Geochimica et Cosmochimica Acta, Vol. 66, No. 5, pp.

903–911, 2002
Copyright © 2002 Elsevier Science Ltd
Pergamon Printed in the USA. All rights reserved
0016-7037/02 $22.00 ⫹ .00
PII S0016-7037(01)00820-1

Silicate-Silicate liquid immiscibility and graphite ribbons in Libyan desert glass

GIOVANNI PRATESI,1,2* CECILIA VITI,3 CURZIO CIPRIANI,4 and MARCELLO MELLINI5
1
Museo di Storia Naturale, sezione di Mineralogia e Litologia, Università di Firenze, Via G. La Pira 4, 50121 Firenze, Italy
2
Museo di Scienze Planetarie, Provincia di Prato, Via Galcianese, 59100 Prato, Italy
3
Dipartimento di Scienze della Terra, Università di Siena, Via Laterina 8, 53100 Siena, Italy
4
Museo di Storia Naturale, sez. Mineralogia e Litologia, Università di Firenze, Via G. La Pira 4, 50121 Firenze, Italy
5
Dipartimento di Scienze della Terra, Università di Siena, Via Laterina 8, 53100 Siena, Italy

(Received January 22, 2001; accepted in revised form August 21, 2001)

Abstract—Transmission electron microscopic (TEM) investigation of the dark (brown or bluish) streaks
occurring in Libyan Desert Glass reveals the common presence of small glass spherules. The spherules, mostly
100 nm in size, are homogeneously dispersed within the silica-glass matrix. The complete absence of electron
diffraction effects confirms their amorphous nature. The spherules are Al-, Fe- and Mg-enriched with respect
to the surrounding silica matrix and their (Mg ⫹ Al ⫹ Fe) : Si ratio is close to 1.
The silica-glass matrix and amorphous spherules form an emulsion texture (i.e., globules of one glass in a
matrix of another glass), which originates from silicate-silicate liquid immiscibility. This texture has also been
observed in other impact-derived glasses.
The silica glass also contains carbonaceous inclusions consisting of 5–50 nm thick, polygonalized graphite
ribbons that form closed structures up to 200 nm in diameter.
These observations are in agreement with an impact origin for Libyan Desert Glass. Copyright © 2002
Elsevier Science Ltd

1. INTRODUCTION
Libyan Desert Glass (LDG) is a natural silica glass occurring
in the western part of the Egyptian Great Sand Sea over an area
of about 80 ⫻ 25 km2. LDG chunks weigh from less than one
gram up to over 25 kg. As reported by Barakat et al. (1997),
LDG occurs in wide corridors between dunes and is concen-
trated in two main zones: a larger ring-shaped area to the south
and a smaller oval area to the north. Sandstones of the Creta-
ceous Nubian Formation crop out in the larger zone. Oxidized
blackish iron beds of uncertain age are exposed in the smaller
area.
LDG was used by prehistoric man in making various arti-
facts, as seen in several findings (Oakley, 1952; Roe et al.,
1982; Negro and Damiano-Appia, 1992). It was also used in
dynastic times; the non destructive analysis of De Michele
(1998) on the scarab-shaped central motif of Tutankhamon’s
pectoral suggest that it was carved from LDG.
Clayton and Spencer (1933) wrote the first scientific report
on LDG which led to its official discovery. Since Clayton’s
discovery, many field expeditions have been carried out and
more than 2 䡠 105 kg of material have been collected. The
original mass is estimated to be greater than 1010 kg (Weeks et
al., 1984). Fission track dating indicates formation ages ranging
from 28.5 ⫾ 2.3 to 29.4 ⫾ 0.5 My (Storzer and Wagner, 1977),
as confirmed by the recent findings (estimated age of 28.5 ⫾
0.8 My) of Bigazzi and de Michele (1996) and Horn et al.
(1997).
Different origins have been proposed for this enigmatic
natural glass. Although most authors attribute its origin to
impact processes (Barnes and Underwood, 1976; Koeberl,
* Author to whom correspondence should be addressed (gpratesi@
geo.unifi.it).
903
1997; Murali et al., 1997; Rocchia et al., 1997), other origins
have been proposed. A sedimentary origin involving a sol-gel
process is suggested by Jux (1983) and Feller (1997), whereas
Futrell and O’Keefe (1997) hypothesize that the glass formed
from welded, lunar volcanic glass particles.
The impact origin is supported by mineralogical evidence
such as lechatelierite, a high-temperature melt-product of
quartz (Diemer, 1997) and baddeleyite, a high-temperature
breakdown product of zircon (Storzer and Koeberl, 1991; Roc-
chia et al., 1997).
In spite of the increasing evidence for an impact origin of
LDG, the source crater has not been identified. Relations
among LDG and the BP and Oasis impact structures were
recently suggested by Abate et al. (1999). This suggestion
stems from previous geochemical investigations (Barrat et al.,
1997; Horn et al., 1997; Koeberl, 1997) which support the idea
that the target rocks of the BP and Oasis structures are good
candidates for the source material of LDG.
One of the most interesting features of LDG is the occur-
rence of layering which suggests a flow structure. Wasson and
Boslough (2000) suggest that this structure is due to the down-
slope flow of a melt sheet after a large aerial burst.
Irregular, dark (brown or, more rarely, bluish) streaks also
occur in some LDG. Many authors (e.g., Koeberl, 1997; Murali
et al., 1997) examined these streaks to seek further evidence for
an impact origin. Geochemical data shows that the dark streaks
are enriched in siderophile elements (including Ir). This evi-
dence suggests the presence of an extraterrestrial chondritic
(Rocchia et al., 1995; Koeberl, 1997; Murali et al., 1997;
Rocchia et al., 1997) or cometary (Seebaugh and Strauss, 1984;
Murali et al., 1997) component. Unfortunately, neither optical
nor scanning electron microscopy were able to identify the
presence and nature of discrete single particles in the dark
904 G. Pratesi, C. Viti, C. Cipriani, and M. Mellini
Fig. 1. Dark band in LDG. The band, about 1.5 cm across, is
composed of many subparallel streaks which define a flow pattern.
streaks. We therefore decided to use transmission electron
microscopy (TEM) to investigate the dark streaks.
2. EXPERIMENTAL
2.1. Samples
We investigated two samples containing brown streaks (Fig. 1) given
to us by Alain Carion (Paris) and Vincenzo de Michele (Milan) and
now preserved at the Natural History Museum-Section of Mineralogy
and Lithology-of Florence University (no. RI-2732 and RI-2733). One
additional sample with unusual, faint bluish streaks comes from the
Planetary Sciences Museum of the Prato Province (no. 1430). Thin
sections were cut perpendicular to the streaks.
Transmission electron microscopy specimens were prepared sam-
pling the most intense brown or bluish streaks. Grids were thinned by
Ar⫹ ion milling using a Gatan Dual Ion Mill (5 kV and 20° in the first
Fig. 2. a, b) TEM pictures of the emulsion texture; small spherules, 80 to 100 nm in size and consisting of Mg-, Fe- and
Al-enriched glass, are hosted within the silica-glass matrix.
step; 1.5 kV and 12° in the final step of the thinning process). Thinning
of the LDG grids took several hours (more than 10 in the first step).
2.2. Transmission Electron Microscopy
Transmission electron microscopy (TEM) was performed with a Jeol
2010 operating at 200 kV and equipped with an ultra high resolution
(UHR) pole piece capable of point-to-point resolution close to 1.9 Å.
The microscope is equipped with a semi-STEM system and an ultra-
thin window energy dispersive spectrometer (EDS-ISIS Oxford) capa-
ble of detecting all elements heavier than boron. The electron probe can
be focussed to a 50 Å spot. Raw data were corrected by the thin-film
approximation (Cliff and Lorimer, 1975) and using experimentally
determined elemental proportionality factors. Accuracy and precision
depend on counting statistics. They are better than 1% for major
elements and better than 10% for minor elements; the detection limit is
0.5%. Data for oxygen and the lightest elements are affected by
absorption effects that may introduce inaccuracies of up to 15–20 %
relative (depending on specimen thickness).
Electron images have been recorded either on normal photographic
film or imaging plates (Fuji film FDL5000).
3. RESULTS
3.1. LDG emulsion texture
Microstructural analyses of the brown or bluish streaks re-
veal an emulsion texture. This texture consists of tiny glassy
spherules dispersed within a glassy matrix (Fig. 2a and b). The
two glasses (spherules and matrix) have different chemical
compositions.
The dark, rounded spherules have an almost constant diam-
eter of 80 to 100 nm. In a few cases, a second spherule
population with average diameter of about 20 nm was also
observed. Large and small spherules are usually intermingled;
in a few cases, local concentrations of small spherules were
observed. Nano-beam electron diffraction on single particles
 Liquid immiscibility in Libyan desert glass 905

Table 1. TEM-EDS analyses from the matrix and the spherules.

at. % an1 an2 an3 an4 an5 an6 an7 an8 an9 an10 an11 an12

Matrix glass
O 66.3 57.9 58.8 56.1 67.2 67.1 65.4 62.8 66.3 66.2 61.7 63.9
Mg 0.4 0.4 0.4 0.4 0.3 0.5 0.4 0.4 0.4 0.3 0.2 0.3
Al 0.1 0.6 0.5 0.7 0.3 0.5 0.5 0.4 0.6 0.3 0.9 1.0
Si 33.0 41.1 40.1 42.7 32.0 31.8 33.6 36.0 32.5 33.0 37.1 34.7
Fe 0.2 0.1 0.1 0.2 0.1 0.1 0.2 0.3 0.2 0.2 0.1 0.1
SUM 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Spherules glass
O 67.4 61.8 66.8 62.8 58.7 75.2 69.3 67.5 71.4 64.7 69.0 66.5
Mg 9.5 6.8 6.7 2.9 4.2 4.0 3.6 4.0 3.0 6.7 3.2 2.4
Al 3.5 2.7 2.77 1.5 1.9 1.8 1.9 2.2 1.9 3.1 1.4 1.1
Si 16.0 26.1 21.3 31.4 33.6 15.5 23.7 23.6 22.2 22.9 24.7 27.4
S 0.0 0.0 0.0 0.0 0.0 0.5 0.1 0.2 0.1 0.1 0.2 0.3
Ca 0.1 0.1 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.0 0.1
Ti 0.1 0.1 0.1 0.1 0.1 0.1 0.0 0.0 0.0 0.1 0.1 0.1
Cr 0.2 0.1 0.1 0.1 0.1 0.3 0.1 0.1 0.1 0.1 0.1 0.3
Fe 3.1 2.3 2.1 1.2 1.4 2.4 1.3 2.2 1.3 2.2 1.4 1.8
Ni 0.1 0.1 0.1 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.0 0.0
SUM 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

shows no diffraction effects and demonstrates their amorphous
nature. No lattice fringes or crystal faces are visible. The
spherules are entirely surrounded by fresh glass. Nano-chan-
nels, possibly associated with late fluid circulation, were not
observed. This emulsion texture, given by guest droplets dis-
persed within the silica-glass matrix, is consistent with an
origin from immiscible liquids. The LDG texture closely
matches the immiscibility textures observed by Zolensky and
Koeberl (1991) in the blue zhamanshinite impact glasses. In
particular, the two impact glasses have similar textures in spite
of compositional differences (occurrence of P together with Ca,
Al, Fe in zhamanshinite). However, this is not surprising since
all the high-silica melts, whatever their composition, are char-
acterized by immiscibility features (Hess, 1977).
We were aware of the possible instability of glass under the
electron beam (Howitt et al., 1988; Zolensky and Koeberl,
1991), and we therefore constantly checked samples to deter-
mine whether the spherical glass inclusions evolved with in-
creasing electron exposure. We conclude that the observed
texture is not induced by electron beam exposure.
3.2. TEM-EDS analyses
3.3. Graphite inclusions
Rare carbon-bearing inclusions randomly occur within the
silica-glass matrix (Figs. 4a, b and c). Their presence is ubiq-
uitous and not limited to the regions with dark streaks.
C-bearing inclusions produce an evident C peak in the EDS
spectra. The inclusions consist of ring-shaped polygonalized
ribbons, 5–50 nm thick, typically forming closed structures
with an overall diameter of ⬃200 nm. Their SAED patterns
(inset, Fig. 4d) consist of rings with d-spacings of 3.35, 2.09
and 1.67 Å: these values correspond to graphite (3.36, 2.13-
2.03, 1.678 Å, JCPDS 23-64). Lattice imaging shows 3.35 Å
polygonized (002) lattice fringes (Figure 4d). The fringes are
quite regular, thus indicating good structural order with no
evidence of deformation or defects. Dark vertical bands are
evident at the polygonal edges and are interpreted as Moiré
textures.
Similar features have been already described by Buseck and
Huang (1985). These authors have studied the structural evo-
lution with temperature (in terms of ribbon width, dislocation
frequency, regularity and planarity of lattice fringes, SAED) of
poorly-crystalline carbonaceous material to well-crystallized
graphite.

The Libyan Desert Glass matrix mostly consists of contrast-

free, homogeneous silica-glass. Selected area electron diffrac-
tion (SAED) shows no diffraction effects (neither spots nor
rings) and confirms that, at the TEM scale, the glass is not
affected by devitrification. At first glance, EDS analyses reveal
quite a homogeneous composition for this glass matrix which
mainly consists of SiO2 plus minor amounts of Mg, Al and Fe
(Table 1). The mean composition (obtained over 12 analyses
from different LDG grids and expressed as atomic percentages)
is O 63.3, Si 35.6, Mg 0.4, Al 0.5, Fe 0.2.
Nanochemical data for the spherules are variable (Table 1).
Data indicate that the spherules are definitely Al-, Fe- and
Mg-enriched with respect to the matrix and also slightly Ca-,
Ti-, Cr- and Ni-enriched. Variation diagrams reveal that Al, Fe
and Mg are positively correlated (Fig. 3).
4. DISCUSSION
4.1. Chemical composition of the glass spherules
The variability observed in TEM-EDS data (Table 1) does
not correspond to actual chemical variability among the differ-
ent spherules but arises from analytical contamination by the
surrounding silica-glass matrix. Spherule composition can be
estimated considering that analyses derive from two sources:
the silica-glass matrix and the actual Al-, Fe- and Mg-enriched
compositions. By plotting Al ⫹ Fe ⫹ Mg vs. Si (Fig. 5), two
extreme compositions are identified: the silica-glass matrix
itself and spherule analysis n°1. The latter analysis was ob-
tained from a spherule located on the rim of the hole resulting
from ion bombardment and presumably represents the purest
906 G. Pratesi, C. Viti, C. Cipriani, and M. Mellini
Fig. 3. a) Fe vs. Mg, b) Mg vs. Al and c) Fe vs. Al contents,
expressed as atomic percentages. Open squares refer to the silica-glass
matrix, filled circles refer to TEM-EDS analyses (best possible focus on
the guest spherules).
composition for the dark particles. Other analyses plot along a
mixing line and represent variable contamination by the silica-
glass matrix. This interpretation is further supported by X-ray
semi-STEM maps for Mg, Al and Fe (Fig. 6) which show that
these elements are mainly concentrated within the spherules.
Due to the small size and contamination, we were unable to
identify possible chemical differences between large and small
spherules.
Similar results were obtained by Fudali (1981) for Al, Fe and
Ti; however, this author reports that the presence of Mg is very
limited and only correlated with Fe, strongly suggesting a
precursor Mg-Fe oxide or silicate.
4.2. Liquid immiscibility and high temperature origin
Immiscibility in impact glasses has already been described in
literature. Dence et al. (1974) observed spheroids filled with
montmorillonite or, rarely, with calcite or silica in the West
Clearwater Lake glass. Zolensky and Koeberl (1991) found 100
nm-diameter inclusions of a separate Ca-Fe-Mg-P-rich silicate
glass in blue zhamanshinites. Microcrystalline tagamites from
the Popigai crater contain globular glasses which are inter-
preted as products of impact anatexis (Vishnevsky and Mon-
tanari, 1999). Graup (1999) observed carbonate-silicate liquid
immiscibility in the glass from the Ries Crater. Textural fea-
tures indicating silicate-silicate liquid immiscibility were pre-
viously described by Oberdorfer (1905) for the Ries suevite; he
observed dark brown glass differentiating as spherical bodies
from light brown glass.
The examined LDG particles also seem to derive from sili-
cate-silicate liquid immiscibility; they display an emulsion tex-
ture consisting of spherules of one melt in a matrix of another
melt (Treiman and Essene, 1985). Whereas the immiscibility
texture of the Ries suevite (Graup, 1999) consists of deformed
and coalescing spheres, that of the LDG consists of regularly
shaped spherules. The regular shape rules out deformation
effects and indicates similar viscosities for the two silicate
liquids. In fact, when immiscibility occurs in silicate-carbonate
liquids, the large viscosity difference between unpolymerized
carbonate and highly polymerized silicate melts produces de-
formation of the carbonate droplets with formation of cusps
(Treiman and Schedl, 1983). According to Freestone and Pow-
ell (1983), the absence of cuspate boundaries may also be
related to the low number of crystals. They observed that when
crystalline phases are abundant there is considerable distortion
of the droplets and cuspate boundaries occur.
As reported by Wolf and McMillan (1995), the response of
silicate melts to pressure is variable. Low-silica melts undergo
densification with increasing pressure; their fluidity decreases
as does atomic diffusion. Conversely, the viscosity of high-
silica liquids decreases with increasing pressure, thus leading to
an increase in atomic diffusion. In the system K2O-FeO-Al2O3-
SiO2-CO2 increasing pressure favors liquid immiscibility
(Watson and Naslund, 1977). Although impact melts may form
under high pressure conditions, they cool under major decom-
pression (Zolensky and Koeberl, 1991). The effect of pressure
on the silicate-silicate liquid immiscibility of the LDG may
therefore not be important; however, pressure could have
played a role in favoring diffusivity of network ions. The
“anomalous” pressure-dependent behavior in atomic diffusivity
of high-silica liquids might account for the irregular distribu-
tion of immiscibility in LDG. Moreover, the presence of five-
coordinated aluminum in LDG, detected by Pratesi et al. (2001)
employing the 27Al NMR-MAS technique, suggests that this
coordination could be an important intermediate state which
 Liquid immiscibility in Libyan desert glass 907

Fig. 4. a, b and c) Polygonyzed graphite packets in LDG (note that in panels a and b, graphite occur in spherules-free
glass, whereas in panel c it is associated with dark spherules). d) Polygonized (002) lattice fringes (spacing of 3.35 Å) of
graphite. The inset shows the corresponding electron diffraction pattern.
908 G. Pratesi, C. Viti, C. Cipriani, and M. Mellini
Fig. 5. Si vs. Mg ⫹ Al ⫹ Fe contents, expressed as atomic percent-
ages. Data identify a mixing line whose extremes correspond to the
silica-glass matrix and to the purest spherule composition (an.1 of
Table 1).
facilitates ion exchange (Wolf and McMillan, 1995 and refer-
ences therein).
Associated phases have been reported in several natural and
experimental occurrences of liquid immiscibility. In the Ries
glass, glass vesicles are more abundant when associated with
mineral debris (Engelhardt, 1972). In the Clearwater glass, the
spheroids have no apparent relationship to any inclusions but
lechatelierite (Dence et al., 1974). Greig (1927) experimentally
found cristobalite, formed during cooling, associated with the
least siliceous of the two immiscible liquid phases. Wood and
Hess (1980) report that at 1440°C cristobalite coexists with an
immiscible liquid pair. In the LDG we observed macroscopic
cristobalite grains along the dark streaks.
Fig. 6. X-ray semi-STEM images showing the heterogeneous distribution of magnesium, aluminum and iron across LDG;
these elements are mainly concentrated in the dark spherules (spherule size as in Fig. 2).
The high temperature origin of LDG was previously sup-
ported by the discovery of the high-temperature silica poly-
morphs cristobalite and lechatelierite (the latter requires a min-
imum formation temperature of 1713°C) and of baddeleyite
ZrO2, a breakdown product of zircon at temperatures higher
than 1676°C (Kleinmann, 1969; Storzer and Koeberl, 1991).
The temperature range experienced by LDG is much higher
than liquidus temperatures of any common igneous rock. Ex-
periments on dry SiO2-rich melts (Greig, 1927) show that during
cooling at atmospheric pressure, two immiscible liquids separate
between 2100° and 1700°C. The first is a nearly pure SiO2
melt, while the composition of the second is about 70% SiO2.
Silicate-silicate fluid immiscibility (Wood and Hess, 1980)
arises from the conflict between enthalpy and entropy. Cations
in the silicate melt are surrounded by oxygen coordination
polyhedra which minimize intercationic electrostatic repulsion.
Depending on the tendency to polymerize, cations are “network
formers” (primarily Si4⫹) or “network modifiers”. The random
distribution of network-modifier cations lowers free energy by
increasing configurational entropy. The higher the temperature,
the larger the contribution of configurational entropy. However,
a random distribution results in a structure having cations screened
by only a small number of non-bridging oxygens. This repulsive
term leads to increasing enthalpy (Hess, 1977). When enthalpy
prevails (i.e., at low temperatures), minimal free energy is
achieved by the separation of two coexisting liquids: the first
one SiO2-rich and poor in network-modifier cations, the second
one SiO2-poor and enriched in network-modifier cations.
Liquid immiscibility like that of LDG was predicted by Hess
and Rutherford (1975) and Wood and Hess (1980). Namely,
cations of higher field strength (including Mg2⫹, Fe2⫹ and
Al3⫹) are concentrated in the less polymerized melt. Although
 Liquid immiscibility in Libyan desert glass
Al may prefer SiO2-rich melts in some natural immiscible
melts (Roedder and Weiblen, 1972; Hess and Rutherford,
1975), its role as a network-forming cation in LDG is limited
by low concentrations (Pratesi et al., 2001). Although Al is
present in lower concentrations even in the SiO2-rich matrix of
LDG (Fig. 6 and Table 1), it is preferentially partitioned in
spherules as a network modifier. A similar behavior was pre-
viously observed by Wood and Hess (1980); their results show
that at 1440 °C, Al2O3 prefers SiO2-poor melts. These studies
suggest that partitioning is due to the absence of charge-
balancing monovalent or divalent cations in the silica-rich
glass. This limits AlO4 solubility and accounts for the sharp
compositional difference between silica-rich glass and spherule
glass. The presence of small amounts of aluminum in the
silica-rich matrix can be explained if one considers that Al can
behave both as network-former and a network-modifier cation.
The faint bluish color of some LDG samples probably results
from scattering of light according to the Tyndall effect (or
Rayleigh scattering). This phenomenon is responsible for the
blue color of some zhamanshinites (Zolensky and Koeberl, 1991).
It arises when sufficiently small particles are present; the smaller
size of inclusions in some samples can therefore account for the
faint bluish color present in a few LDG samples. According to
Zolensky et al. (1988), inclusions ⱕ60 nm in diameter produce
the blue color effectively, while particles ⱖ100 nm are too
large to produce a blue color by Rayleigh scattering.
4.3. Graphite ribbons
Carbon compounds in LDG were previously reported by Jux
(1983); he found saturated and unsaturated hydrocarbons with
8 to 26 carbon atoms, especially in the brown streaks. This
finding has been questioned by Rocchia et al. (1996). Accord-
ing to our observations, carbon does occur in LDG but as
graphite ribbons rather than hydrocarbons.
The source of the carbonaceous material in the graphite
ribbons is not known. The target rocks (Lower Cretaceous
sandstone of the Nubia Group) may have contained carbon, but
Abate et al. (1999) found no trace. Alternatively, the impactor
(meteorite or cometary body) may have contained carbon. As
for the present state of this material, HRTEM images indicate
a high degree of crystallinity which is not compatible with the
unmodified, amorphous or poorly crystalline carbon typical of
sedimentary rocks. Conversely, it suggests impact-related an-
nealing effects. Buseck et al. (1987) demonstrated that carbon
becomes structurally ordered following heating. In their exper-
iments, ribbons or polygonal structures similar to those under
examination and characterized by well-developed layers that
look like graphite, formed by one hour long thermal treatments
at 2500°C. In our case temperatures did not exceed 2230°C, as this
temperature would determine silica vaporization. The occurrence
of lechatelierite and baddeleyite (Kleinmann, 1969; Storzer and
Koeberl, 1991) and of immiscibile liquids (Greig, 1927) further
constrain the temperature range of LDG to 1700 –2100°C.
As several types of carbon polymorphs occur in terrestrial
impact rocks (graphite, diamond, fullerenes and carbynes),
carbon may constrain the shock conditions in impact processes
(Gilmour, 1998). Experimental calibrations (Bundy, 1989) in-
dicate that in the 1700 – 2100°C range, graphite transforms into
diamond at pressures higher than 5–7 GPa. Therefore the
909
occurrence of graphite (if it is primary) seems to suggest that
the pressure was within the 5–7 GPa range. However, it cannot
be excluded also that the graphite is secondary. If this is so,
then pressure could have been higher, diamond could have been
formed, and, successively, because of decreasing pressure cou-
pled with the maintenance of high temperatures, the diamond
could have been converted back to graphite, as observed at the
Popigai crater by Masaitis (1998).
4.4. Precursor rock
The most likely precursor rocks for LDG are the Lower
Cretaceous sandstones of the Nubia Group (Abate et al., 1999).
They consist of quartz grains locally associated with a mixture
of kaolinite, Fe-Ti oxides and accessory phases (e.g., Fudali,
1981, Barrat et al., 1997).
Our TEM-EDS data agree with this proposal. In particular,
the high Al content (already mentioned by Barrat et al., 1997)
is reasonably inherited from terrestrial sources, in particular
from the kaolinite-rich sediments in the quartz arenite.
As for major elements, no chemical evidence for a meteoritic
or cometary component is revealed by the low-sensitivity
TEM-EDS analyses. We note, however, that several authors
have measured significant amounts of platinum-group elements
(PGE) in the dark streaks of the LDG (e.g., Koeberl, 1997;
Murali et al., 1997).
5. CONCLUSIONS
a) The dark streaks in the Libyan Desert Glass do not consist
of crystalline debris (as previously supposed) but of unmixed
silicate melt drops. TEM investigation of the dark (brown or
bluish) streaks revealed the common presence of small glass
spherules homogeneously dispersed within the silica-glass ma-
trix. The spherules are Al-, Fe- and Mg-enriched with respect to
the surrounding silica matrix, and their (Mg ⫹ Al ⫹ Fe):Si
ratio is close to 1.
b) Silica-glass matrix and amorphous spherules form an
emulsion texture which originates from silicate-silicate liquid
immiscibility. This feature indicates quenching from high tem-
peratures ranging from 1700 to 2100 °C. Quenching preserved
the two pristine immiscible phases.
c) Carbonaceous inclusions of polygonized graphite ribbons
are found in the silica glass. Their presence limits pressures to
below 5–7 GPa but only if they are primary.
d) On the whole, evidence indicates an impact origin for
Libyan Desert Glass.
Acknowledgements—We express our gratitude to Drs. Alain Carion,
Vincenzo de Michele and Romano Serra for kindly providing the
Libyan Desert Glass samples containing dark streaks. We also ac-
knowledge the associated editor Prof. C. Koeberl and the two referees,
Dr. M.E. Varela and Dr. M. Zolensky, for useful suggestions. Research
was supported by grants from the University of Florence (ex 60%).
Associate editor: C. Koeberl
REFERENCES
Abate B., Koeberl C., Kruger F. J., Underwood J. R. Jr. (1999) BP and
Oasis impact structures, Libya, and their relation to Libyan Desert
Glass. In Large Meteorite Impacts and Planetary Evolution II (eds.
Dressler, B. O. and Sharpton, V. L.), Geological Society of America
Special Paper 339, 177–192.
910 G. Pratesi, C. Viti, C. Cipriani, and M. Mellini
Barakat A. A., de Michele V., Negro G., Piacenza B. and Serra R.
(1997) Some new data on the distribution of Libyan Desert Glass
(Great Sand Sea, Egypt). In Silica ’96 (ed. V. de Michele) Proceed-
ings of Meeting on Libyan Desert Glass and related desert events:
Milan, Italy, Pyramids, 29 –36.
Barnes V. and Underwood, J. R. Jr. (1976) New investigation of the
strewn field of Libyan desert glass and its petrography. Earth Planet.
Sci. Lett. 30, 117–122.
Barrat, J. A., Jahn, B. M., Amosse, J., Rocchia, R., Keller, F., Poupeau,
G. R. and Diemer, E. (1997) Geochemistry and origin of Libyan
Desert glasses. Geochim. Cosmochim. Acta 61, 1953–1959.
Bigazzi G. and de Michele V. (1996) New fission-track age determi-
nation on impact glasses. Meteoritics and Plan. Sci. 31, 234 –236.
Bundy F. P. (1989) Behaviour of elemental carbon up to very high
temperatures and pressures. In High Pressure Science and Technol-
ogy. Proceedings XI Airapt International Conference, I, Kiev,
Naukova Dumka Press, 326 –336.
Buseck P. R. and Huang B.-J. (1985) Conversion of carbonaceous
material to graphite during metamorphism. Geochim. Cosmochim.
Acta 49, 2003–2016.
Buseck P. R., Huang B.-J. and Keller L. P. (1987) Electron Microscope
Investigation of the Structures of Annealed Carbons. J. Energy &
Fuels 1, 105–110.
Clayton P. A. and Spencer L. J. (1933) Lecture on the Libyan Desert
Glass presented on the 9 November 1933 at the Anniversary meeting
of the Mineralogical Society. Nature 278.
Cliff G. and Lorimer G. W. (1975) The quantitative analysis of thin
specimens. J. Microscopy, 103, 203–207.
De Michele V. (1998) The “Libyan Desert Glass” scarab in Tutankha-
men’s pectoral. Sahara 10, 107–109.
Dence M. R., Engelhardt W. v., Plant A. G., Walter L. S. (1974)
Indications of Fluid Immiscibility in Glass from West Clearwater Lake
Impact Crater, Quebec, Canada. Contrib. Mineral. Petrol. 46, 81–97.
Diemer E. (1997) Libyan Desert Glass: an impactite. State of the art in
July 1996. In Silica ’96 (ed. V. de Michele) Proceedings of Meeting
on Libyan Desert Glass and related desert events: Milan, Italy,
Pyramids, 29 –36.
Engelhardt W. v. (1972) Shock produced rock glasses from the Ries
crater. Contrib. Mineral. Petrol. 36, 265–292.
Feller M. (1997) Vitreous silica from the Sahara. In Silica ’96 (ed. V.
de Michele) Proceedings of Meeting on Libyan Desert Glass and
related desert events: Milan, Italy, Pyramids, 111–114.
Freestone I. C. and Powell R. (1983) The low-temperature field of
liquid immiscibility in the system K2O-Al2O3-FeO-SiO2 with special
reference to the join fayalite-leucite-silica. Contrib. Mineral. Petrol.,
82, 291–299.
Fudali R. F. (1981) The major element chemistry of Libyan Desert
Glass and the mineralogy of its precursor. Meteoritics 16, 247–259.
Futrell D. S. and O’Keefe J. A. (1997) A brief discussion of the
petrogenesis of Libyan Desert Glass. In Silica ’96 (ed. V. de
Michele) Proceedings of Meeting on Libyan Desert Glass and related
desert events: Milan, Italy, Pyramids, 115–120.
Gilmour I. (1998) Geochemistry of carbon in terrestrial impact pro-
cesses. In Meteorites: Flux with Time and Impact Effects (eds. Grady
M.M., Hutchison R., McCall G.J.H. & Rothery D.A.). Geological
Society, London, Special Publications 140, 205–216.
Graup G. (1999) Carbonate-silicate liquid immiscibility upon impact
melting, Ries Crater, Germany. Meteoritics and Plan. Sci. 34, 425– 438.
Greig J. W. (1927) Immiscibility in silicate melts. Am. J. Sci. 73, 1– 44
(Part I) and 133–154 (Part II).
Hess P. C. (1977) Structure of silicate melts. Canad. Mineral. 15,
162–178.
Hess P. C. and Rutherford M. J. (1975) Element fractionation between
immiscible [abs.]. In Lunar Science V, pp. 328 –329. Houston: Lunar
Science Institute.
Horn P., Müller-Sohnius D., Schaaf P., Kleinmann B. and Storzer D.
(1997) Potassium-argon and fission-track dating of Libyan Desert
Glass, and strontium and neodymium isotope constraints on its
source rocks. In Silica ’96 (ed. V. de Michele) Proceedings of
Meeting on Libyan Desert Glass and related desert events: Milan,
Italy, Pyramids, 59 –73.
Howitt D. G., Medlin D. L. and Walker T. M. (1988) Radiation induced
signal losses in analytical electron microscopy. Elect. Microsc. Soc.
Amer. Bull. 18, 69 –74.
Jux U. (1983) Zusammensetzung und Ursprung von Wüstengläsern aus
der Gro␤en Sandsee Ägyptens. Zeitschrift der deutschen geologis-
chen Gesellschaft 134, 521–553.
Kleinmann B. (1969) The breakdown of zircon observed in the Libyan
Desert Glass as evidence of its impact origin. Earth Planet. Sci. Lett.
5, 497–501.
Koeberl C. (1997) Libyan Desert Glass: geochemical composition and
origin. In Silica ’96 (ed. V. de Michele) Proceedings of Meeting on
Libyan Desert Glass and related desert events: Milan, Italy, Pyra-
mids, 121–131.
Masaitis V. L. (1998) Popigai crater: Origin and distribution of dia-
mond-bearing impactites. Meteoritics and Plan. Sci. 33, 349 –359.
Murali A. V., Zolensky M. E., Underwood J. R. Jr and Giegengack
R. F. (1990) Cometary signatures in the Libyan Desert Glass. EOS
Trans. Am. Geoph. Un. 71, 43, 1425.
Murali A. V., Zolensky M. E., Underwood J. R. Jr and Giegengack
R. F. (1997) Chondritic debris in Libyan Desert Glass. In Silica ’96
(ed. V. de Michele) Proceedings of Meeting on Libyan Desert Glass
and related desert events: Milan, Italy, Pyramids, 133–142.
Negro G. and Damiano-Appia M. (1992) II “Silica Park”: un centro di
lavorazione del LDSG nel Great Sand Sea. Sahara 5, 105–108.
Oakley K. P. (1952) Dating the Libyan Desert Silica Glass. Nature 170,
447– 449.
Oberdorfer R. (1905) Die vulkanischen Tuffe des Ries bei Nördlingen.
Jahreshefte Verein für vaterländische Naturkunde Württemberg 61,
1– 40.
Pratesi G., Capitani D., Cipriani C., Giuli G., and Ziarelli F. (2001) A
29
Si-27Al magic-angle spinning NMR study of natural silica glass
from the Libyan desert (Egypt). J. Non-Cryst. Solids 279, 88 –92.
Rocchia R., Robin E., Froget L., Méon H., Gayraud J. and Diemer E.
(1995) The meteoritic content of Libyan Desert Glasses. Lun. Planet.
Sci. Conf. XXVI, 1179 –1180.
Rocchia R., Robin E., Fröhlich F., Méon H., Froget L. and Diemer E.
(1996) L’origine des verres du Désert Libyque: un impact météori-
tique. Comp. Rend. Acad. Sci. Paris 322, 839 – 845.
Rocchia R., Robin E., Fröhlich F., Amosse J., Barrat J.-A., Méon H.,
Froget L. and Diemer E. (1997) The impact origin of Libyan Desert
Glass. In Silica ’96 (ed. V. de Michele) Proceedings of Meeting on
Libyan Desert Glass and related desert events: Milan, Italy, Pyra-
mids, 143–149.
Roe D. A., Olsen J. W., Underwood Jr. and Giegengack R. F. (1982)
A handaxe of Libyan Desert Glass. Antiquity LVI, 88 –92.
Roedder E. and Weiblen P. W. (1972) Petrology of melt inclusions
Apollo 11 and Apollo 12 and terrestrial equivalents. Proc. Lunar.
Sci. Conf. 2th, 507–528.
Seebaugh W. R. and Strauss A. M. (1984) A cometary impact model for
the source of Libyan Desert glass. Journ. Non-Cryst. Solids 67, 511–519.
Storzer D. and Koeberl C. (1991) Uranium and zirconium enrichments
in Libyan Desert Glass. Zircon, baddeleyite and high temperature
history of the glass. Lunar Planet. Sci. XXII, 1345–1346.
Storzer D. and Wagner G. A. (1977) Fission-track dating of meteorite
impacts. Meteoritics 12, 368 –369.
Treiman A. H. and Essene E. J. (1985) The Oka carbonatite complex,
Quebec: geology and evidence for silicate-carbonate liquid immis-
cibility. Amer. Mineral. 70, 1101–1113.
Treiman A. H. and Schedl A. (1983) Properties of carbonatite magma and
processes in carbonatite magma chambers. J. Geol. 91, 437– 447.
Vishnevsky S. and Montanari A. (1999) Popigai impact structure
(Arctic Siberia, Russia): Geology, petrology, geochemistry, and
geochronology of glass-bearing impactites. In Large Meteorite
Impacts and Planetary Evolution II (eds. Dressler, B. O. and
Sharpton, V. L.), Geological Society of America Special Paper
339, 19 –59.
Wasson J. T. and Boslough M. B. E. (2000) Large aerial bursts; an
important class of terrestrial accretionary events. In Catastrophic
Events and Mass Extinctions: Impacts and Beyond, p. 239 –240. LPI
contribution n. 1053, Lunar and Planetary Institute, Houston.
Watson E. B. and Naslund H. R. (1977) The effect of pressure on liquid
immiscibility in the system K2O-FeO-Al2O3-SiO2-CO2. Geophys.
Lab. Carnegie Inst. Yrbk. 1976, 410 – 414.
 Liquid immiscibility in Libyan desert glass 911

Weeks R. A., Underwood J. R. Jr and Giegengack R. (1984) Libyan
Desert glass: A review. J. Non-Cryst. Solids 67, 593– 619.
Wolf G. H. and McMillan P. F. (1995) Pressure effects on silicate melt
structure and properties. In Structure, dynamics and properties of
silicate melts (eds. Stebbins J. F., McMillan P. F. and Dingwell
D. B.), Mineralogical Society of America, Reviews in Mineralogy
32, 505–561.
Wood M. I. and Hess P. C. (1980) The structural role of Al2O3 and
TiO2 in immiscible silicate liquids in the system SiO2-MgO-CaO-
FeO-TiO2-Al2O3. Contrib. Mineral. Petrol. 72, 319 –328.
Zolensky M. E. and Koeberl C. (1991) Why are blue zhamanshinites
blue? Liquid immiscibility in an impact melt. Geochim. Cosmochim.
Acta 55, 1483–1486.
Zolensky M. E., Sylvester P. J. and Paces J. B. (1988) Origin and
significance of blue coloration in quartz from Llano rhyolite (Ilanite),
north-central Llano County, Texas. Amer. Mineral. 73, 313–323.