Bull. Mater. Sci., Vol. 31, No. 2, April 2008, pp. 155–158. © Indian Academy of Sciences.

Fourier–transform infrared spectroscopic characterization of natu-

rally occurring glassy fulgurites

B J SAIKIA†, G PARTHASARATHY*, N C SARMAH† and G D BARUAH†

National Geophysical Research Institute, Uppal Road, Hyderabad 500 007, India
†
Department of Physics, Dibrugarh University, Dibrugarh 786 004, India

MS received 7 August 2007

Abstract. We report here for the first time the spectroscopic characterization of natural fulgurites of Garua-
mukh. On April 22, 2005 at 04 : 00 local time, large amounts of black-brown colour of colloidal solution came
out from below the earth’s surface at Garuamukh near Nagaon town (latitude 26°20′39″N, longitude
92°41′39″E, Assam, India) with fire and smoke. This colloidal solution got transformed into fulgurites, glassy
material, within a few hours. We present here the characterization of the fulgurites by Fourier transform in-
frared (FTIR) absorption, X-ray diffraction and X-ray fluorescence methods. The amorphous nature of the
substance has been confirmed by Fourier transform infrared spectra of the fulgurites, which exhibit promi-
nent absorption band in the region 400–1200 cm–1, the basic component of amorphous silica. The present study
might have significant implications in understanding the thermodynamic properties of naturally occurring
glasses, which are formed by shock metamorphism.

Keywords. Glasses; infrared spectroscopy; fulgurites.

1. Introduction glass-lined tubes with sand adhering to the outside. Rock

fulgurites are formed when lightning strikes the bare sur-
Natural glass on Earth occurs due to either meteorites face of rocks. Rock fulgurites are relatively low in silica
impact or lightning strike. The glass formed as a result of and exhibit a wide variety of colours, depending on the
the collision of a meteorite with the Earth’s surface is composition of the host rock. Each cloud-to-ground light-
called meteoritic glass or tektite (Carron and Lowman ning involves energy of about 109–1010 Joules. The peak
1961; Essen and Fisher 1986). Glass (a glassy object, to temperature of lightning channel is in the order of 30,000 K,
be exact) that is made as a result of a cloud-to-ground which is five times higher than the surface temperature of
lightning discharge is called a fulgurite, from the Latin the Sun. The process of lightning strike in rock and sand
word ‘fulgur’ which means lightning. It is worth noting that is chemically similar to the micrometeorite impacts (Sheffer
lechatelierite (natural silica glass) is not present in obsidian, et al 2006). In both cases there is a rapid rise of tempera-
a glass-like material associated with volcanic activity. On ture followed by a rapid cooling. The peak temperature of
the other hand, lightning strikes on sandy soil may pro- lightning is in between 1900 and 2300 K depending on
duce fulgurites (Yavuz and Can 1999). Such a silica- moisture content, which is higher than the melting point
based natural glass has also been produced at the nuclear of silica. Since all rocks and soil contain silica, so at this
explosion sites. The mineralogical composition (lechatelirite, high temperature silica melts and passes through a relati-
cristobalite, chalcedony, opal) of fulgurites is related to vely rapid cooling which causes the glass to solidify.
the palaeo-environmental conditions of the semi-arid re- Jayakaran (1998) reported the occurrence of fulgurites in
gions and to the melting conditions during the fulgurite Udhiyur, Tamil Nadu, in a short note. However, there are
forming lightning strike to the ground (Sponholz 2004). no previous reports on any physical properties studies on
Fulgurites are also very resistant to weathering and hence Indian fulgurites.
the study of properties of fulgurites may be helpful in On April 22, 2005 at 04 : 00 local time, large amounts
understanding the ultra-high temperature natural pheno- of black-brown fulgurites were formed at Garuamukh near
mena during lightning (Clocchiatti 1990). Nagaon town (latitude 26°20′39″N, longitude 92°41′39″E,
There are two major types of fulgurites: sand fulgurites Assam, India). The melt formed on the earth’s surface
and rock fulgurites. Sand fulgurites are usually hollow, with fire and foul odour smoke and the upper part of it
gradually solidified. The solid material has been found to
have a temperature of about 350 K even after a lapse of
*Author for correspondence ([email protected]) two days after occurrence of the event whereas the room

155
156 B J Saikia et al

Table 1. Comparison of chemical compositions of the Garuamukh fulgurites with other fulgurites.
Garuamukh (G-01) Garuamukh (G-02) Garuamukh (G-03) Germany New Jersey Illinois Holland

SiO2 97⋅5 96⋅8 97⋅2 93⋅8 99⋅0 91⋅66 90⋅2

Fe2O3 0⋅6 0⋅8 0⋅7 – 0⋅3 – 0⋅7
Al2O3 1⋅4 2⋅0 1⋅6 3⋅8 0⋅7 6⋅69 0⋅9
TiO2 0⋅5 0⋅3 0⋅6 – – – –
CaO – – – 0⋅6 – 0⋅38 0⋅1
MgO – – – – – 0⋅12 0⋅5
Na2O – – – – – 0⋅77 0⋅6
K2O – – – – – 0⋅73 0⋅5
Note: The data for Germany, New Jersey, Illinois and Holland are taken from Frondel (1962).

Figure 1. X-ray diffraction pattern of the Garuamukh fulgurites sample.

temperature during that period was 300 ± 5 K. The aim of Hyderabad, India. In X-ray fluorescence method, typical
this study is to analyse FTIR spectra of the sample with uncertainty involved in oxide analyses was about 0⋅01 wt%.
reference to 10 μm and 20 μm bands, because these ab- One part of the sample was crushed into fine powder for
sorption bands at middle infrared wavelengths detected the analysis. The powdered sample was homogenized in
valence vibrations or deformation vibration of SiO4 tetra- spectroscopic grade KBr (1 : 20) in an agate mortar and
hedrons in silicate. The spectral characteristics of the pressed into 3 mm pellets with a hand press. We tried to
fulgurites would be helpful in determining the peak shock minimize the grinding time to avoid the deformation of
temperature by identifying high-temperature phase of the crystal structure, the ion exchange and the water absorp-
silica. The present study describes, for the first time, the tion from atmosphere. The infrared spectra was acquired
FT–IR spectroscopic characterization of the fulgurites using Perkin-Elmer system 2000 FTIR spectrophotometer
found at Garuamukh. at Guwahati University, Guwahati, India, with helium–neon
as the reference, at a resolution of 4 cm–1. The spectra
were taken in the region 400–4000 cm–1. The room tem-
2. Experimental
perature was 30°C during the experiment.
The glassy nature of the samples were confirmed by powder
X-ray diffraction (XRD) analysis, by using the Philips 3. Results and discussion
PW 3710 XRD system which was operated at 40 KV and
45 mA, with a CuKα (λ = 1⋅54 Å) radiation and a graphite Sand fulgurites are usually created when lightning strikes
monochromator. The composition of the fulgurites was the Earth and locally melts quartz sand, and the sand is
determined by using a Philips X-ray fluorescence (XRF) instantly heated up to ultra high-temperatures (air tempe-
machine at the National Geophysical Research Institute, ratures may temporarily reach 10,000–30,000° Celcius)
 FT–IR characterization of naturally occurring glassy fulgurites 157

and fulgurites can then form, tracing the path the light- tions of the natural fulgurites sample from Garuamukh
ning took, generally decreasing in diameter and sometimes and their comparison with earlier data on fulgurites pro-
branching as they descended. Fulgurites often take the duced by lightning. The absence of diffraction peaks in
form of tubes, sometimes exceeding 30 mm or more in the broad pattern indicates that quartz is amorphous or
diameter, and are known to exceed 8 meters in length glassy. The spectrum shows a slope of peak around 23°
(although this great length makes their recovery as a whole corresponding to the amorphous matrix of SiO2. The
impossible as they are extremely fragile). The outer sur- overall pattern is that of amorphous silica. The sharp
faces are often rough with adhering, unfused quartz sand peaks observed in XRD (figure 1) are due to the presence
grains. If they are tubular, the inner surfaces are usually of crystalline quartz as impurities.
smooth and glassy. Because of the rare occurrence, typical The FTIR spectrum reveals a few absorption bands.
fulgurites cost from 50–150 US dollars.The XRF results The groups of bands in the region 400–700 cm–1 and 800–
show the major component of the sample to be SiO2. The 1175 cm–1 are assigned as 20 μm and 10 μm, respectively.
results are compared with that of the previous work on In the Si–O stretching vibration region (800–1175 cm–1),
fulgurites found elsewhere in similar geological settings the bands at 787, 952, 1069, 1170 cm–1 are identical to the
(Frondel 1962). Table 1 shows the chemical composi- bands at 800, 958, 1088 cm–1 due to amorphous silica
(Ojama 2003). The 10 μm and 20 μm bands of Garua-
mukh fulgurites and the amorphous silica is shown in
figure 2. It is seen that the characteristic frequencies
slightly differ but the relative intensities vary in both sili-
cates. Amorphous silica exhibited a relatively strong peak
at 800 cm–1 and it can be distinguished from the band of
crystalline silicate (Ojama 2003).
The structure of most SiO2 polymorphous, both crystal-
line and amorphous, is based on tetrahedral unit of silicon
coordinated to four oxygen atoms. Amorphous silica is
one of the polymorphous of silica and at high temperature
it can easily transform from quartz. In the Si–O–Si bend-
ing vibration region (400–700 cm–1) of quartz, the band at
695 cm–1 is determinative whether it is crystalline or
amorphous (Parthasarathy et al 2001). In the amorphous
state this band will be missing. In the fulgurites sample,
we did not get 695 cm–1 peak which indicates that the
silica mineral in this sample is in amorphous form. The
absorption band at 695 cm–1 is due to the vibrations in
octahedral site symmetry and at 780 cm–1, it is due to the
Figure 2. Comparison of FT–IR spectra of the natural fulgu- vibration in tetrahedral site symmetry (Schneider 1974;
rites sample (A) and the spectra of the amorphous silica (B) Parthasarathy et al 2001). The tetrahedral symmetry is
(Ojima 2003) in the 20 μm (500 cm–1) and 10 μm (1000 cm–1) stronger than that of octahedral symmetry. Therefore, for
regions. any structural change, the damage occurs first in octahe-
dral then in tetrahedral symmetry. When the temperature
Table 2. The observed absorption frequencies (cm–1) of Fou-
rier transform infrared spectra of the natural fulgurites and the
assignments.
Wave number (cm–1) Assignments

459 Si–O asymmetrical bending vibration

787 Si–O symmetrical stretching vibration
952 Si–O stretching vibration
1069 Si–O asymmetrical stretching vibration
1170 Si–O asymmetrical stretching vibration
1392–1476 CO23– stretching
1508–1560 CO23– symmetric stretch (ν3)
1635 OH bending vibration
1684–1720 CO23– symmetric stretch (ν3)
2868–2969 C–H stretching vibration
(organic contaminants)
Figure 3. The IR spectra of the natural fulgurites sample from
3452 OH stretching vibration
Garuamukh, Assam (India) in between 400 and 4000 cm–1.
158 B J Saikia et al

generally quenched so rapidly to 600–700°C, the SiO4 be SiO2. The broad Bragg peaks observed in X-ray di-
tetrahedral could not be ordered to crystalline state and ffraction studies reveal that the sample could be nano-
were preserved in an amorphous silicate phase. crystalline quartz. The temperature required for the for-
The transmission FTIR spectrum of the fulgurites sample mation of octahedral symmetry in glassy fulgurites is
is shown in figure 2. The frequencies of IR bands and the found to be much lower than that of crystalline samples.
possible assignments are listed in table 2. In the 20 μm The present characterization study of fulgurites could be
region only one band is found at 459 cm–1 corresponding useful in understanding the short-range order in fulgurites
to the Si–O asymmetrical mode of vibration. The carbo- produced by shock metamorphism.
nate structure contains isolated CO23– group with a doubly
degenerate symmetric stretch (ν3) at the region 1508–
Acknowledgements
1560 cm–1 (Parthasarathy et al 2002). The IR bands at
1684–1720 cm–1 could be assigned to the bending vibra-
We thank Directors of NGRI and IICT, for providing the
tion of H–O–H dissolved volatile species. The bands at
analytical facilities. We also thank Prof. A J Choudhury,
2868–2969 cm–1 could be assigned to stretching vibration
Gauhati University and N K Gogoi, NGRI, for useful
of C–H band which may be introduced during sample
discussions. One of us (GP) is thankful to ISRO, Depart-
handling or some hydrocarbon present in the soil con-
ment of Space, Government of India, for financial support
taminant. The bands at 1392–1476 cm–1 is due to the Na-non-
under PLANEX program.
bridging oxygen–carbonate ion stretching vibration (Na–
NBO–CO3–) (King et al 2004). The speciation of water in
silicate glass formed by rapid quenching from melt References
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1635 cm–1 arise due to adsorbed water molecule commonly Frondel C 1962 in Dana’s system of minerology, ‘Fulgurite’
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