Journal of Non-Crystalline Solids 323 (2003) 8490

www.elsevier.com/locate/jnoncrysol

Devitrication of natural rhyolitic obsidian glasses:

petrographic and microstructural study (SEM+EDS)
of recent (Lipari island) and ancient (Sarrabus,
SE Sardinia) samples
Domingo Gimeno

Dept. Geoqu
mica, Petrologia i Prospecci

o Geol
ogica, Fac. de Geologia, Universitat de Barcelona, 08028 Barcelona, Spain

Abstract
Microstructural evolution of devitrication of obsidian glasses is a process not fully understood, especially with
reference to preferred nucleation sites and anisotropic development of spherulites. Evidence is commonly hidden in
advanced devitrication textures. Two sets of naturally devitried obsidian rocks, calcoalkaline rhyolitic in composition, have been used to test how this process develops. A petrographic and SEM+EDS comparative study of incipient
devitried recent obsidian (from Lipari island) and advanced devitried ancient rhyolitic rocks (from Sarrabus region,
Sardinia island, Italy) allows following successive stages in the generation of K-feldspar spherulites in natural glasses.
Spherulites show a preference for epitaxial nucleation over previous minute idiomorphic crystals and a number of
processes including rearrangement of initial mineral bers and interstitial voids lead to the formation of blade-like
crystals and denser spherulites. In some cases bubbles with an inferred origin associated to secondary boiling of magmas
also favour spherulitic nucleation.
2003 Elsevier B.V. All rights reserved.

1. Introduction
Natural glasses are unusual in the geologic
record. Most such glass is produced on the earth
surface during volcanic processes [1]. Volcanism
is widespread on the earth surface, but is strictly
related to particular geodynamic settings and
shows local tectonic control [1]. This fact is related to the required conditions for magma pro-

Tel.: +34-93 402 1404; fax: +34-93 402 1340.

E-mail address: domingo@natura.geo.ub.es (D. Gimeno).

duction and transport from crust or upper mantle

to the surface (positive thermal anomalies, regional decompression, local availability of water)
[1]. Most current volcanism is developing on midocean ridges under submarine conditions and is
mainly basaltic in character; on the other hand,
rhyolitic volcanism is prevalent in convergent
margin plates and back arc environments [1,2].
This situation has been maintained with minor
variations at least since the Paleozoic times over
600 Ma; anyway rhyolitic volcanism is well represented over the entire geologic scale of time
[1,2].

0022-3093/03/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-3093(03)00294-1

D. Gimeno / Journal of Non-Crystalline Solids 323 (2003) 8490

Eusive rhyolitic volcanoes are known in a

number of subaerial environments. They consist
of single to clustered mushroom-shaped high ratio
dome structures, kilometer in size, that in their
initial phases of eruption can erupt massive to
poorly vesiculated rhyolitic obsidians [3]. Analogous rhyolitic volcanoes erupted in a submarine environment have been recognized in the
geological record [46] and, more recently, in recent sea oor [7,8]. Thus scarcity of rhyolitic glass
in the geologic record is only due to its instability.
Late devitrication of obsidian occurs when
hydrous uids, alkalies and secondary heating act
on the glass [9]. Independently of this fact,
obsidian glass undergoes a series of textural
modications related to high temperature crystallization (mainly feldspars and silica phases),
the most prominent being the generation of a
spherulitic texture. This fact has been studied
under the microscope [912] but a more detailed
microstructural study is required to understand
the patterns of devitrication and the relationships with other textures. The current study to
describe all the stages of this process of devitrication started with the characterization of ancient (early Paleozoic) devitried obsidian rocks
in Sarrabus region (SE Sardinia, Italy) and was
complemented with analogous study of recent
obsidians from Lipari showing an incipient stage
of spherulitic growth.
Explosive silicic volcanism largely exceeds in
volume the eusive one. This dierence results in
the case of explosive volcanism in the formation
of large volume of fragmentary vesiculated silicic
glass that is deposited mainly as planar beds on
the earth surface after an excursion through the
atmosphere [1,13]. Rocks made in this way are
labeled pyroclastic and glass fragments can be
totally or partially welded after their emplacement. Pyroclastic fragmentary volcanic rocks are
usually devitried to zeolitic and clay mineral
assemblages; more rarely can undergo high temperature spherulitic devitrication [14] and
therefore some of the evidence provided in this
paper can be applied in their study. We use the
terminology developed in [9] as recently revised in
[14].

85

2. Volcanic rocks studied

2.1. Sarrabus white porphyries (pordi bianchi del
Sarrabus)
The Paleozoic sequence in Sarrabus region (SE
Sardinia, Italy) is a thick (up to 1000 m) siliciclastic and volcano-sedimentary succession deposited within a shallow marine basin, ranging
from Upper Ordovician to Carboniferous in age
[4,5]. This succession contains a large quantity of
volcanic and volcano-sedimentary rocks with a
predominance of calcoalkaline products (mainly
silicic) distributed in several volcanic episodes
throughout Paleozoic time [4,5]. In a broad sense,
we can classify the white porphyries [15] as
aphyric to poorly porphyritic rhyolites and
rhyodacites of several volcanic lithofacies (lava
ows, ignimbrites, minor sills, marginal border
lithofacies of compositionally zoned domes and
cryptodomes), while grey porphyries (Pordi
grigi) mainly correspond to holocrystalline main
bodies of domes of kilometric dimensions and
dacitic (and locally andesitic) character. Most silicic magmas were placed on (or near to) the sea
bottom as non-vesiculated domes, dikes and lava
ows; therefore explosive character was greatly
reduced [4,5,15].
All lava ow lithofacies of white porphyries
exhibit conspicuous devitrication in the spherulitic stage [9]. This devitrication was locally described [11] near the old silver mine of Tuviois but
remained forgotten over a century [4,16]. As a
general rule we can remark that more viscous
erupted submarine dome and lava ow facies (as
inferred by aspect ratio of ows and domes) show
a less developed spherulitic devitrication pattern
as well as poor evidence of magmatic ow, while
low viscosity lava ows of metric thickness are well
banded and show prominent magmatic folds, as
well as marginal borders of intrusive sectors of
domes are sharply spherulitic [4,5,16]. The studied
samples in this work are calc-alkali rhyolites with
Na2 O+K2 O near to 9% (K slightly exceeds Na).
They come from the Punta Serpedd, Bruncu
Mauru Lecca, Bruncu Murdegu and Rocca Arricelli localities in Western-Central Sarrabus region
and can be considered representative of the entire

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D. Gimeno / Journal of Non-Crystalline Solids 323 (2003) 8490

region with an approximate range of age of 450

360 Ma [4].
2.2. Lipari obsidian
Lipari is the most prominent volcanic island in
the Aeolian (or Lipari) volcanic archipelago placed
north of Sicily island, Italy. Rocce Rosse is a
classical site [17] of massive to highly vesiculated
recent obsidian ows in N of the Lipari island that
shows a very incipient process of spherulitic devitrication. The sampling site is crossed by the
eastern road of the island. Rocce Rosse corresponds to a lavic emission from Monte Pilato
volcano, belonging to Cycle X of evolution of
Lipari island and corresponding to an 580 A.D.
age [18]. It is calc-alkalic rhyolitic in composition
with alkali values near to the 9% (and where like in
Sarrabus samples K slightly exceeds Na contents)
[4,18]. These rocks are glassy aphyric in texture,
massive to highly vesiculated with attened
(compared to initial spherical ones) [1,13] and deformed vesicles and glassy cell walls, ow banded
with prominent ow folds, and possibly also affected by diapiric folds related with gravitative
desequilibrium [19,20]. They originated from early
eruption of coarsely vesiculate obsidian followed
by successive overlapping by massive obsidian, as
suggested by aerial photographs and eld features.
Flow banding in black obsidian is locally increased
by sparse spherulitic to continuous white axiolitic
spherulite disposition, spherulites being in general
lesser than 1 mm in size.

spherulites was investigated by means of X-ray

powder diraction (Siemens D500). Mineral
characterization of spherulites (microtextural and
semiquantitative chemistry) was carried out by
means of scanning electron microscopy (SEM,
JEOL J3M-840) served with an energy dispersive
spectrometer (EDS) system (LINK Microanalysis)
with variable operating conditions (1015 kV,
1833 mm of window conditions). The treatment
includes dehydration to remove environmental
moisture, mounting on a metal stub with Ag solution, and metal coating with vaporized Au. A
combination of thin polished samples and irregularly crushed sample surfaces of the same samples
was studied. The homogeneity of chemical composition of the glasses as well as of the devitried crystal matrix was controlled by wavelength
dispersive spectrometer (WDS) electron microprobe analysis (Cameca Camebax SX-50) at Serveis Cient
co-Tecnics, University of Barcelona
(SCT-UB) calibrated with dierent natural and
synthetic silicates and oxides of certied composition. To avoid the eect of alkali migration in
glass irradiated by electrons [21] a strategy of
electron microprobe analysis including defocusing
of beam, rst testing for Na and a more reduced
time of acquisition in alkali elements to avoid
reaching an incubation time was developed [22].
Results in glass are consistent with those obtained
from whole rock XRF analysis. A set of certied
geological standards provided by Geological Survey of Japan has been used as internal standards in
XRF analyses; the analytical precision is within
1% for SiO2 , TiO2 , Al2 O3 , Fe2 O3 , CaO, K2 O and
MnO, and 4% for MgO, Na2 O and P2 O5 .

3. Experimental
Thin sections of natural glasses and devitried
obsidians were studied under the petrographic
microscope. Whole rock composition was determined by X-ray uorescence (XRF), by means of a
sequential X-ray spectrophotometer (Philips PW
1400) calibrated with a set of international standards using fused pearls (lithium tetraborate pearls
at a dilution 1/20). Na2 O was determined by
atomic absorption spectrometry (AAS). Loss on
ignition (LOI) was performed in an oxidizing
furnace. The mineralogical composition of the

4. Results
Lipari obsidians under the microscope show a
glassy to hypocrystalline character. Most crystals
are acicular to ber-like microliths that show hyalopilitic disposition parallel to magmatic ow
banding. Composition of microliths is not determinable under the microscope in most cases. Since
standard thickness of the section is calculated for
holocrystalline granular rocks where a section of a
crystal occupies all the section apparent crystal

D. Gimeno / Journal of Non-Crystalline Solids 323 (2003) 8490

content is increased in thin section. By contrast in

obsidian we see by transparency a volume of glass
where there are only some small crystals immersed
in. Under the microscope the zenithal view of the
obsidian substitutes the volume that we explore by
a orthogonal projection on a plane (the thin slide
surface) and therefore suggests that sparse crystals
in the glass are much more closer than really they
are. Devitrication is manifested in some poorly
resolved dots ordered following magmatic ux
bands. SEM images (Figs. 1 and 2) show that these
dots are incipient spherulites growing on quartz
idiomorphic crystals; most spherulites are constituted of irregularly shaped amalgamated bers,
with a presence of original porosity in between.
EDS spectra show that most of the bers are K-

Fig. 1. SEM image of an incipient K-feldspar growing on a

quartz crystal, Rocce Rosse, Lipari.

Fig. 2. Close-up of Fig. 1 showing the spherulite surface constituted by packed bers leaving abundant interstitial cavities.

87

Fig. 3. Thin section of a totally devitried glassy porphyric

rock from Sarrabus region showing spherulite growth on feldspar (F) and quartz (Q) phenocrysts, as well as on the matrix.

feldspar, with some intercalated silica phase. XRD

has not provided more details on the composition.
Sarrabus thin sections are now holocrystalline,
with a prevalent spherulitic and micropoikilitic
texture overprinted to a porphyritic hypo- to
mesocrystalline glassy texture (Fig. 3). Phenocrysts
are idiomorphic feldspars (K-felspar, NaCa
plagioclase) and idiomorphic skeletal quartz.
Spherulites selectively overgrow phenocrysts and
eventually include microliths and dendritic to
skeletal crystalline forms (quartz, feldspar, iron
ore). Matrix ranges from poorly spherulitic with a
micropoikilitic [9] (quartz, feldspar) texture that
includes spherulites, to totally spherulitic. Based

Fig. 4. SEM image of sample from Fig. 3 showing spherulite

growth on feldspar crystal (left).

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D. Gimeno / Journal of Non-Crystalline Solids 323 (2003) 8490

on petrographic evidence we can infer that some

matrix spherulite grew on hollow gas vesicles, now
lled with a mosaic of microcrystalline quartz.
SEM images show an evolved spherulitic texture
mainly composed of thin blades of K-feldspar
(determined by EDS) and in a lesser degree silica
phases (Fig. 4); some residual porosity between
blades also exists (Fig. 5). The nal evolution of
this process shows evidence of replacement of the
K-feldspar blades for massive laths of the same
composition with associated elimination of porosity (Fig. 6).

Fig. 5. Magnication of Fig. 5. See text for explanation.

Fig. 6. SEM image of spherulite growing on a quartz phenocryst. Spherulite is constituted by compact packed tabular laths
of K-feldspar (Sarrabus region, Sardinia).

5. Discussion
A large number of authors have described devitrication processes in natural rhyolitic systems
[1,10,11,13,14,23,24], but most of the works
available refer to an advanced devitrication process. Lofgren [9] produced devitrication of obsidian glass and studied this process and
characterized it in successive stages: glassy (hydrated, with some spherulite), spherulitic and micropoikilitic. Lofgren [9] also provided most of
available evidence on these processes but his study
did not include SEM studies of devitried samples.
Several authors have recently used SEM studies
to obtain information on crystallization and devitrication processes in natural rhyolitic glasses
[23,24]. Transmission electron microscopy has
been proposed as a good experimental approach to
study it [25]. Most of these reports are about recent
volcanism and therefore do not provide much information of advanced spherulitic stages of devitrication or evolution of devitrication with time.
In Sarrabus samples, aphyric devitried obsidians largely coexist with moderately porphyric
quartz- and feldspar-bearing (devitried) glassy
rhyolites [4]. Phenocrysts of quartz commonly
show a skeletal character. The so-called embayed
quartz phenocrysts have a large tradition in petrographic literature as being due to corrosion by
magma; nevertheless experimental work [26,27]
has demonstrated that true skeletal quartz phenocrysts are produced by supercooling of rhyolitic
magma, while more rapid supercooling forms of
dendritic silica phases. In Sarrabus samples this
supercooling is consistent with submarine emplacement of lava ows and associated shallow
intrusion in water saturated unconsolidated sedimentary rocks.
Sometimes it is dicult to distinguish early
crystallization (i.e. under the solidus) in a supercooled liquid from devitrication processes. Despite this diculty experimental work [9] and
geological evidence [14,28] show that K-feldspar spherulites in rhyolitic glasses form during
high temperature crystallization processes. A high
water content greatly increases crystallization [28].
In our cases, macroscopic spherulitic and axiolitic textures mimic the magmatic ow banding.

D. Gimeno / Journal of Non-Crystalline Solids 323 (2003) 8490

Taking into account that in most cases there is

no evidence of dierential chemical composition
between bands, this fact might be related to nucleation. SEM images (Figs. 16) show that phenocrysts, microphenocrysts and, in general, all
kinds of previous crystalline materials act as
nucleation sites for spherulites. Mineralogical and
chemical composition of crystalline substrate
and spherulitic bers have no direct relationships
and therefore spherulites grow epitaxially. The
comparison between Lipari and Sarrabus distribution and abundance of spherulites is illustrative,
since advanced spherulitic devitrication prevents
resolution of processes. Lipari spherulites develop
over idiomorphic quartz microphenocrysts that are
not evident under the petrographic microscope.
Nevertheless, some of the matrix spherulites in
Sarrabus samples seem to nucleate on gas vesicles;
vesicles that are also arranged following ow
banding. This process can be related to the viscosity of the magma, while [20] the process also
increases the role of crystallization during gas liberation (secondary boiling) [14,24].

6. Conclusions
SEM+EDS study shows, in all studied cases,
that K-feldspar and silica spherulitic bers selectively overgrow previous crystalline magmatic
phases. Sarrabus samples are Paleozoic in age and
correspond to a submarine volcanism that underwent supercooling. While the more viscous ows
and lavas show poor development of spherulites
and show microcrystalline devitrication, the inner
sectors of these lavas (and therefore aected by
supercooling to a lesser degree) show incomplete
development of spherulites and in some cases
hollow spherulites (microlithophysae) indicating
secondary boiling [4]. Low viscosity rhyolitic ows
and associated dikes show an advanced spherulitic
stage of devitrication as well as marginal sectors
of intrusive domes at contact with host rock [4].
The studied devitried samples of Lipari and
Sarrabus can be considered successive stages of the
same process. Therefore, this process is described
here entirely for the rst time. SEM studies, especially SEM conducted on irregularly crushed

89

spherulitic samples (associated with petrographic

study of thin samples), provide evidence of the
degree of developing of the process and can be
useful in the characterization of ancient obsidian
rocks. These spherulitic textures are particularly
sensitive to deformation and metamorphism and
therefore their widespread nding in cases as in the
case of Sarrabus provides evidence of rare development of regional deformation and associated
regional metamorphism.
In the case of archeological pieces e.g. arrowheads made in obsidian can be placed on metal
stub and coated with a thin lm of Au or graphite,
easily removable, in order to conduct a nondestructive study obtaining a semiquantitative
chemical analysis as well as eventually good information of macroscopically non-evident devitrication features.
Acknowledgements
This study is a part of a larger one and was nanced by several institutions: CIRIT of Autonomous Government of Catalonia, Spain; Ministry of
Education of Spain; Ministry of Foreign Aairs,
Italy; and Regione Autonoma della Sardegna,
Italy. It was carried out in the Istituto di Giacimenti Minerari (now DIGITA, Univ. Cagliari, Italy)
and Dept. Geoqu
mica, Petrolog
a i Prospecci

o
Geol
ogica (Universitat de Barcelona, UB). Analytical study was developed at SCT-UB. The author specially thanks all people who provided
valuable help and council, both in Italy and Spain.
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