun-
tion to the unusually high contents of precious metals, tains, the base of the Carboniferous series consists of
these metasedimentary rocks contain unusual associa- chert beds (“lidites”). These beds, up to 10 m thick, are
tions of V- and Cr-rich minerals. Our aim in this contri- regionally attributed to the Tournaisian, and they contain
bution is to describe these mineral associations and their several Mn deposits of sedimentary-exhalative affinity
evolution during the geological history of the area. (Melgarejo & Ayora 1992). A thick sequence of detrital
series (up to 2 km), ranging in age from Visean to Lower
GEOLOGY OF THE PRADES MOUNTAINS Westphalian, contains many sedimentary-exhalative
stratiform Pb–Zn–Cu–(Ag) deposits (Melgarejo 1992,
The Prades Mountains are located at the southern Canet 2001).
part of the Catalonian Coastal Ranges (Fig. 1). They The above rocks have been deformed at several
consist of a Hercynian basement unconformably cov- stages during the Hercynian Orogeny. Regional meta-
ered by Mesozoic and Cenozoic series. The basement morphism and deformation took place in the epizone.
consists of Silurian and Devonian series unconformably The main phases of deformation gave NW–SE folds
overlain by Carboniferous rocks, essentially sedimen- with an axial plane dipping toward the northeast; cleav-
tary in origin. age usually is poorly developed, and thrust structures
A stratigraphic profile of the Lower Paleozoic series were formed in the flanks of folds. The Silurian sedi-
from the Southern Catalonian Coastal Ranges is pre- ments (ore-rich sediments and black shales) and the
sented in Figure 2. The early Silurian series starts with Upper Devonian black shales acted as the detachment
a 20-m-thick unit made up of interbeddings of quartzite levels of the Hercynian thrusts. A second phase of de-
and black shale. Above, an ore-bearing unit (up to 30 m formation produced chevron folds trending NW–SE
thick) contains a complex interbedding of various with an axial plane dipping to the southwest. Hercynian
metasedimentary rocks: chert, phosphate, anorthite-rich regional metamorphism in the southwest of Catalonia
beds, calc-silicate beds and sulfide-rich shales. On the attained in the lowest part of the greenschist facies
basis of the graptolite fauna in the black shales, these (Melgarejo 1992).
lowest units have been regionally attributed to the Lower
Llandoverian (Melgarejo 1992).
The intermediate units of the Silurian series essen-
tially consist of 50 m of graptolite-rich black shale, dated
by Ashauer & Teichmuller (1935) as Upper Llando- FIG. 1. Distribution of Silurian stratiform occurrences in the
verian and Wenlockian. In spite of the fact that Catalonian Coastal Ranges, and geological map of the
Ludlovian–Pridolian outcrops (mainly limestones) only northern part of the Prades Mountains. Simplified after
appear in eastern areas of the Catalonian Coastal Ranges Melgarejo (1992).
V-RICH MINERALS IN SEDEX DEPOSITS, SOUTHWESTERN CATALONIA 563
564 THE CANADIAN MINERALOGIST

Late Hercynian granitic rocks, ranging in composi- mainly NW–SE- and NE–SW-trending, cross-cuts the
tion from quartz diorite to leucogranite, intruded all of above granites and the Paleozoic metasedimentary se-
the above series, and produced a contact-metamorphic ries. Scheelite-bearing quartz veins occur into these
aureole up to 500 m wide (Melgarejo 1992, Serra & granites. Fluid inclusions in quartz and scheelite indi-
Enrique 1989). A suite of porphyritic granitic dikes, cate conditions that agree with the epizonal emplace-
ment of these granitic rocks (400°C and 0.8 kbar; Ayora
et al. 1987).
Contact metamorphism produced mineral associa-
tions up to the pyroxene hornfels facies in the proxim-
ity of the granite intrusions. Andalusite poikiloblasts
developed in the Silurian black shale, whereas cordier-
ite was mainly produced in Carboniferous metapelite
and metagreywacke. The occurrence of almandine +
biotite in pelitic hornfels, and of diopside in the calc-
silicate hornfels, suggests temperatures higher than
500°C in the innermost aureole.
A Triassic megasequence (Germanic facies), up to
200 m thick, unconformably overlies the Paleozoic
basement. The boundary between the Prades Mountains
and the Cenozoic Ebro and Prelitoral basins consists of
faults of Alpine age. Some of these faults host low-tem-
perature Ba–F–Pb–Zn–Cu–Ni–Co–Ag veins, as at the
Atrevida mine, the largest Ba deposit in the southwest-
ern Catalonian Coastal Ranges (Melgarejo & Ayora
1985a, b, Canals et al. 1992).

STRUCTURE OF THE SULFIDE-RICH UNITS

FROM THE LOWER SILURIAN SERIES

Many Llandoverian-hosted stratiform deposits and

showings have been discovered on the northern slopes
of Prades Mountains. Usually, the Llandoverian
metasedimentary units acted as detachment horizons of
Hercynian thrusts, and therefore, they crop out as thin
belts approximately parallel to the direction of the folds
and thrusts of the first tectonic phase (N130°). Further-
more, these Llandoverian series were affected by vari-
ous grades of thermal metamorphism. The most
important ore-bearing outcrops in extent, thickness, and
mineral contents are Roca de Ponent, Coma Fosca and
Sant Miquel (Fig. 1).
The stratigraphy of the ore-bearing interval can be
described as an interbedding of roughly monomineralic
beds: anorthite-rich beds, phosphate beds, sulfide-rich
shales, massive sulfides and more unusual calc-silicate
beds. The thickness of individual beds ranges from some
millimeters to several decimeters. An example of the
distribution of these units is provided by the Roca de
Ponent occurrence (Fig. 3).
The contact between these units is sharp and con-
cordant. No evidence of replacements of precursor rocks
has been found. The lateral continuity of the stratiform
mineralization is on the scale of tens or hundreds of
FIG. 2. Stratigraphic profile of the Lower Paleozoic series in meters.
the study area. 1. Grey shale, 2. sulfide-rich shale, 3. black
shale, 4. quartzite, 5. planar lamination, 6. disseminated
pyrite, 7. disseminated pyrrhotite, 8. PGE mineralization,
9. graptolites, 10. cross-lamination.
V-RICH MINERALS IN SEDEX DEPOSITS, SOUTHWESTERN CATALONIA 565

CONDITIONS OF ANALYSIS

The mineral associations have been studied in thin

and polished sections. Scanning electron microscope
(SEM) images and qualitative analyses were produced
using a JEOL scanning electron microscope and a Cam-
bridge Stereoscan 120 at the Serveis Científico-Tècnics
de la Universitat de Barcelona (Spain). The samples
were carefully examined in the back-scattered electron
(BSE) mode, in order to examine the distribution of
minerals containing heavy elements. The minerals were
quantitatively analyzed with a JEOL electron micro-
probe in the energy-dispersion mode at Carleton Uni-
versity, Ottawa, Canada, and by wavelength-dispersion
mode using a CAMECA SX–50 electron microprobe at
the Serveis Científico-Tècnics of the University of
Barcelona, and a CAMEBAX electron microprobe at the
Muséum d’Histoire Naturelle, at Paris. Conditions of
analysis for the ore minerals were: 15 keV, 20 nA (ex-
cept in hydrated silicates), beam diameter of 1 ␮m, and
a counting time of 10 s. We used the following stan-
dards: orthoclase (SiK␣, AlK␣, KK␣), rutile (TiK␣),
chromium oxide (CrK␣), V metal (VK␣), scandium
metal (ScK␣), hematite (FeK␣), rhodonite (MnK␣),
wollastonite (CaK␣), albite (NaK␣), nickel oxide
(NiK␣), barite (BaL␣), silver chloride (ClK␣), corun-
dum (AlK␣), LaB6 (LaL␣), CeO2 (CeL␣), YAG (YL␣),
ThO2 (ThM␣), ZnS (ZnK␣, SK␣), ZrO2 (ZrL␣), and
cobalt metal (CoK␣).

MINERALOGY OF THE ANORTHITE-RICH BEDS

The anorthite-rich fine-grained metasedimentary

rocks are common in all the occurrences, and in the Roca
de Ponent outcrop, they attain up to 1 m in thickness.
They consist mainly of anorthite, with lesser amounts
of quartz and K-feldspar. The proportion of quartz is
very variable, but normally smaller than that of anorth-
ite. K-feldspar is usually associated with quartz. Other
minerals found in anorthite-rich beds are: V-rich titanite
(very common), smaller amounts of V-bearing amphi-
boles, goldmanite [the V-dominant garnet: Ca3(V,Cr,Al,
Fe3+)2(SiO4) 3] and muscovite. Rutile, ilmenite and
coulsonite [V-bearing spinel: (Fe,Mn)(V,Cr)2O4] are
also abundant. Monazite-(Ce), xenotime-(Y), thorianite
and uraninite occur in lesser amounts, generally en-
closed in the above-mentioned minerals as small inclu-
sions (1–5 ␮m in diameter).

FIG. 3. Stratigraphic profile of the Roca de Ponent occur-

rence, indicating the distribution of the mineralization
facies. 1. Massive sulfides, 2. sulfide-rich shale, 3. quartz-
ite, 4. calc-silicate rocks, 5. black shale, 6. chert, 7. apatite-
rich beds, 8. feldspar beds, 9. disseminated sulfides, 10.
arsenopyrite-rich horizon.
566 THE CANADIAN MINERALOGIST

Sulfides are not common in these beds, and pyrrho- Anorthite

tite is the most abundant among them. The pyrrhotite,
usually in anhedral disseminated grains in some cases Anorthite occurs as anhedral grains that generally
included in V-bearing silicates, is locally replaced by display polysynthetic twinning. Usually, these grains
late pyrite (bird’s-eye texture). have an elongate shape, and their c axis defines a linea-
Textural features in these feldspathic beds indicate tion. The grain size, up to 50 ␮m, strongly depends on
that they have been affected by the Hercynian episode the metamorphic grade that affected each occurrence.
of deformation and metamorphism. Tight folds are well Anorthite-rich beds affected by low- to medium-grade
developed, in addition to axial plane cleavage. The an- metamorphism are very fine-grained, but in those af-
orthite-rich beds that are hosted by sulfide-rich schists fected by high-grade contact metamorphism, as in Roca
usually display boudinage structures, indicating a more de Ponent and Coma Fosca occurrences, anorthite de-
rigid behavior than the host sediments during the re- velops a coarse granoblastic texture with quartz and pyr-
gional metamorphism and deformation. Anorthite, rhotite. This metamorphic recrystallization overprints
quartz and most of the above-mentioned minerals dis- the Hercynian foliation (Fig. 4). In addition, anorthite
play annealing and granoblastic textures (with rounded fills open spaces in the necking zones of boudinage
grain-boundaries and triple points) due to the Late structures, thus suggesting a recrystallization during the
Hercynian thermal metamorphism. Hercynian regional metamorphism. The chemical com-
Some anorthite-rich beds are partly replaced by position of anorthite from all the occurrences ranges
white mica. between An96.9 and An99.5, with an average composition
of An98.5.
Quartz
K-feldspar
In some cases, quartz is scarce and occurs dissemi-
nated in the anorthite groundmass, but in other cases, it K-feldspar is less common than anorthite; it is also
constitutes more than the 50% of the rock. Its grain size fine-grained (up to 200 ␮m) and it is associated with
also is variable, although generally close to 50 ␮m enhanced amounts of quartz. K-feldspar is generally rich
across, and the crystals have a polygonal texture. in inclusions of anorthite and organic matter. Rutile is

FIG. 4. Textural pattern of the anorthite-rich beds annealed during thermal metamorphism:
granoblastic aggregates and rounded borders involving quartz (Q), anorthite (An),
pyrrhotite (Po) and titanite (Ttn). SEM, BSE image. Scale bar: 100 ␮m.
 V-RICH MINERALS IN SEDEX DEPOSITS, SOUTHWESTERN CATALONIA 567

also found as small inclusions (up to 5 ␮m). Most of the wt.%, Table 1). The K-feldspar crystals are unaffected
crystals correspond to a rather pure low-temperature by either deformation or schistosity, thus suggesting a
microcline, with a very low Na content but a noticeable formation related with the Alpine low-temperature Ba-
celsian content (up to 2 wt.% BaO, usually about 1 veins, common in the vicinity of these deposits.
568 THE CANADIAN MINERALOGIST

Titanite Vanadoan amphiboles

Titanite develops euhedral to subhedral crystals, Vanadoan amphiboles develop mainly at the Roca
widely distributed in the anorthite-rich beds. Titanite de Ponent and Coma Fosca occurrences, where the
grains from these deposits display a strong reddish black metamorphic grade is higher (amphibole to pyroxene
pleochroism, are slightly radioactive, and possess a thin hornfels facies). They form poikiloblastic subhedral
metamict aureole. The mineral is very rich in small in- crystals of prismatic habit, up to two centimeters in
clusions of Ti oxides (rutile and ilmenite). In addition, length. These crystals include anorthite and biotite
titanite also occurs as a rim around ilmenite crystals. grains, whereas inclusions of V–Ti oxides are rarer. The
Therefore, titanite can be interpreted as having formed crystals are randomly oriented, and in some cases, they
by a metamorphic reaction between ilmenite or rutile form veins. These amphiboles probably formed during
and the host anorthite. The titanite is vanadoan (up to contact metamorphism related to the Late Hercynian
8.37 wt.% V2O3) and chromian (up to 0.6 wt.% Cr2O3; granitic intrusive bodies that crop out near the occur-
Table 1). Titanite can accommodate variable amounts rences sampled. They are calcic amphiboles according
of V, as described in Hemlo, Canada (Harris 1989, Pan to the classification of Leake et al. (1997). The
& Fleet 1992) and in Andros Island, Greece (Bernau & ferroactinolite and tschermakite components are very
Franz 1987). Assuming that all the vanadium is triva- variable at all scales: district, deposit and individual
lent in titanite, and in absence of significant replacement grain (Fig. 5, Table 1). As a distinctive feature, most of
of Ca, the OH content is expected to be high, as a result the amphiboles from the Prades Mountains occurrences
of the coupled substitution Ti4+ + O2– = (Al3+ + Fe3+ + have high levels of V (ranging between 0.6 and 5.8 wt.%
V3+ + Cr3+) + OH–. Nb and Ta, mentioned in other de- V2O3, 1.5 wt.% on average) and Cr contents (0.1–0.6
posits, are absent in titanite at this locality. The associa- wt.% Cr2O3). Moreover, the Sc content is relatively high
tion of titanite with the above-mentioned oxides and (up to 0.05 wt.% Sc 2O 3). Vanadium occupies the
anorthite strongly suggests that it formed during con- octahedral sites in the structure, and has a negative cor-
tact metamorphism. This interpretation could also ex- relation with Si, thus suggesting a mechanism of substi-
plain the V content, because the rutile grains of these tution of the type: IVSi4+ VIFe2+ = IVAl3+ VIV3+. The
deposits have significant contents of vanadium. crystals are irregularly zoned; the external part is the

FIG. 5. Classification of the calcic amphiboles from the occurrences studied. 1. Coma
Fosca, 2. Roca de Ponent, 3. Sant Miquel. Amphibole diagram of Leake et al. (1997).
 V-RICH MINERALS IN SEDEX DEPOSITS, SOUTHWESTERN CATALONIA 569

richest in V and Cr and the poorest in Si. Therefore, this atmosphere. These conditions are compatible with the
V-enrichment occurs mainly in the ferrohornblende metamorphic conditions inferred for the Prades Moun-
domain. tains and the carbonaceous nature of the Silurian series.
The compositions obtained in our study area are similar
Goldmanite to those reported worldwide (Fig. 7, Table 1).

Goldmanite, Ca3(V,Cr,Al,Fe3+)2(SiO4)3, occurs ex- Hedenbergite

clusively within the anorthite-rich bands; the crystals are
green, up to 2 mm across, and develop as poikiloblastic Fe-rich members of the diopside–hedenbergite se-
anhedral domains (Fig. 6) that include anorthite, V-rich ries have been found only in the occurrences affected
amphibole, pyrrhotite, chalcopyrite and vanadium ox- by the highest metamorphic grade, such as at Roca de
ides. Its chemical composition is very variable, as Ponent. The crystals occur sparsely disseminated in the
commonly reflected in the concentric or patchy zoning, anorthite groundmass. Hedenbergite is anhedral and
and can be expressed in terms of the end members: occupies the interstices between the anorthite grains, or
Gm55–81Uv7–29And5–20Gr20–30. In the zoned crystals, the forms poikiloblastic crystals rich in anorthite inclusions.
core is richer in the grossular end-member, and the rim, Hedenbergite is devoid of significant amounts of V, Cr
in goldmanite and uvarovite. Similar V-enrichment in or Sc.
the external part of calc-silicate crystals was reported in
the Hemlo gold deposit, Canada (Pan & Fleet 1992). Muscovite
Goldmanite is the rare vanadium-dominant end-
member of the garnet group. V-rich garnet has been re- There are two generations of muscovite. The first one
ported in many environments, such as metamorphosed is related to early metamorphic processes, and is one of
uranium–vanadium deposits (Moench & Meyrowitz the main components of the pelitic rocks that host the
1964), skarns or skarnoids (Benkerrou & Fonteilles ore-bearing horizons. The second generation of musco-
1989, Mueller & Delor 1991), and metamorphosed vite is fine grained and occurs close to late fractures, as
black shales (Jeong & Kim 1999). In all cases, it occurs a result of replacement of anorthite.
in association with carbonaceous sediments (Uher et al. The muscovite structure can accommodate signifi-
1994, and references therein). Ito (1965) synthesized cant amounts of Ba and Cr (e.g., Pan & Fleet 1991a,
goldmanite at temperatures above 450°C in a reducing Chabu & Boulègue 1992) and V (e.g., Kazachenko et

FIG. 6. Poikiloblastic goldmanite (Gld) enclosing pyrrhotite grains (Po). Pyrite (Py) re-
places the association. SEM, BSE image. Scale bar: 200 ␮m.
570 THE CANADIAN MINERALOGIST

al. 1993). As a result, we systematically analyzed mus- size), which excludes a detrital origin (Fig. 8). The
covite for these elements, but only negligible amounts pyrophanite and geikielite components are absent in
were found. these crystals.

Allanite-(Ce) MINERALOGY OF THE SULFIDE-RICH SHALES

Allanite-(Ce) is very common in the Coma Fosca and The sulfide-rich shale horizons contain fine-grained
Roca de Ponent occurrences. The crystals are usually minerals: V-rich biotite, muscovite, quartz and pyrrho-
zoned and display different shades of pale rose to tite. Accessory amounts of chalcopyrite, Ti–V oxides
salmon pink. Allanite-(Ce) occurs in the feldspathic and titanite are present, as well as lesser contents of
beds as euhedral poikiloblastic crystals, up to 300 ␮m native bismuth, bismuth tellurides, sphalerite, löllingite,
across, displaying concentric zoning, or as a product of arsenopyrite, clausthalite (PbSe), altaite (PbTe), mona-
infilling in late undeformed veins. In these veins, zite, xenotime, wolframite, scheelite, uraninite and zir-
allanite-(Ce) is associated with calcite and epidote. The con. The sulfides occur disseminated or as thin discrete
V and Cr contents are noticeable (up to 0.4 wt.% Cr2O3 beds (less than 1 mm). All these minerals are affected
and 1.5 wt.% V2O3); much higher Cr contents have al- by the regionally developed cleavage. In these beds, the
ready been reported in Outukumpu, Finland (up to 5 thermal metamorphism led to recrystallization and de-
wt.% Cr2O3, Treloar & Charnley 1987), and Pan & Fleet velopment of cordierite and andalusite.
(1991b) reported up to 7.8 wt.% V2O3 in allanite-(La) These beds provide the highest concentrations in
and 8.5 wt.% V 2O 3 in allanite-(Ce) from Hemlo, precious metals; in the Sant Miquel deposit, they con-
Canada. Allanite-(Ce) from the Prades Mountains is rich tain up to 0.6 ppm Pd, 0.2 ppm Au and 0.1 ppm Pt. These
in all the light rare-earths (Table 1). The allanite occur- elements have been found in the following situations:
rence can be interpreted in terms of REE-, V- and Cr- a) as discrete grains disseminated in the sulfide-rich
remobilization during thermal metamorphism. shale matrix (sperrylite, hessite), b) in the löllingite
structure, i.e., Pd-bearing löllingite, c) as native ele-
Ilmenite ments, arsenides, tellurides and selenides related to the
löllingite sulfidation process, and d) as late vein
Ilmenite is a rather common component of the anor- infillings (acanthite).
thite-rich beds and, as mentioned above, it has been
partly replaced by titanite. The crystals are poikiloblas- Vanadoan biotite
tic and include small grains of scheelite (up to 2 ␮m in
Vanadoan biotite is the most common mineral in the
sulfide-rich beds. In contrast, biotite is nearly absent in
the other units of the deposits. It occurs as reddish brown
subhedral tabular crystals of about 100 ␮m across. Gen-
erally, these crystals are arranged according to the re-
gional schistosity associated with Hercynian folds,
except in the zones most affected by thermal metamor-
phism. Biotite from the sulfide-rich beds has high vana-
dium contents (more than 4 wt.% V2O3 and up to 0.5
wt.% Cr2O3). The level of vanadium may even exceed
that of titanium (Table 1). These vanadium contents are
relatively high, although higher vanadium contents in
phlogopite (up to 10.1 wt.% V2O3) were reported in
Hemlo, Canada (Pan & Fleet 1992). The biotite crystals
from the ore horizons are very rich in small inclusions
of radioactive minerals (uraninite, zircon, monazite),
which produce metamict aureoles.

Andalusite

Andalusite occurs as euhedral prismatic crystals,

corresponding to the variety “chiastolite”. It is sparsely
FIG. 7. Compositions of goldmanite from the Silurian occur- distributed in bands of Al-rich black shale interbedded
rences of the Prades Mountains (black triangles) and world within the sulfide-rich bands. Andalusite is usually al-
occurrences reported in Uher et al. (1994) (circles). Dashed tered to white mica and kaolinite. The crystals are ran-
areas represents the compositional fields reported: O: domly oriented; thus, they are related to the
Outukumpu, K: Malé Karpaty. post-tectonic contact metamorphism.
 V-RICH MINERALS IN SEDEX DEPOSITS, SOUTHWESTERN CATALONIA 571

FIG. 8. Ilmenite crystal (Ilm) containing tiny inclusions of scheelite (Sch). Notice the
subhedral rim of titanite (Ttn) at the contact between ilmenite and the silicate matrix,
composed of quartz (q), amphibole (Amp) and anorthite (An). SEM, BSE image. Scale
bar: 100 ␮m.

Cordierite However, coulsonite from Sant Miquel is very rich in

Cr and Zn, though its contents are not as high as those
Cordierite only occurs in the Roca de Ponent and reported by Dimitrieva et al. (1990) (Table 2, Fig. 9).
Coma Fosca occurrences. It develops anhedral poikilo- These crystals are poikiloblastic and contain many in-
blastic crystals, up to 250 ␮m in diameter. This mineral clusions of quartz, micas and sulfides; therefore, a de-
formed during an episode of thermal metamorphism, as trital origin can certainly be discarded. The analyzed
indicated by the random arrangement of the crystals. grains show small compositional variations, but they are
Cordierite is strongly altered to white mica, and does internally homogeneous.
not show an abnormal composition (e.g., V or Cr en-
richment). Chromite

Rutile Chromite is very rare, and only a few grains in a

sample from the Sant Miquel deposit have been found
Rutile develops subhedral prismatic crystals, up to now. These are anhedral and fine-grained (up to
sparsely distributed in the pelitic matrix. Most of rutile 40 ␮m). Although the Fe/(Fe + Mn) and V/(V + Cr)
grains from occurrences in the Prades Mountains con- values are very similar to those reported from the
tain noticeable contents of V (up to 3 wt.%) and Cr (up Rampura Agucha massive sulfide deposit (Höller &
to 0.4 wt.%, Table 2). Stumpfl 1995), chromite crystals from Sant Miquel have
higher Zn contents (Table 2, Fig. 9).
Coulsonite High proportions of the zincochromite component
are typical of many chromite occurrences in sedimen-
Coulsonite, (Fe,Mn,Zn)V2O4, a rare member of the tary rocks worldwide (e.g., Weiser & Hirdes 1997, and
spinel group, is rather abundant in the Sant Miquel de- references therein). In many cases, chromite of compa-
posit, where it develops anhedral poikiloblastic grains rable compositions has been attributed to metamorphic
scattered in the pelitic bands. These crystals may attain processes affecting chromite of ultramafic provenance
100 ␮m across. Fe is the main cation in tetrahedral po- in placer deposits (Challis et al. 1995, López Sánchez-
sitions, unlike the classic Mn-rich vuorelainenite from Vizcaíno et al. 1995), or to alteration zones developed
the Sätra deposit, Sweden (Zakrzewski et al. 1982). at the expense of basic rocks (Bernier 1990, Béziat &
572 THE CANADIAN MINERALOGIST
 V-RICH MINERALS IN SEDEX DEPOSITS, SOUTHWESTERN CATALONIA 573

intergrowth with the silicate matrix and sulfides do not

allow us to obtain structural information.

Rutile

Rutile is very common in these beds, and forms

single anhedral, poikiloblastic crystals. Its size varies
between 30 and 200 ␮m. It is rich in inclusions of pyr-
rhotite, quartz and micas. Thus, a detrital origin is ex-
cluded. Rutile from these beds is enriched in V and Cr
(Table 2).

Uraninite

Uraninite develops small euhedral cubes or rounded

grains, up to 5 ␮m in size. Uraninite is abundant in some
beds. In most cases, it is included in pyrrhotite crystals,
but it can also occur as inclusions in pyrite crystals from
late veins. In spite of its small size, uraninite crystals
have inclusions of other minerals. Uraninite crystals
have a variable composition, and some of them are Th-
rich.

FIG. 9. Compositions of the Cr–V spinel in the deposits stud- Zircon

ied (black circles) plotted in the diagram of Höller &
Stumpfl (1995). Zircon is rather common as a detrital mineral, and
occurs as small crystals (about 5 ␮m) included in bi-
otite, in which it produces a metamict aureole.
Monchoux 1991). In other cases, hydrothermal pro-
cesses without a magmatic chromite precursor are well Apatite
established (von Knorring et al. 1986, Ashley & Martyn
1987, Mogessie et al. 1988, Hottin & Aloub 1990, Anhedral crystals of an apatite-group mineral, up to
Bermanec et al. 1999). In our case, the magmatic 50 ␮m across, are rather widespread in the pelitic ma-
chromite precursor is lacking, and the formation of trix. These apatite grains commonly contain inclusions
chromite may well be due to the metamorphism of Cr- of a monazite-group mineral.
rich black shales.
Monazite
Berdesinskiite
A monazite-group mineral is very abundant in some
Berdesinskiite, V2TiO5, is very rare, and occurs as discrete beds, where it forms clouds of small anhedral
small grains up to 25 ␮m across dispersed in the schists. crystals (usually less than 5 ␮m in diameter, but in some
Its chemical composition (Table 2) shows higher Cr cases up to 100 ␮m). It generally it is included into bi-
contents than the type-locality material reported from otite, apatite and sulfide grains. The monazite is Th-
Kenya (Bernhardt et al. 1983). poor.

Ti–V–Cr–Sc–REE–U phase Xenotime

The structural formula derived for what may be a A xenotime-group mineral occurs at the same beds
new species, (Ca,La,Ce)(U, Sc)(Ti,V,Fe,Cr,Mg)20O38, as monazite, but it is less common. As the monazite, it
is close to the general formula of the crichtonite group. forms anhedral crystals, less than 50 ␮m in diameter.
However, the Sc-, V- and Cr-contents are higher than
those reported for crichtonite-group members (Table 2). MINERALOGY OF THE PHOSPHATE BEDS
This phase is rather common throughout all the deposit,
in roughly subhedral tabular poikiloblastic crystals Phosphate beds are very common in the sulfide-rich
(Fig.10). In polished section, it has a low reflectance, units of the Lower Llandoverian series of all the
similar to that of sphalerite, and displays a brownish hue. Catalonian Coastal Ranges. In most localities, they con-
The grain size (lesser than 100 ␮m) and the intimate sist of an apatite-group mineral, with the exception of
574 THE CANADIAN MINERALOGIST

the Gavà and Montcada areas (central part of the MINERALOGY OF THE CALC-SILICATE BANDS
Ranges), where aluminous and ferroan phosphate beds,
consisting of variscite and strengite, are interbedded Calcic clinopyroxenes (Fe-rich members of the di-
with apatite beds (Costa et al. 1993, Camprubí et al. opside–hedenbergite series) are the most common min-
1994). In the Prades Mountains deposits, these Al- and erals in the calc-silicate beds. They occur as fine-grained
Fe-phosphates are absent, and minerals of the apatite crystals (up to 50 ␮m) that form granoblastic aggregates,
group are found as the dominant components of the with minor contents of titanite (scarce in these bands).
phosphate beds. The phosphate beds can be interbedded A late association of minerals replaces the pyroxene
within sulfide-rich bands or anorthite-rich beds. Their grains along the rim of the grains, and consists of quartz,
thickness is very variable, from some tens of microme- grossular–andradite garnet (with up to 20% of the
ters up to a few centimeters. The apatite beds are almost spessartine end-member), epidote or an allanite-sub-
monomineralic, but minor amounts of pyrrhotite, quartz, group mineral in zoned crystals, calcite and actinolite.
muscovite, monazite and uraninite also occur (Fig. 11). All these minerals clearly developed during the thermal
Uraninite crystals are rather common as disseminations metamorphism produced by the emplacement of bodies
through the phosphate beds. Uraninite is fine-grained of Late Hercynian granite.
(up to 5 ␮m), and usually euhedral (cubes). Unclassi- The silicates from the calc-silicate bands, in contrast
fiable fossil remains occur in rare cases into these beds, with those from the anorthite or sulfide-rich shales,
and they probably correspond to highly recrystallized never contain noticeable amounts of V, Cr or Sc, and
radiolarian skeletons. their chemical composition is very close to that of calc-
Although the apatite-group mineral is usually cryp- silicates from many skarns worldwide.
tocrystalline, it can increase slightly in grain size in the
deposits affected by a higher metamorphic grade. The MINERALOGY OF THE QUARTZITE BEDS
phosphate beds acted as rigid units during the deforma-
tion in comparison to the more ductile sulfide-rich Quartzites consist mainly of quartz, with lesser
shales, and therefore they are usually affected by amounts of fine-grained micas located at the borders of
boudinage structures. In this case, the necking-down the quartz grains. Sulfides are very scarce. Pyrrhotite
zones between the apatite boudins are infilled by a sec- occurs in the interstices between quartz grains, and the
ond generation of apatite (as euhedral short prismatic mineral association show textural evidence of re-equili-
crystals, up to 50 ␮m in length), together with quartz, bration during the thermal metamorphism.
anorthite, pyrite, uraninite and monazite.

FIG. 10. Poikiloblastic development of a possible Cr-, V- and Sc-rich member of the
crichtonite group. SEM, BSE image. Scale bar: 50 ␮m.
 V-RICH MINERALS IN SEDEX DEPOSITS, SOUTHWESTERN CATALONIA 575

FIG. 11. Apatite-rich phosphate beds (Ap), interbedded with an anorthite-rich band com-
posed of anorthite (An), amphibole (Amp) and pyrrhotite (brighter grains). Notice the
presence of small grains of uraninite (U) disseminated in the phosphate beds. SEM,
BSE image. Scale bar: 2 mm.

PARAGENETIC SEQUENCE existing mineral associations, the recrystallization of

micas and the annealing of the sulfide associations (de-
The V- and Cr-rich minerals occur disseminated velopment of granoblastic decussate textures). Contact
among Llandoverian sulfide-rich metasedimentary metamorphism also caused changes in the mineral as-
units. The textural patterns indicate that most of these sociations. In the innermost part of the contact aureoles,
minerals formed or re-equilibrated during the regional biotite appears as randomly oriented grains. On the other
or contact metamorphism. hand, many poikiloblastic V- and Cr-minerals occur in
The regional metamorphism (Westphalian in age) this stage. The mineral association encountered depends
produced the recrystallization of many minerals; how- on the average composition of the protolith. In the va-
ever, the regionally developed cleavage is only pre- nadium-rich shales, the V phases are oxides and biotite,
served in the outermost parts of the contact aureole. whereas in the anorthite-rich rock, the minerals are prin-
Muscovite is largely produced at that stage. Moreover, cipally V-rich calc-silicates (garnet, amphibole). As a
textural relationships suggest that ilmenite and rutile rule, the highest V and Cr contents of amphibole and
also may be formed at that stage. Firstly, they cannot be garnet grains are found in the outermost part of the crys-
considered as detrital minerals, since they have inclu- tals. This distribution of V and Cr in the silicates sug-
sions of the accompanying minerals (for example, sul- gests that the equilibrium was not achieved during the
fides in rutile, and scheelite in ilmenite). Moreover, thermal metamorphism, and that V and Cr were con-
these poikiloblasts are arranged along the schistosity tributed from the host sediments. Goldmanite occurs in
and, therefore, they are anterior to the Late Hercynian areas of higher metamorphic grade, and it formed after
contact metamorphism. the V-rich amphiboles.
The intrusion of the Late Hercynian granitic magma A more detailed paragenetic sequence of these min-
(Serra & Enrique 1989) produced contact metamorphic eral associations, that also comprises the ore minerals,
aureoles. The occurrence of cordierite and andalusite in is found in Canet et al. (2003).
the black shales is indicative of a medium-grade con-
tact metamorphism, in the amphibole hornfels facies. DISCUSSION
Cordierite is mainly found in the Fe- and Mg-rich beds,
whereas andalusite formed in the Al-rich black shales. The Lower Llandoverian sulfide-rich metasedimen-
These minerals enclose sulfides. The contact metamor- tary rocks of the Prades Mountains show V and Cr en-
phism produced the textural re-equilibration of the pre- richment related to a noticeable PGE mineralization of
576 THE CANADIAN MINERALOGIST

sedimentary-exhalative primary origin (Melgarejo 1992, elements; these elements could be enriched in the
Melgarejo et al. 1994). The association V–Cr–PGE has exhalative particles by a scavenging process. However,
been reported in some exhalative deposits. For example, hydrothermal transport of Ti–U–V–Cr–Ba–REE–(Au)
chromian spinel and vanadoan amphiboles, associated and sulfides by the same fluid is already known to oc-
with Pd minerals, have been described in Nairne, Aus- cur in some hydrothermal veins (Johan et al. 1995), and
tralia (Graham 1978). Treloar & Charnley (1987) pointed out that the Cr im-
The V content in the Llandoverian sulfide-rich mobility at Outukumpu seems established in metamor-
metasedimentary rocks of the Prades Mountains attains phic environments, but not in hydrothermal systems.
0.54 wt.% V in the Coma Fosca outcrop (Canet & In the Prades Mountains deposits, V and Cr were
Melgarejo 2001). The V–Cr distribution in the minerals immobilized by new minerals produced during meta-
has been modified by metamorphic recrystallization. morphism at short distances from the precursor mineral:
Vanadium (and Cr) were probably linked to the organic in coronas (titanite, garnet) and veinlets (allanite). A
matter in the sedimentary protoliths, or to sheet silicates, similar conclusion can be reached concerning U and the
as observed in many other V- and Cr-rich sediments REE.
related with hydrothermal deposits (e.g., Pouit & Bois Otherwise, the common occurrence of uraninite in
1986, Meyer & Robb 1996). These elements presum- the Prades deposits suggests that oxidizing fluids acted
ably were accommodated in the structure of Ca-rich sili- as carriers of these elements to a reducing sea bottom.
cates (vanadoan garnet, amphiboles, etc.) during the Moreover, the role of such oxidizing brines in the trans-
contact metamorphism, when the sheet silicates equili- port of metals during the formation of Ba-poor sedex
brated with anorthite-rich sediments. deposits has recently been envisaged (Cooke et al. 2000).
Geochemical anomalies in V and Cr are not excep- Another unusual occurrence in these showings is that
tional in exhalative deposits and have also been reported of the feldspathic beds. The occurrence of massive Na-,
in present-day metalliferous sediments. Damman (1988) K- and Ca-rich feldspar horizons is common in many
described Mn and V geochemical anomalies in sedex- exhalative deposits worldwide. They have been attrib-
type deposits, and concluded that the vanadium enrich- uted to metamorphism of tuffaceous sediments (Plimer
ments are representative of facies near the emitting 1977), to diagenetic processes (Goodfellow 1984), or
center, whereas Mn-rich facies occur at more distal po- to reaction of alkaline marine water in Pre-Carbonifer-
sitions. High concentrations of V, leading to the pres- ous seas with acid hydrothermal fluids (Russell 1988).
ence of vuorelainenite, occur in the massive sulfide Moreover, Ba-rich feldspar occurs in many metamor-
deposits at Sätra, Sweden (Long et al. 1963, Zakrzewski phosed exhalative deposits. These occurrences have
et al. 1982). Cr–V spinels also occur in the Rampura been explained as a product of metamorphism of barite
Agucha Pb–Zn–(Ag) deposit in Rajasthan, India (Höller protoliths in environments of reduction (Chabu &
& Stumpfl 1995). Moreover, although V-rich sedimen- Boulègue 1992).
tary rocks are rare in relation to stratiform mineraliza-
tion in the Pyrenean deposits, chromian muscovite CONCLUSIONS
(“fuchsite”) and Ti–Cr oxides are common in some de-
posits (Bois et al. 1976, Melgarejo 1992). Therefore, The V- and Cr-rich mineral associations from the
these minerals can give rise to a wide variety of mineral southwestern part of the Catalonian Coastal Ranges are
species during the regional or contact metamorphism. the result of the regional and contact isochemical meta-
Gabriel (1991) described an interesting association of morphism. Contact metamorphism took place in
cherts with disseminations of crandallite (with Ba, Pb, epizonal conditions, and produced mineral associations
Cr and V), florencite-(Ce), monazite-(Ce) and cerium typical of amphibole to pyroxene hornfelses. The min-
oxides in the low-grade metamorphosed Proterozoic eral associations produced are a function of the precur-
series from Bohemia. Veins with roscoelite and barite sor sedimentary rocks. Therefore, the composition of the
(with native gold and nickel in the gangue) cut the as- metamorphic rocks can be described in terms of the
semblage. Other V oxides are common in massive sul- protoliths. The metamorphism of rocks containing abun-
fide ores, like karelianite in Outukumpu, Finland (Long dant organic matter favored the development of V3+- and
et al. 1963). Bermanec et al. (1999) described a case of Cr3+-bearing minerals.
stratiform sulfide mineralization containing hyalophane Contact metamorphism of V-rich aluminous shales
and chromite in Bosnia. Finally, it is worth mentioning produces the development of V-rich aluminosilicates
the occurrence of authigenic V oxides in recent metal- (mainly biotite) and V oxides. The presence of V ox-
liferous sediments from the Red Sea (Jedwab et al. ides in apparent equilibrium with V-rich silicates sug-
1989). In our opinion, the textural patterns of V- and gests a upper limit for the V and Cr activities in these
Cr-rich minerals indicate a premetamorphic origin. The aluminosilicates at the conditions of the thermal meta-
V and Cr enrichment could be syngenetic with respect morphism. Furthermore, both in medium- to high-grade
to the formation of the sulfide-bearing sediments. contact metamorphism, V and Cr tend to be partitioned
The hydrothermal supply of V and Cr seems to be in the biotite structure, and muscovite does not seem to
problematic owing to the apparent immobility of these accommodate these elements.
 V-RICH MINERALS IN SEDEX DEPOSITS, SOUTHWESTERN CATALONIA 577

Metamorphism of anorthite- and V-, Cr-rich sedi- BÉZIAT, D. & MONCHOUX, P. (1991): Les spinelles chromo-
mentary rocks led to the development of V- and Cr-rich zincifères du district aurifère de Salsigne (Montagne Noire,
calc-silicates, such as goldmanite, vanadoan tremolite, France). Eur. J. Mineral. 3, 957-969.
V-rich titanite and V-rich allanite-(Ce).
BOIS, J.P., POUIT, G., GROS, Y., GUÉRANGE, B. & PICOT, P.
(1976): Les minéralizations de Zn (Pb) de l’anticlinorium
ACKNOWLEDGEMENTS de Pierrefitte: un exemple de gisements hydrothermaux et
sédimentaires associés au volcanisme dans les Paléo-
We are indebted to M. Barrandon (Muséum zoïques des Pyrénées centrales. Bull. Bureau de Recherches
d’Histoire Naturelle de Paris) and Drs. X. Llovet and X. Géologiques et Minières (sér. II) 6, 543-567.
García Veigas (Serveis Científico-Tècnics, Universitat
de Barcelona) for their assistance during the analyses C AMPRUBÍ , A., C OSTA , F. & M ELGAREJO , J.C. (1994):
with EMP. We also thank Dr. R.P. Taylor and P. Jones Mineralizaciones de fosfatos férrico-alumínicos de Gavà:
(Carleton University) for carrying out the quantitative tipología. Bol. Geol. Min. 105, 26-35.
EDS analyses. We thank Drs. Yuanming Pan, L. Bernier CANALS, A., CARDELLACH, E., RYE, D. & AYORA, C. (1992):
and R.F. Martin for reviews of the manuscript. This is a Origin of the Atrevida vein (Catalonian Coastal Ranges,
contribution to the Spanish CICYT project AMB94– Spain): mineralogic, fluid inclusion and stable isotope
0953–C02–01. study. Econ. Geol. 87, 142-153.

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