CRYSTAL MORPHOLOGY AND MINERAL CHEMISTRY OF GARNETS

FROM LOS GUINDOS SKARN, CÓRDOBA, ARGENTINA: A USEFUL

COMBINED VECTOR TOWARD SCHEELITE MINERALIZATION

María José ESPECHE*1,2 and Raúl LIRA1,2

1: Laboratorio de Microscopía Óptica y Microtermometría – Museo de Mineralogía y Geología

“Dr. Alfred W. Stelzner” – Universidad Nacional de Córdoba. Av. Vélez Sarsfield 299, X5000JJC,
Córdoba, Argentina.

2: Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET).

*: majo.espeche@unc.edu.ar

RESUMEN
MORFOLOGÍA CRISTALINA Y QUÍMICA MINERAL EN GRANATES DEL SKARN LOS
GUINDOS, CÓRDOBA, ARGENTINA: UN VECTOR COMBINADO ÚTIL HACIA LA
MINERALIZACIÓN DE SCHEELITA. El análisis cristalográfico y mineraloquímico de los
granates presentes en los cuerpos de skarn scheelítico del grupo minero Los Guindos,
Córdoba, Argentina, han permitido identificar diferentes morfologías cristalinas en las
principales zonas identificadas desde las estructuras que canalizaron el ascenso de los
fluidos metasomáticos hacia los protolitos metamórficos sucesivamente reemplazados.
Los granates subcálcicos ricos en spessartina, presentan la forma dominante {211}
y se han desarrollado en el contacto entre un protolito granítico y el mármol en la zona
de máxima circulación fluida (W>R) y de mayor temperatura, mientras que los granates
asociados paragenéticamente a la mineralización de scheelita son cálcicos, con desarrollo
preferencial dominio de la forma {110}, en menor grado {211}, y minoritariamente {123} y
{111} y han cristalizado en el mármol, distalmente de los canales de ascenso de los fluidos.
La discriminación en el campo y a simple vista de tales formas en los cristales de granate
permite discernir sobre la localización de las zonas que alojan la mayor concentración de
scheelita. Si bien se desconocen los factores intrínsecos que controlan la relación entre
morfología cristalina y composición química, sí es factible reconocer que los cambios
composicionales expresados por una decreciente relación (Mn+Fe)/Ca acompañada del
abandono de la forma trapezoédrica {211} hacia un crecimiento paulatino hasta dominante
del dodecaedro rómbico {110} dentro de la holoedría del sistema cúbico (clase de simetría
), se manifiestan con el descenso térmico.

Keywords: ZONATION – GARNET GROUP – PROGRADE MINERAL – SKARN

-CRYSTALLOGRAPHIC FORMS

INTRODUCTION
The emplacement and cooling of magma at different crustal levels might lead to the
liberation of large volumes of metal-rich fluids into the surrounding country rocks and the
records about the evolution of hydrothermal systems controlled by the flow of such fluids
might be acquired by diverse techniques. These include fieldwork, mineralogical and
petrologic studies on mineral assemblages and rocks of different chemistry, isotope histories
and relative/absolute ages; such studies give information about a period of time of the
equilibrium state of the hydrothermal systems and its integration helps to infer the evolution
of the whole system.
Due to the fact that skarn are mostly the product of metasomatic processes, it is their

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zoning style and composition that allow them to be characterized, and vectoring the processes
that favor their formation as well as delimiting or locating potentially mineralized zones
(Khorzhinskii, 1968; Zharikov, 1970). In this regard, and considering that garnet is one of the
most common minerals found in skarns, either the regional scale zonation of the mineralized
skarn bodies or the intracrystalline patterns in skarn minerals can provide information about
the fluid/rock interaction process and about the evolution and physicochemical conditions of
the fluids that generated/produced these rocks (Einaudi et al., 1981; Kwak, 1987; Meinert et
al., 2005; Chang and Meinert, 2008). Several studies about zoning patterns on skarns have
been made, covering major and trace element chemistry (e.g., Newberry, 1983; Jamtveit,
1991; Jamtveit et al., 1993; Karimzadeh Somarin, 2004; Ranjbar et al., 2016,) and isotope
geochemistry (Clechenko and Valley, 2003). However, we have not found research data
that indicate possible variations of crystallographic morphologies dependent on mineral
chemistry and skarn zonation. In this paper we report variations of the crystallographic forms
and major element chemical zonation patterns in garnets from Los Guindos scheelite skarn,
which characterize different skarn zones.

METHODOLOGY
Major elements of garnet were measured by wavelength-dispersive spectrometry
at the Laboratorio de Microscopía Electrónica y Difracción de Rayos X (LAMARX), in the
Facultad de Matemática, Astronomía, Física y Computación of Universidad Nacional de
Córdoba, Argentina. It was used a JEOL JXA 8230 electron microprobe operating at an
accelerating voltage of 15 kV with a 20 nA beam curred, 3 beam spot and 10-20 s counting
time. The following natural and synthetic minerals were used for calibration: forsterite (Mg,
Si), anorthoclase (Al), rodonite (Mn), fayalite (Fe), CaWO4 (Ca). Garnets, samples were
taken from representative areas of the main scheelite skarn mines. The crystallographic
reconstruction of garnets was made using Shape v7.4 Software, from detailed observations
in hand sample whenever possible, but mostly under the stereographic microscope. Mineral
abbreviations are following Whitney and Evans (2010).

GEOLOGICAL SETTING
Los Guindos Mining Group (31°10’ - 31°12’S / 64°32’ - 64°35’W) has been one of the
main tungsten producers of Argentina, between the 40’s and 60’s (Valdez, 1984; Espeche
and Lira, 2018). The scheelite mineralization is hosted in coarse grained irregular shaped
skarn bodies from a few up to some hundreds of m2 area, developed after the replacement
of marbles through distal travelled, structurally infiltrated metasomatic fluids. The basement
where skarns developed is composed mainly of metamorphic rocks of high amphibolite to
granulite facies, characterized by sillimanitic and biotite-garnetiferous gneisses, migmatites,
marbles, amphibolites, hornblendites, aplitic granite and tonalitic dikes as well as widely
distributed granitic pegmatite dikes.
The widespread and representative mineralogy that defines the ore-bearing skarn
bodies is characterized by three zones recognized from narrow fractured zones developed
along aplitic granite dikes/pegmatite-marble contacts towards the marbles: zone I composed
by garnet + helvine, zone II of clinopyroxene + garnet and zone III of vesubianite + garnet.
Retrograde skarn minerals are epidote, actinolite, chlorite, potassium feldspar, fluorite,
calcite and quartz. Epidote, actinolite, chlorite, scheelite, sulphides, fluorite, calcite and
quartz constitute the main hydrothermal infilling phases. Zone II and scarcely zone III host
the highest concentration of scheelite while zone I is barren. Even though in some mines or
outcrops some zones might be absent or with scarce development, this variability is caused
by locally restricted physico-chemical variations that does not condition the representative
regional zoning of the scheelite skarn bodies.

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GARNET CRYSTAL MORPHOLOGY
Garnet crystals in the scheelite-bearing skarn zones are idiomorphic and their edge
sizes oscillate from a couple of millimeters up to ~10 centimeters long. Crystals of zone I
are dark reddish while the zone III skarn crystals are mostly light orange (Fig. 1). However,
the color transitions from dark reddish to orange between garnets of zones I and III are not
regular. Garnets from the Zone I commonly show a dominant trapezohedron {211} form (Fig.
1a), though a few crystals show small, poorly developed dodecahedron {110} forms. Garnets
of zone II are reddish and still have a dominant trapezohedron {211} form but an incipient and
well-formed dodecahedron {110} form is clearly identified (Fig. 1b). Garnets of zone III are
reddish to orange and their morphology is variable; garnet crystals of zone III which are close
to zone II, are more reddish than the most distal garnet crystals from zone III formed close to
the marble contact, which are usually orange. The former crystals show the combination of
{211} and {110} forms, and small faces corresponding to the hexaquisoctahedron {123} form
(Fig. 1c). The latest garnets, besides the two principal forms coincident with the other zones,
present poorly developed octahedron faces {111} (Fig. 1d).

Fig. 1. a) Trapezohedron garnet crystals (form {211}) from Zone I. The yellow dotted line show the
contact between crystals. b) Trapezohedron dominant form {211} with scarcely developed rhombic
dodecahedron {110} from Zone II. c) Rhombic dodecahedron dominant form {110} with subordinated
but well-formed hexaquisoctahedron forms {123}). d) Rhombic dodecahedron dominant form {110} with
trapezohedron {211} and octahedron {111} well-crystallized forms.

CHEMISTRY OF GARNETS
Under the microscope, all garnets show distinct oscillatory zoning with anomalous
anisotropism. Zone I garnets vary from spessartine-rich grossular core to spessartine (+
almandine)-rich rim (Gr59Sp23Alm9Ad9 to Sp59Alm23Gr17Ad1; n= 31). Zone II garnets vary also from
grossular core to spessartine-rich grossular rim (Gr79Ad18Sp2Alm1 to Gr53Sp25Ad20Alm2; n= 35)
although the solid solution substitution is less pronounced than in zone I. Zone III garnets vary
also from grossular core to spessartine-rich grossular rim (Gr84Ad14Alm2 to Gr52Sp28Ad17Alm3;
n= 47) although the solid solution substitution, like in zone II, is less pronounced than in
zone I. Figure 2 shows the projection of the molar proportions of garnets in a pyramidal plot,
differentiated by zones. There is a continuum between high subcalcic compositions (spessartine
+ almandine) towards grossular (+ andradite) compositions corresponding to proximal and

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distal skarn zones. This solid solution substitution is shown on an x-y profile in figure 3 and its
relation with crystal morphology is shown. The term “proximal” indicates the proximity of the
fluid circulating structure in contact with an aplitic granite dike and the term “distal” stands for
the farthest located replaced marble. Because the thermal source of Los Guindos metasomatic
fluids is interpreted as distal with respect to skarn replaced lithologies, at the outcrop scale
“proximal” and “distal” just reflect the relative proximity of replaced protholiths in relation to the
emerging source fluid which are, indeed, strongly controlled by the compositional nature of the
protholith.

Fig. 2. Compositional tetraplot diagram of Los Guindos garnets,differentiated by skarn zones. The
paucity of data between zones I and II is due to the significant contrast between replaced protholiths:
zone I is mostly developed after the replacement of an aplitic granite dike and the contact between
zones I and II is abrupt. Grossular-rich zones II and III were developed after marble replacement.

Fig. 3. X-Y diagram showing the variation between spessartine + almandine molar proportions (%)
versus the grossular content (%) of the Los Guindos garnets, discriminated by zones. The morphology of
crystals was projected for comparison. This compositional and crystal shape variation can be vectorized
from proximal skarn zones to distal skarn zones, where “proximal” refers to the proximity of ascending
fluid circulation in structures, while “distal” refers to the maximum reach of the replaced marble.

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DISCUSSION
Garnets of Los Guindos scheelite skarn show a solid solution substitution between
subcalcic members (spessartine and almandine) and grossular (+andradite) calcic members.
This substitution follows the transition through proximal zone 1 (Grt + Hlv) to distal zone III
(Grt + Vsb, fig. 3). Spessartine-dominant garnets have crystallized under the single form of
trapezohedron {211}, whereas calcic-dominant garnets are characterized by well-developed
dodecahedron {110} combined with less grown octahedron ({111} and hexaquisoctahedron
{123}).
The dominant {211} trapezohedron form in spessartine-rich garnets is consistent with a
couple of previous studies such as the one published by Van Haren and Woensdregt (2001)
who realized analyses on experimental synthetic melts and concluded that the trapezohedron
form is the dominant form for garnets of Mn dominant composition. To the same conclusion
arrived Sepahi (2007) on analyzed natural garnets from schists, migmatites, hornfelses,
aplites-pegmatites and granitic rocks.
The chemical variations of analyzed garnets show a transition from a high subcalcic
component in zone I to a high grossular, dominant garnet in zone III. Intracrystalline zonation
shows in all cases an increase of Mn and Fe+2 content from core to rim, although in distal
zone III this variation is less pronounced due to the poor availability of Mn and Fe+2 relative
to Ca. This tendency is characteristic of reduced W skarn deposits and is recognized in other
worldwide W skarn deposits (Shimazaki, 1977; Einaudi et al., 1981; Newberry, 1983; Kwak,
1987). Scheelite mineralization is clearly related to zone II and to a lesser extent to zone III,
while is absent in zone I.

CONCLUSIONS
The morphological and chemical studies on the garnet crystals of scheelite skarn in Los
Guindos Mining Group show that zone I garnets have a trapezohedron dominant form while
zones II and III have a major development of rhombic dodecahedron and other less developed
combined forms such as hexaquisoctahedron and octahedron (holohedric class
). This variation is mainly related to varying compositions of spessartine (+ almandine)
and grossular molar proportions from the structurally controlled fluid source (i.e., proximal) to
distally replaced marble. The scheelite mineralization in Los Guindos is related to intermediate
Mn(+Fe+2)/Ca proportions and corresponds to the development of form {211} dominant over
form {110}. Variable crystal morphologies depend on compositional differences, and the latter
seem to be controlled by decreasing temperature with increasing aCa. Recognition in the
field of the crystalline morphologies of garnet makes it possible to estimate the proximity of
potential scheelite mineralized areas of the skarn. Further studies about P-T-X garnet formation
conditions are in progress.

ACKNOWLEDGEMENTS
This study was supported by the Secretaría de Ciencia y Tecnología, Universidad
Nacional de Córdoba, Argentina (Res. SeCyT-UNC N° 411/18 and N° 99/19). The authors are
grateful for the assistance of Dr. Alina B. Guereschi during microprobe analyses and for the
improvements introduced through the reviews of Lic. Miguel A. Del Blanco and Dr. Raúl E. de
Barrio.

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