Cretaceous Research 24 (2003) 105–110

Co-existent cristobalite and iridium at 65 Ma, Anjar Intertrappeans,

Kachchh, western India
Dhananjay A. Sant a, George Mathew b, Aniruddha S. Khadkikar c*, V. Gogte d,
T.K. Gundurao e
a
Department of Geology, Faculty of Science, M. S. University of Baroda, 390 002, Vadodara, India
b
Physical Research Laboratory, Navarangpura, 380 009, Ahmedabad, India
c
Geology & Palaeontology Group, Agharkar Research Institute, G.G. Agarkar Road, 411 004, Pune India
d
Department of Archaeology, Deccan College, Postgraduate and Research Institute, 411 006, Pune, India
e
RSIC, Indian Institute of Technology – Bombay, Powai, Mumbai, India

Accepted 6 February 2003

Abstract

Cristobalite (a high-temperature low-pressure silica polymorph) is reported for the first time from the 65 Ma Anjar intertrappean
deposits. It is characterized by a sharp, intense peak (X-ray diffraction) at d-spacing value 4.055Å, followed by a moderate peak at
2.489Å. Its presence is confirmed through Fourier Transform Infrared spectroscopy with absorption bands at 620 and 380 cm
1.
The distribution of volcanic cristobalite coincides with the distribution of iridium in the deposits. When taken in tandem with the
absence of shocked quartz, spinels, stishovite and other signatures of an impact origin, this co-existence suggests that the iridium at
Anjar is probably of volcanic origin.
 2003 Published by Elsevier Ltd.

Keywords: K/T; Deccan; Anjar; Cristobalite; Mineralogy; Meteorite; Iridium

1. Introduction
Since the discovery of a global iridium anomaly at the
Cretaceous/Tertiary boundary, two schools of thought
have evolved (Sutherland, 1994 and references therein).
The meteoritic school explained the iridium anomaly
through an extraterrestrial body impact (Alvarez et al.,
1980). The proof for an extraterrestrial origin came in
the presence of shocked quartz, nickel enriched spinels,
nanodiamonds and stishovite. The alternative hypoth-
esis, the volcanic theory, has been the stronger con-
tender, being supported by the discovery of high iridium
levels in volcanic gases and sublimates (McLean, 1985;
Sutherland, 1994) and the existence of flood basalt
volcanism in India during this time interval. Lately, it
has been realized that these two scenarios may not
strictly be exclusive of each other, especially in view of
* Corresponding author
E-mail address: askhadkikar@yahoo.com (A.S. Khadkikar).
0195-6671/03/$ - see front matter  2003 Published by Elsevier Ltd.
doi:10.1016/S0195-6671(03)00028-4
the fact that both Deccan volcanism and the meteoritic
impact structure have been dated to 65 Ma (Sutherland,
1994). Also, in principle, as both are potential con-
tributors to iridium anomalies (regional or global), it
becomes particularly important to discriminate between
volcanic and meteoritic iridium.
The distinction becomes all-important when its origin
is used to draw critical conclusions on whether or not
the impact induced Deccan Trap volcanism. This is true
for the site at Anjar, western India, where an iridium
anomaly is observed in lacustrine deposits sandwiched
between basalts (i.e. intertrappean beds). This led
Bhandari et al. (1995) to conclude that the terminal
Cretaceous impact had no role in triggering Deccan
volcanism. Subsequent search for a meteoritic signature
(Courtillot et al., 2000) in the form of nickel-rich spinels
yielded negative results. Nonetheless, the presumption
that the iridium (Ir) was extraterrestrial was maintained.
In this paper we report the results of a mineralogical
study of the same sedimentary deposits that contain
106 D.A. Sant et al. / Cretaceous Research 24 (2003) 105–110
Fig. 1. Location map of the Anjar intertrappean site.
cristobalite, a high-temperature low-pressure polymorph
of silica (Heaney, 1994), which commonly forms in
volcanic environments. The abundance of cristobalite
roughly coincides with the Ir peak, suggesting that the
iridium anomaly at Anjar may be of volcanic origin.
2. The intertrappean deposits of Anjar
The Anjar intertrappean succession (Fig. 1) repre-
sents the only sedimentary record that documents the
environmental conditions that existed within the Deccan
volcanic province at the Cretaceous/Tertiary transition
(Upper flow: 64.90.8; Lower flow: 65.70.7 Ma;
Venkatesan et al., 1996). These deposits consist of
interlayered limestone beds and stringers in shales that
contain shell hash, and reflect accumulation in an
alkaline lacustrine environment (Khadkikar et al., 1999;
Fig. 2). Ghevariya (1988) first documented dinosaurian
fossils at a level just below that for which Bhandari et al.
(1995) demonstrated the presence of iridium and trace
element enrichment at several times the background
value. The iridium-rich layers are distinguished by a
reddish-brown to chocolate-brown colouration and have
values of about 1440 pg/g in pit 1, with background
concentrations in the sediment and underlying basalt
between 80 and 200 pg/g (Bhandari et al., 1996) along
with unusually high Os (1414 pg/g) Fe, Co, Sb, Zn, Se,
As, Ag. The upper shale unit (about 1.5 m thick) is
devoid of fossils, cristobalite and anomalous Ir, Os and
platinum group elements. The controversy regarding the
origin of iridium necessitates that such questions be
addressed using evidence other than geochemical to
advocate a meteoritic or volcanic origin.
3. Methodology
For the present study five pits were excavated and
logged in the field. Fig. 2 shows the logs for these pits. A
composite log has deliberately not been constructed
owing to the intricate facies variation in the succession.
Seventy samples were collected at 10-cm intervals of
which 30 were studied in this section under a petro-
graphic microscope. Thirteen samples were analysed
on a Rigaku D max IIvc XRD system, operated at 45 Kv,
30 mA, at a scan speed of 2 min sec
1 for bulk mineralogi-
cal analysis (Fig. 3). Two samples for which we obtained a
high intensity cristobalite peak were further studied with
a step-scan technique with a step-width of 0.03( 2
and a
counting time of 10 s. 2
values were corrected using
silicon (a=5.43088(4)Å) as an internal standard. Those
samples that showed the presence of cristobalite in our
XRD study were further examined using Fourier-
Transform infrared spectroscopy (FT-IR) in order to con-
firm the presence of cristobalite. The spectra were taken
from 2000–360 cm
1 using a Nicolet Magna IR 550
FT-IR spectrometer. Compressed discs were prepared
using the KBr technique with 0.3 mg of sample and
300 mg of KBr. Background effects due to atmospheric
H2O, CO2 and other volatiles were subtracted.
4. Results
Under the petrographic microscope, the various silica
mineral phases are observed as an isotropic groundmass,
microcrystalline quartz and chalcedony (i.e. various
types of chert). Mineralogically these petrographically
distinct forms of silica minerals are quartz or opal-CT.
This has been confirmed by X-ray diffractometry of
chert isolated from the sediments. The other minerals
that have been identified in the deposit are sepiolite,
calcite, goethite and cristobalite, which dominate the
shale and limestone units in pits 1–3 from AS 49 to
AS 30 (Fig. 2, Fig. 3).
Cristobalite first occurs at the base of the section
(AS 49), and becomes increasingly abundant through
AS 43 and AS 39. Thereafter it decreases and finally
disappears above AS 30 (Fig. 3). The upper unit of pit 3
(shale-limestone intercalation) and pits 4 and 5 contain
calcite, quartz, nontronite and palygorskite.
Cristobalite is characterized by a sharp, intense peak
at d-spacing values 4.055Å, followed by a moderate
peak at 2.489Å (Tada & Iijima, 1983; Graetsch et al.,
1994) (Fig. 4A). Weak peaks are also observed at 3.140Å
and 2.851Å. The (101) reflection is sharp and acute with
a full-width-at-half-maximum-height of 0.463–0.625Å.
Although the intensity of peaks varies throughout the
section, the maximum intensity is found in sample AS 43
 D.A. Sant et al. / Cretaceous Research 24 (2003) 105–110
Fig. 2. Lithological logs of five pits showing ages of the sandwiching basalt flows. Samples analysed at different levels are indicated by dashed lines
and labelled AS 49 etc.; Ir 1, Ir 2 and Ir 3 are iridium-rich levels.
(limestone unit) and AS 39 (shale unit). These two
samples show a split cristobalite peak at a higher resol-
ution with much lower scan speed (Fig. 4B). This split in
the peak is represented by 4.074 and 4.044Å respectively.
The peak at 4.074Å is characteristic of disordered cristo-
balite with tridymite stacking, while the other peak at
4.044Å is characteristic of a well-ordered low cristoba-
lite, thus a mixture of both (Iijima & Tada, 1981; Tada
& Iijima, 1983).
Infrared (IR) spectroscopy (Fig. 4C) of the Anjar
samples revealed absorption bands characteristics of low
cristobalite at 620 and 380 cm
1 bands (Etchpare &
Kaplan, 1978; Graetsch et al., 1994) in AS 39 and AS 43.
The minor 300 cm
1 band is not observed as it is beyond
the limit of the spectrometer. Intense IR bands are char-
acteristic of ordered low cristobalite, which are absent
in opal-CT (Graetsch et al., 1994). Other vibrations
observed in Fig. 4C at 1472 (V3), 873 (V2) and 716 (V4)
cm
1 are due to carbonate (CO2
3 ) vibration. The Si-O-Si
asymmetric stretch is observed at 1100 cm
1, whereas the
Si-O-Si symmetric stretch and the O-Si-O bending band
are seen at 798 cm-1 and 483 cm
1 respectively.
5. Discussion
The chert isolated in the sediments is represented
mineralogically by the silica polymorphs quartz and
107
opal-CT. Hence, it appears that the cristobalite seen in
the sediments is probably microcrystalline and cannot be
identified under a petrographic microscope. The iso-
tropic groundmass indicates that it formed through
precipitation from alkaline lake waters (Khadkikar
et al., 1999), and consists of amorphous silica, whereas
the latter two forms of chert (microcrystalline and
chalcedonic) are distributed sporadically throughout the
section, replacing bone or infilling the shells of bioclasts.
The chalcedonic chert and microcrystalline quartz
are infills from percolating hydrothermal solutions
(Khadkikar et al., 1999).
-cristobalite (well-ordered low cristobalite) found in
the Anjar sedimentary deposits is similar to cristobalite
commonly found associated with vitric tuff owing to
alteration of silicic volcanic glass (Iijima & Tada, 1981),
or directly as fine matter in volcanic ash (Baxter et al.,
1999). Cristobalite is also reported as a ground mass and
cavity filling in tholeiitic basalts, andesite, rhyolite
(Hunter, 1998, table 1) and volcanic hydrothermal
deposits.
We examined the possibility of various origins for
cristobalite. The overlying basalts in the Anjar section
are not thick enough to have caused burial diagenesis,
thus negating transformation from a precursor opal-CT
(silica polymorph with disordered cristobalite tridymite
stacking). Moreover, the distribution of cristobalite
108 D.A. Sant et al. / Cretaceous Research 24 (2003) 105–110
Fig. 3. X-ray diffractogram showing cristobalite dominance at the
Anjar section. Cr, cristobalite; C, calcite; Q, quartz; N, nontronite;
P, palygorskite; S, sepiolite (for sample locations, see Fig. 2).
Fig. 4. A, X-ray diffractogram for sample AS 43 showing characteristic cristobalite peaks, sharp and intense peak (4.055Å), moderate peak (2.489Å)
and weak peak (3.140Å and 2.851Å). Cr, cristobalite, C, calcite, Q, quartz. B, split in cristobalitic peaks characteristed by opal-CT peak at 4.074 and
low cristobalite at 4.044Å when run at a step-width of 0.03( 2
. C, FT-IR spectra of Anjar sample (AS 43) revealing characteristic absorption bands
of low cristobalite at 620 cm
1 and 380 cm
1.
would then have been uniform throughout the deposit,
which is not the case. The second alternative is the
transformation of cristobalite from opal-CT as a result
of thermal ordering of the silica phase owing to heating
by the overlying basalt flow. If cristobalite were to
have formed through the above mechanism, it would
have become enriched at the contact with the lava
flows, where the temperature required for a well-
ordered -cristobalite would have been more congenial.
Consequently, the distribution of cristobalite in Anjar
may be ascribed to the sedimentation of fine silica ash
that may have come from a proximal vent. The intro-
duction of silica ash into the relatively cooler lake
waters facilitated rapid quenching, which inhibits the
conversion of cristobalite to quartz (Heaney, 1994).
Thus in the Anjar intertrappeans, the origin of micro-
crystalline quartz and opal-CT, and cristobalite are from
two different sources. Microcrystalline quartz and
opal-CT probably precipitated from silica-rich inter-
stitial solutions (mechanisms discussed in Khadkikar
et al., 1999), while cristobalite is a remnant of volcanic
ash that was deposited in the lake.
The presence of silica ash in a continental flood-basalt
province might appear to be paradoxical. However,
numerous studies have shown that magma fractionation
may provide an explanation. For example, the 1875
eruptions of the Akja volcano in Iceland (Sigurdson
& Sparks, 1981) produced predominantly basaltic,
andesitic or icelanditic (54–63% SiO2) lava flows. Each
eruption began with the eruption of acidic ash, and
was followed rapidly by increasingly basic lava as the
eruptions continued. Also, the amount of SiO2 in the
initially erupted magma was greatest where the volcano
had been inactive for a long time, suggesting that the
magmas underwent fractionation in a subsurface
magma chamber between two successive eruptions. The
 D.A. Sant et al. / Cretaceous Research 24 (2003) 105–110
build-up of volatiles associated with fractionation trig-
gered each new eruption (Baldridge et al., 1973). The
Icelandic volcano, Mount Hekla (Thorarinsson &
Sigvaldason, 1971), and the Hawaiin and Galapagos
volcanoes (McBirney et al., 1985) are other modern
examples of episodic silicic volcanism in a dominantly
basaltic province. Fine cristobalite ash has also been
reported from the Soufrière Hills eruption, Monsterrat,
in June 1997 (Baxter et al., 1999).
The presence of the iridium anomaly at Anjar may
well be explained from a volcanic perspective. High
iridium concentrations have been reported from Kilauea
volcanic emissions (Olmez et al., 1986) and the Piton de
la Fournaise hotspot volcano (Toutain & Meyer, 1989)
on Reunion Island that produced the Deccan basalts.
Iridium up to 7 ppb also occurs in volcanic dust bands in
the Blue Ice Field of Antarctica (Koeberl, 1989).
Courtillot et al. (2000) made a detailed search for
Ni-rich spinels at Anjar with a negative outcome. None-
theless, they preferred an extraterrestrial origin for the
iridium anomaly at Anjar. However, the concordant
distribution of cristobalite and iridium in the Anjar
deposits suggests that the iridium anomalies are prob-
ably related to volcanism. Silica minerals, which are
common in sediments, thus provide a valuable discrimi-
nator of volcanic and extraterrestrial iridium. While
iridium has been demonstrated here to be of volcanic
origin when associated with cristobalite, the association
of stishovite (a high-pressure polymorph) with iridium
establishes an extraterrestrial origin (McHone et al.,
1989).
6. Conclusions
The intertrappean lacustrine deposits of Anjar,
western India, are important because they record
environmental conditions during Deccan volcanism
(Khadkikar et al., 1999) and also contain an iridium
anomaly (Bhandari et al., 1995). Detailed mineralogical
analyses reveal the presence of cristobalite in the sedi-
ments. Cristobalite, which is a high-temperature poly-
morph of silica, is commonly of volcanic origin and its
concordance with iridium distribution indicates a terres-
trial origin for the iridium anomaly at Anjar. Silica
polymorphs may thus act as discriminators of volcanic
and extraterrestrial iridium as in the latter case stishovite
(also a high-pressure polymorph of silica) is found
associated with iridium anomalies (McHone et al.,
1989).
Acknowledgements
We thank N. Bhandari, Physical Research Labora-
tory (Ahmedabad) for inviting us to study the deposits.
Anil Shukla is thanked for his company and help in the
109
field. We thank D. M. McLean, S. Self and J. Sinton for
discussions. David Batten, G. Price and A. Ruffell are
thanked for their critical reviews of the paper.
References
Alvarez, L.W., Alvarez, W., Asaro, F., et al., 1980. Extraterrestrial
causes of the Cretaceous-Tertiary extinction. Science 208,
1095–1108.
Baldridge, W.S., Thomas McGetchin, R., Frey, F.A., et al., 1973.
Magmatic evolution of Hekla, Iceland. Contr. Mineral. Petrol. 42,
245–258.
Baxter, P.J., Boridonna, C., Dupree, R., et al., 1999. Cristobalite in
volcanic ash of the Soufrière hills volcano, Montserrat, British
West Indies. Science 283, 1142–1145.
Bhandari, N., Shukla, P.N., Ghevariya, Z.G., et al., 1995. Impact did
not trigger Deccan volcanism: evidence from Anjar K/T boundary
intertrappean sediments. Geophys. Res. Lett. 22, 433–436.
Bhandari, N., Shukla, P.N., Ghevariya, Z.G., et al., 1996. K/T
boundary layer in Deccan Intertrappeans at Anjar, Kutch. In:
Ryder, G., Fastovsky, D., Gartner, S. (Eds.), The Cretaceous-
Tertiary event and other catastrophes in earth history, Geol. Soc.
Am., Spec. Pap., 307, pp. 417–424.
Courtillot, V., Gallet, Y., Rocchia, R., et al., 2000. Cosmic markers,
40Ar/39Ar dating and paleomagnetism of the KT sections in the
Anjar area of the Deccan large igneous province. Earth Planet. Sci.
Lett. 182, 137–156.
Etchpare, J.M., Kaplan, P., 1978. Vibrational normal modes of SiO2
II. Cristobalite and tridymite. J. Chem. Phys. 68, 1531–1537.
Ghevariya, Z.G., 1988. Intertrappean dinosaurian fossils from Anjar
area, Kachchh district, Gujarat. Curr. Sci. 57, 248–251.
Graetsch, H., Gies, H., Topalovic, I., 1994. NMR, XRD and IR study
of microcrystalline opals. Phys. Chem. Min. 21, 166–175.
Heaney, P.J., 1994. Structure and chemistry of the low pressure silica
polymorphs. In: Heaney, P.J., Prewitt, C.T., Gibbs, G.V. (Eds.),
Silica: physical behaviour geochemistry and materials applications,
Rev. Mineral., 29, pp. 1–40.
Hunter, A.G., 1998. Intracrustal controls on the coexistence of
tholeiitic and calc-alkaline magma series at Aso volcano, SW
Japan. J. Petrol. 39, 255–1284.
Iijima, A., Tada, A., 1981. Silica diagenesis of Neogene diatomaceous
and volcano clastic sediments in northern Japan. Sedimentology
28, 185–200.
Khadkikar, A.S., Sant, D.A., Gogte, V., et al., 1999. The influence
of Deccan volcanism on climate: insights from lacustrine inter-
trappean deposits, Anjar, Western India. Palaeogeogr.,
Palaeoclimatol., Palaeoecol. 147, 141–149.
Koeberl, C., 1989. Iridium enrichment in volcanic dust from blue ice
fields, Antarctica, and possible relevance to the K/T boundary
event. Earth Planet. Sci. Lett. 92, 317–322.
McBirney, A.R., Cullen, A.B., Geist, D., et al., 1985. The Galapagos
volcano Alcedo: a unique ocean caldera. J. Volcanol. Geotherm.
Res. 26, 173–177.
McHone, J.F., Nieman, R.A., Lewis, C.F., et al., 1989. Stishovite at
the Cretaceous-Tertiary boundary, Raton, New Mexico. Science
243, 1182–1184.
McLean, D.M., 1985. Deccan traps mantle degassing in the terminal
Cretaceous marine extinctions. Cret. Res. 6, 235–259.
Olmez, I., Finnegan, D.I., Zoller, W.H., 1986. Iridium emission from
Kilauea Volcano. J. Geophys. Res. 91, 653–663.
Sigurdson, H., Sparks, R.S.J., 1981. Petrology of rhyolite and mixed
magma ejecta from the 1875 eruption from Askja, Iceland. J.
Petrol. 22, 41–84.
110 D.A. Sant et al. / Cretaceous Research 24 (2003) 105–110
Sutherland, F.L., 1994. Volcanism around K/T boundary time – its
role in an impact scenario for the K/T extinction events. Earth Sci.
Rev. 36, 1–26.
Tada, R., Iijima, A., 1983. Identification of mixtures of opaline silica
phase and its implication for silica diagenesis. In: Iijima, A., Hein,
J.R., Siever, R. (Eds.), Siliceous deposits in the Pacific region,
Elsevier, Amsterdam, pp. 229–246 pp.
Thorarinsson, S., Sigvaldason, G.E., 1971. The Hekla eruption
of 1970. In Symposium on acid volcanism, pp. 269–288 (15th
International Union of Geology and Geophysics, General
Assembly, Moscow).
Toutain, J., Meyer, G., 1989. Iridium-bearing sublimates at the
hotsopot volcano (Piton de la Fournaise, Indian Ocean). Geophys.
Res. Lett. 16, 1391–1394.
Venkatesan, T.R., Pande, K., Ghevariya, Z.G., 1996. 40Ar-39Ar ages
of Anjar Traps, Western Deccan Province (India) and its relation
to the Cretaceous-Tertiary Boundary events. Curr. Sci. 70,
990–996.